Printed Wiring Board
Surface Finishes
VOLUME 2:
Appendices
Cleaner
Technologies
Substitutes
Assessment
Jack R. Geibig, Senior Research Associate
Mary B. Swanson, Research Scientist
and the
PWB Engineering Support Team
This document was produced by the University of Tennessee
Center for Clean Products and Clean Technologies under grant
#X825373 from EPA's Design for the Environment Branch,
Economics, Exposure, & Technology Division, Office of
Pollution Prevention and Toxics.
ur
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Appendix A
Data Collection Sheets
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Contents
Workplace Practices Questionnaire A-l
Facility Background Information Sheet A-58
Observer Data Sheet A-67
Supplier Data Sheet A-74
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Workplace Practices Questionnaire
Design for the Environment
Printed Wiring Board Project
Workplace Practices Questionnaire
Please complete this questionnaire, make a copy for
your records, and send the original to:
Jack Geibig
UT Center for Clean Products
311 Conference Center Building
Knoxville TN 37996
Phone: (423) 974-6513
Fax: (423) 974-1838
FACILITY AND CONTACT INFORMATION
F acility Identification
Company Name:
Site Name:
Street Address:
City:
State: Zip:
ContactIdentification^nterthejMmes_ofthej3ereonsjYho_canbecontactedregardi^^
Name:
Title:
Phone:
Fax:
E-Mail:
A-l
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—INSTRUCTION SHEET—
FOR THE DESIGN FOR THE ENVIRONMENT (DFE)
ALTERNATIVE SURFACE FINISHES (ASF) PROJECT
WORKPLACE PRACTICES QUESTIONNAIRE
INTRODUCTION
This questionnaire was prepared by the University of Tennessee Center for Clean Products and Clean Technologies
in partnership with The US EPA Design for the Environment (DfE) Printed Wiring Board (PWB) Program, IPC, and
other members of the DfE PWB Industry Project Work Groups.
The purpose of this questionnaire is to collect data that will be used in preparation of a Design for the Environment
(DfE) Alterative Surface Technologies report. This report will present an analysis and evaluation of the risk,
performance, and costs associated with operating each of the alternative surface finish processes. Much of this report
will be based on data submitted by PWB manufacturing facilities. You can obtain more information about this
project and other DfE PWB projects from the US EPA's website at http://www.epa.gov/opptintr/dfe/pwb/pwb.html).
CONFIDENTIALITY
All information and data that is entered into this questionnaire is confidential. The sources of responses are only
known to the IPC and have been coded by the IPC for industry research purposes. Any use or publication of the data
will not identify the names or locations of the respondent companies or the individuals completing the forms.
INSTRUCTIONS
Respondents must complete Sections 1 (Facility Characterization) and Section 2 (HASL Process) of
this questionnaire.
Section 3 is divided into five processes (3 A through 3E) as shown below:
3A. Organic Solder Preservative (OSP) Process
3B. Immersion Silver Process
3 C. Immersion Tin Process
3D. Electroless Nickel/Immersion Gold Process
3E. Electroless Nickel/Electroless Palladium/Immersion Gold Process
Of these five subsections, 3A-3E, please fill out only the top two alternative processes, based on PWB
through-put, that are currently being implemented at your facility.
If your responses do not fit in the spaces provided, please photocopy the section to provide more space or use
ordinary paper and mark the response with the section number to which it applies.
Please make a copy of the completed sections and retain them for your records.
If you have questions regarding the survey, please contact Jack Geibig of the University of Tennessee Center for
Clean Products and Clean Technologies at (telephone 423/975-6513; fax 423/974-1838; emailjgeibig@utk.edu) or
Star Summerfield at IPC (telephone 847/790-5347; fax 847/509-9798; email summst@ipc.org).
Please return the completed questionnaire by January 8,1999 to:
Star Summerfield, IPC
2215 Sanders Road, Northbrook, IL 60062-6135
Phone: 847/790-5347, FAX 847/509-9798, email summst@ipc.org
A RETURN LABEL TO IPC IS ENCLOSED FOR YOUR CONVENIENCE.
A-2
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Section 1. Facility Characterization
This section focuses on general information specific to the facility. This information is not process-specific. Please
estimate manufacturing data for the previous 12 month period, or other convenient time period of 12 consecutive
months (e.g., FY97). Only consider the portion of the facility dedicated to PWB manufacturing when entering
employee and facility size data.
1.1 General Information
Size of portion of facility used for
sq. ft.
Overall amount of PWB produced
ssf/yr
manufacturing PWBs:
in surface square feet (ssf):
1.2 Process Type
Estimate the percentage of PWBs manufactured at your facility using the following methods for surface finishing
(SF). Specify "other" entry.
Surface Finish Process
Percent of Total
Surface Finish Process
Percent of Total
HASL
%
Electroless Nickel/ Immersion Gold
%
OSP-Thick
%
Electroless Nickel/Electroless
Palladium/ Immersion Gold
%
OSP-Thin
(benzotriazole-based)
%
Other:
%
Immersion Tin
%
Other:
%
Electroless Palladium
%
Other:
%
Immersion Silver
%
Total
100%
1.3 Wastewater Discharge and Sludge Data
Wastewater discharge method
(circle one):
Direct Indirect Zero
(to stream) (to POTW)
Throughput of facility wastewater treatment system:
gals/day
Annual weight of sludge generated:
lbs
Is sludge dewatered prior to disposal (circle one)?
Yes No
Water content prior to dewatering:
%
Water content after dewatering:
%
A-3
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Section 2. HASL Process
2.1 Process Schematic: HASL
Fill in the figure below for your HASL surface finishing processses. Using the key at the bottom of the page, identify which letter corresponds w
the first step in your HASL process and write that letter in the first box (see example). Continue using the key to fill in boxes for each step intil y
entire HASL process is represented. If your particular process step is not represented by the key below, complete the figure by writing in the na
of the process step in your particular surface finishing line in the corresponding box(es). Finish by responding, to the questions at the bottom of
page.
A-4
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2.2
General Data—HASL
Number of days HASL line is in
operation:
days/yr
Number of hours per day the HASL
line is in operation:
hrs/day
Estimated scrap rate (% of defective
product) for HASL process:
%
Lotal of PWB surface square feet
processed by HASL line per year:
ssf/yr
2.3 Process Area Employees—HASL
Complete the following table by indicating the number of employees of each type that perform work duties in the
same process room as the HASL line, and for what length of time. Consider only workers who have regularly
scheduled responsibilities that require them to be physically within the process room. Specify "other" entry. Enter
"N/A" in any category that is not applicable.
Type of HASL
Area Worker
Number of Employees
in HASL Process Area
Average Hours per Week per
Employee in HASL Process Area
Line Operators
hrs
Lab Lechnicians
hrs
Maintenance Workers
hrs
Wastewater Lreatment Operators
hrs
Supervisory Personnel
hrs
Other (specify):
hrs
2.4 Physical Settings—HASL
Size of the room containing the HASL
process:
sq. ft.
Height of room:
ft.
Are the overall process areas/rooms
ventilated (circle one)?
Yes
No
Air flow rate:
cu. ft./min.
Do you have local vents (circle one)?
Yes
No
Local vent air flow rate:
cu. ft./min.
Overall surface finishing process line dimensions
Length (ft.): Width (ft.):
Height (ft.):
2.5 Rack Dimensions—HASL
Average number of panels per rack:
Average space between panels in rack:
in.
Average size of panel in rack:
Lengthen.): Width (in.):
Do you purposely slow the withdraw rate of your panels from process baths
to reduce drag-out? (Circle one)
Yes No
A-5
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2.6 Rinse Bath Water Usage—HASL
Consult the process schematic in section 2.1 to obtain the process step numbers associated with each of the water rinse
baths present in your HASL process. Enter, in the table below, the process step number along with the flow control
method and flow rate data requested for each water rinse bath. If the water rinse bath is part of a cascade, you need
only report the daily water flow rate of one bath in the cascade.
Total volume of water used by the HASL line when operating:
gal./day
Process Step
Numbera
Flow Controlb
Daily Water
Flow Rate c
Cascade Water
Process Steps d
Example: 8
R
2,400 gal./day
8-»6
gal./day
gal./day
gal./day
gal./day
gal./day
gal./day
a Process step number - Consult the process schematic in question 2.1 and
enter the process step number of the specific water rinse tank.
b Flow control - Consult key at right and enter the letter for the flow control
method used for that specific rinse bath.
c Daily water flow rate - Enter the average daily flow rate for the specific
water rinse tank.
d Cascade water process steps - Use the step numbers for rinses that are
cascaded together.
Flow Control Methods Kev
[C] - Conductivity Meter
[P] - pH Meter
[V] - Operator Control Valve
[R] - Flow Restricter
[N] - None (continuous flow)
[0] - Other (explain)
2.7 Filter Replacement—HASL
Not Applicable
n
Bath(s) filtered
(enter process step # from flow diagram in 2.1)
Frequency of replacement:
Duration of replacement process:
Personal protective equipment (see key):
Personal Protective Equipment Kev:
[E] - Eye Protection [G] - Gloves [Z] - All except Respiratory Protection
[L] - Lab coat/Sleeved garment [A] - Apron [N] - None
[R] - Respiratory Protection [B] - Boots
A-6
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2.8 Rack or Conveyor Cleaning—HASL
Rack Cleaning Method:
[C]-Chemical bath on SF process line
[D]-Chemical bath on another line
[T]-Temporary chemical bath
[S]-Manual scrubbing with chemical
[M]-Non-chemical cleaning
[N]-None
[0]-Continuous cleaning
Conveyor Qeaning Method:
[C]-Chemical rinsing or soaking
[S]-Manual scrubbing with chemical
[M]-Non-chemical cleaning
[N]-None
[0]-Continuous cleaning
Personal Protective Equipment:
[E]-Eye Protection [G]-Gloves
[L]-Lab coat/Sleeved garment [A]-Apron
[R]-Respiratory Protection [B]-Boots
[0]-Continuous Cleaning [N]-None
2.9 Solder Unit Maintenance and Waste disposal [zj-aii except Respiratory Protection
Complete the following maintenance and waste disposal questions for only the unit of the process that
performs the hot air solder leveling
Frequency of maintenance:
Method of dross removal:
Duration of maintenance :
min.
Frequency of dross removal:
Personal protective equipment
(see key):
Quantity of solder waste disposed
(per day):
Number of personnel involved:
Method of solder waste disposal
(see key):
d Personal Protective Equipment - Enter the letters of all
the protective equipment used by the workers who physically
replace the spent bath.
[E] - Eye protection [B] - Boots
[A] - Apron [G] - Gloves
[L] - Lab coat/Sleeved garment
[R] - Respiratory protection
[Z] - All except Respiratory Protection
[N] - None
Method Of Solder Waste Disposal - Indicate method of
solder waste disposal from key below:
[M] - Metals reclaimed off-site
[R] - Recycled on-site
[RO] - Recycled off-site
[D] - Drummed and treated as hazardous waste
[O] - Other (specify)
Not Applicable Q
Rack Cleaning Method (see key): OR
Conveyor Cleaning Method (see key):
Frequency of rack or conveyor cleaning:
Number of personnel involved:
Personal protective equipment (see key):
Average time required to clean:
min.
A-7
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2.10 Physical Data and Operating Conditions—HASL
Complete the tables below by entering the data requested for each specific type of chemical bath listed. If two tanks of the same type are used within the process,
list the data for each tank separately.
Average cycle time for a panel to complete entire HASL
min.
process
(includes cleaning and post cleaning steps, if any):
Bath
Physical Data
Process Data
Operating Conditions
Length
(inches)
Width
(inches)
Nominal
Volume
(gal)
Immersion
Time3
(seconds)
Drip Time
(seconds)
Temp
(°F)
Agitation
(see key)
Vapor Control
(see key)
Cleaner
in.
in.
gal.
sec.
sec.
°F
Microetch
in.
in.
gal.
sec.
sec.
°F
Flux
in.
in.
gal.
sec.
sec.
°F
Solder
in.
in.
gal.
sec.
sec.
°F
Post-Clean
in.
in.
gal.
sec.
sec.
°F
Other (specify)
a Immersion Time - Enter the average elapsed time a rack of panels is immersed in
the specific process bath.
b Drip Time - Enter the average elapsed time that a rack of panels is allowed to hang
above the specific process bath to allow drainage from panels.
Agitation Methods Kev:
[PA]- Panel agitation
[CP]- Circulation pump
[AS]- Air sparge
[0]- Other (explain)
Vapor Control Methods Kev:
[BC]- Bath cover
[FE]- Fully enclosed
[VO]- Vent to outside
[VC]- Vent to control
[PP]- Push pull
[0]- Other (explain)
2.11 Initial Chemical Bath Make-Up Composition—HASL
A-8
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Complete the chart below for each chemical component of the bath type listed. Provide the manufacturer name if the chemical used is known only by trade name. If more
room is needed, please attach another sheet with the additional information. If two tanks of the same type are used within the process, list the data for a single tank only.
Bath
Chemical Product Name
Manufacturer
(if applicable)
Annual Quantity Used3
(gallons)
Cleaner
1.
2.
3.
4.
Microetch
1.
2.
3.
4.
Flux
1.
2.
3.
4.
Solder
1.
2.
3.
4.
Post-Clean
1.
2.
3.
4.
Other (specify)
1.
2.
3.
4.
a Annual Quantity Used - If the amount of a particular chemical used is measured by weight (i.e., crystalline chemicals) instead of volume, enter the weight in
pounds and clearly specify the units (lbs).
A-9
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2.12 Chemical Bath Bailout and Additions—HASL
Complete the following chart detailing the typical bath bailout and chemical additions that are made to maintain the chemical balance of each specific process
bath. If more than three chemicals are added to a specific bath, attach another sheet with the additional information. If chemical additions to a bath are made
automatically, do not complete the last three columns for that bath. If two tanks of the same type are used within the process, list the data for a single tank only.
Bath Type
Bailout
Frequency
Bailout
Durationc
(minutes)
Bailout
Quantity
Personal
Protective
Equipment11
Chemical Products Added
Criteria for
Addition"
Method of
Chemical
Additioi} to Tank
Duration of
Addition0
(minutes )
Cleaner
min.
1
min.
2
3
Microetch
min.
1
min.
2
3
Flux
min.
1
min.
2
3
Solder
min.
1
min.
2
3
Post-Clean
min.
1
min.
2
3
Other
(specify)
min.
1
min.
2
3
" Criteria for Additions - Enter the
letter for the criteria typically used to
determine when bath additions are
necessary.
[S] - Statistical process control
[P] - Panel square feet processed
[C] - Chemical testing
[T] - Time
[O] - Other
b Method of Chemical Addition to Tank - Enter the letter for
the method typically used to add chemicals to the tanks.
[PR] - Poured
[P] - Pumped manually [O] - Other
c Duration (if BaioifyWftJllffhn - Enter the elapsed time from
the retrieval of the chemical stock through the completion of the
addition of all chemicals. For bailout, enter the time required to
bailout the bath prior to making additions.
d Personal Protective Equipment - Enter the letters of all the
protective equipment used by the workers who physically replace the
spent bath.
E] - Eye protection
A] - Apron
L] - Lab coat/Sleeved garmerHlnt
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2.13 Chemical Bath Replacement — HASL
Complete the chart below by providing information on the process of replacing, treating, and disposing of a spent chemical bath.
Bath Type
Criteria
for
Replacement3
Replacement
F requencyb
Method of Spent
Bath Removalc
Tank
Cleaning Method11
Duration of
Replacement
Procedure6
Personal
Protective
Equipment'
Cleaner
min.
Microetch
min.
Flux
min.
Solder
min.
Post-Clean
min.
Other (specify)
min.
a Criteria for Replacement -
[S] - Statistical process control
[P] - Panel square feet processed
[C - Chemical testing
T] - Time
[0] - Other (specify)
b Frequency - Enter the average amount of time
elapsed, or number of square feet processed, between
bath replacements. Clearly specify units (e.g., hours,
sq.ft.).
c Methods of Spent Bath Removal-
IP] - Pump spent bath from tank
[S] - Siphon spent bath from tank
ID] - Drain spent bath from tank
[0] - Other (specify)
d Tank Cleaning Method -
[C] - Chemical flush
W] - Water rinse
[H] - Hand scrub
[0] - Other (specify)
e Duration of Replacement - Enter the
elapsed time from the beginning of bath
removal until the replacement bath is
finished.
F Personal Protective Equip. - Enter the letters
of all the protective equipment used by the
workers who physically replace the spent bath.
[E] - Eye protection
[G - Gloves
L] - Lab coat/sleeved garment
A - Apron
[R] - Respiratory protection
B - Boots
[Z] - All except respiratory protection
[N] - None
A-ll
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2.14 Chemical Bath Sampling—HASL
Bath Type
Type of
Sampling a
Frequency b
Duration of
Sampling c
Protective
Equipment d
Method of
Sampling e
Example:
A
3 per day
5 min
E, G, A
P
Cleaner
Microetch
Other (specify):
" Type of Sampling
[A] - Automated
[M] - Manual
[N] - None
b Frequency: Enter the average time
elapsed or number of panel sq. ft.
processed between samples. Clearly
specify units (e.g., hours, sq.ft.)
c Duration of Sampling: Enter the
average time required to manually take a
sample from the tank.
11 Protective Equipment: Consult the
key for the above table and enter the
letters for all protective equipment used
by the person performing the chemical
sampling.
e Method of Sampling:
[D] - Drain or spigot
[P] - Pipette
[L] - Ladle
[O] - Other (specify)
2.15 Process Waste Disposal — HASL
Bath Type
Annual Volume
Treated or Disposeda
Method of
T reatment or
Disposalb
RCRA Waste
Code (if
applicable)
Container
Type
Cleaner
Microetch
Flux
Solder
Post-Clean
Other
(specify):
a Annual Volume Treated
or Disposed - Enter the
yearly amount of the specific
bath treated or disposed. Be
sure to consider the volume
treated from both bath
change outs and bailout
before entering the total.
B Methods of Treatment or Disposal -
[P] - Precipitation pretreatment on-site
[N] - pH neutralization pretreatment on-site
[S] - Disposed directly to sewer with no
treatment
[D] - Drummed for off-site treatment or
disposal
[RN] - Recycled on-site
[RF] - Recycled off-site
[0] - Other (specify)
Container Type -
Indicate the type of
container used for
disposal of bath wastes
OH]- Open-head drum
CH]- Closed-head drum
T]- Chemical tote
0]- Other (specify)
A-12
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Section 3. Electroless Nickel/Immersion Gold Process
3.1 Process Schematic: Nickel/Gold
Fill in the figure below for your electroless nickel/immersion gold surface finishing processses. Using the key at the bottom of the page, iedntify
which letter corresponds with the first step in your process and write that letter in the first box (see example). Continue using the key to fill in bo
for each step until your entire electroless nickel/immersion gold process is represented. If a particular process step is not represented by the key
below, complete the figure by writing in the name of the process step in your particular surface finishing line in the corresponding box(es). Finis
by responding to the questions at the bottom of the page.
A-13
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3.2 General Data—Nickel/Gold
Number of days the nickel/gold line
is in operation:
days/yr
Number of hours per day the nickel/gold
line is in operation:
hrs/day
Estimated scrap rate (% of defective
product) for the nickel/gold process:
%
Total of PWB surface square feet
processed by the nickel/gold line per year:
ssf/yr
3.3 Process Area Employees—Nickel/Gold
Complete the following table by indicating the number of employees of each type that perform work duties in the
same process room as the nickel/gold line, and for what length of time. Consider only workers who have regularly
scheduled responsibilities that require them to be physically within the process room. Specify "other" entry. Enter
"N/A" in any category that is not applicable.
Type of Surface Finish
Area Worker
Number of Employees
in Surface Finish Process Area
Average Hours per Week per
Employee in Surface Finish
Process Area
Line Operators
hrs
Lab Technicians
hrs
Maintenance Workers
hrs
Wastewater Treatment Operators
hrs
Supervisory Personnel
hrs
Other (specify):
hrs
3.4 Physical Settings—Nickel/Gold
Size of the room containing the
surface finish process:
sq. ft.
Height of room:
ft.
Are the overall process areas/rooms
ventilated (circle one)?
Yes
No
Air flow rate:
cu. ft./min.
Do you have local vents (circle one)?
Yes
No
Local vent air flow rate:
cu. ft./min.
Overall surface finishing process line dimensions
Length (ft.): Width (ft.):
Height (ft.):
3.5 Rack Dimensions—Nickel/Gold
Average number of panels per rack:
Average space between panels in rack:
in.
Average size of panel in rack:
Lengthen.): Width (in.):
Do you purposely slow the withdraw rate of your panels from process baths
to reduce drag-out? (Circle one)
Yes No
A-14
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3.6 Rinse Bath Water Usage—Nickel/Gold
Consult the process schematic in section 2.1 to obtain the process step numbers associated with each of the water
rinse baths present in your nickel/gold process. Enter, in the table below, the process step number along with the
flow control method and flow rate data requested for each water rinse bath. If the water rinse bath is part of a
cascade, you need only report the daily water flow rate of one bath in the cascade.
Total volume of water used by the surface finish line when operating:
gal./day
Process Step
Numbera
Flow Controlb
Daily Water
Flow Rate c
Cascade Water
Process Steps d
Example: 8
R
2,400 gal./day
8 -> 6
gal./day
gal./day
gal./day
gal./day
gal./day
gal./day
a Process step number - Consult the process schematic in question 2.1 and
enter the process step number of the specific water rinse tank.
b Flow control - Consult key at right and enter the letter for the flow control
method used for that specific rinse bath.
c Daily water flow rate - Enter the average daily flow rate for the specific
water rinse tank.
d Cascade water process steps - Use the step numbers for rinses that are
cascaded together.
Flow Control Methods Kev
C] - Conductivity Meter
P] - pH Meter
V] - Operator Control Valve
ll] - Flow Restricter
N] - None (continuous flow)
0] - Other (explain)
3.7 Filter Replacement—Nickel/Gold
Not Applicable
~
Bath(s) filtered
(enter process step # from flow diagram in 2.1)
Frequency of replacement:
Duration of replacement process:
Personal protective equipment (see key):
Personal Protective Equipment Key:
[E] - Eye Protection [G] - Gloves [Z] - All except Respiratory Protection
[L] - Lab coat/Sleeved garment [A] - Apron [N] - None
[R] - Respiratory Protection [B] - Boots
A-15
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3.8
Rack or Conveyor Cleaning—Nickel/Gold
Rack Cleaning Method:
[C]-Chemical bath on SF process line
[D]-Chemical bath on another line
[T]-Temporary chemical bath
[S]-Manual scrubbing with chemical
[M]-Non-chemical cleaning
[N]-None
[0]-Continuous cleaning
Conveyor Cleaning Method:
[C]-Chemical rinsing or soaking
[S]-Manual scrubbing with chemical
[M]-Non-chemical cleaning
[N]-None
[0]-Continuous cleaning
Personal Protective Equipment:
[E]-Eye Protection [G]-Gloves
[L]-Lab coat/Sleeved garment [A]-Apron
[R]-Respiratory Protection [B]-Boots
[0]-Continuous Cleaning [N]-None
[Z]-A11 except Respiratory Protection
3.9 Chemical Bath Sampling —Nickel/Gold
Bath Type
Type of
Sampling a
F requencyb
Duration of
Sampling c
Protective
Equipmentd
Method of
Sampling e
Example:
A
3 per day
5 min
E, G, A
P
Cleaner/
Conditioner
Microetch
Catalyst
Acid Dip
Acivator
Electroless
Nickel
Immersion Gold
Other (specify):
- Tvrte of Sampling
- Duration of Sampling: Enter the a
- Method of Sampling:
[A] - Automated
M] - Manual
[N] - None
b Frequency: Enter the average
time elapsed or number of panel sq.
ft. processed between samples.
Clearly specify units (e.g., hours, sq.
ft.).
verage time required to manually take
a sample from the tank.
- Protective Equipment: Consult
the key for the above table and enter
the letters for all protective
equipment used by the person
performing the chemical sampling.
[D] - Drain or spigot
[P] - Pipette
{L] - Ladle
[0] - Other (specify)
Not Applicable Q
Rack Cleaning Method (see key): OR
Conveyor Cleaning Method (see key):
Frequency of rack or conveyor cleaning:
Number of personnel involved:
Personal protective equipment (see key):
Average time required to clean:
min.
A-16
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3.10 Physical Data and Operating Conditions—Nickel/Gold
Complete the tables below by entering the data requested for each specific type of chemical bath listed. If two tanks of the same type are used within the process,
list the data for each tank separately.
Average cycle time for a panel to complete entire nickel/gold process
(includes cleaning and post cleaning steps, if any):
Bath
Physical Data
Process Data
Operating Conditions
Length
(inches)
Width
(inches)
Nominal
Volume
(gal)
Immersion
Time a
(seconds)
DripbTime
(seconds)
Temp
(°F)
Agitation
(see key)
Vapor Control
(see key)
Cleaner/
Conditioner
in.
in.
gal.
sec.
sec.
°F
Microetch
in.
in.
gal.
sec.
sec.
°F
Catalyst
in.
in.
gal.
sec.
sec.
°F
Acid Dip
in.
in.
gal.
sec.
sec.
°F
Activator
in.
in.
gal.
sec.
sec.
°F
Electroless Nickel
in.
in.
gal.
sec.
sec.
°F
Immersion Gold
in.
in.
gal.
sec.
sec.
°F
Other (specify);
in.
in.
gal.
sec.
sec.
°F
a Immersion Time - Enter the average elapsed time a rack of panels is immersed in
the specific process bath.
b Drip Time - Enter the average elapsed time that a rack of panels is allowed to hang
above the specific process bath to allow drainage from panels.
Agitation Methods Kev:
Vapor Control Methods Kev:
PA] - Panel agitation
CP] - Circulation pump
AS] - Air sparge
0] - Other (explain)
BC] - Bath cover
FE] - Fully enclosed
VO] - Vent to outside
VC] - Vent to control
PP] - Push pull
0] - Other (explain)
A-17
-------
3.11 Initial Chemical Bath Make-Up Composition —Nickel/Gold
Complete the chart below for each chemical component of the bath type listed. Provide the manufacturer name if the chemical used is known only by trade name. If more
room is needed nlease attach anot
ier sheet with the additional information
f two tanks of the same tvne are used within the
Bath
Chemical Product Name
Manufacturer (if annlicahle)
Annual Ouantitv Used a (gallons')
Cleaner
1.
2.
3.
4.
Microetch
1.
2.
3.
4.
Catalyst
1.
2.
3.
4.
Acid Dip
1.
2.
3.
4.
Activator
1.
2.
3.
4.
Electroless Nickel
1.
2.
3.
4.
Immersion Gold
1.
2.
3.
4.
Other (specify)
1.
2.
3.
4.
a Annual Quantity Used - If the amount of a particular chemical used is measured by weight (i.e., crystalline chemicals) instead of volume, enter the weight in
pounds and clearly specify the units (lbs).
A-18
-------
3.12 Chemical Bath Bailout and Additions—Nickel/Gold
Complete the following chart detailing the typical bath bailout and chemical additions that are made to maintain the chemical balance of each specific process
bath. If more than three chemicals are added to a specific bath, attach another sheet with the additional information. If chemical additions to a bath are made
automatically, do not complete the last three columns for that bath. If two tanks of the same type are used within the process, list the data for a single tank only.
Bath Type
Bailout
Frequency
Bailout
Durationc
(minutes)
Bailout
Quantity
Personal
Protective
EauiDment d
Chemical Products Added
Criteria for
Addition"
Method of
Chemical
Addition to Tankb
Duration of
Addition0
(minutes )
Cleaner/
Conditioner
min.
1
min.
2
3
Microetch
min.
1
min.
2
3
Catalyst
min.
1
min.
2
3
Acid Dip
min.
1
min.
2
3
Activator
min.
1
min.
2
3
Electroless
Nickel
min.
1
min.
2
3
Immersion
Gold
min.
1
min.
2
3
Other
(specify)
min.
1
min.
2
3
" Criteria for Additions - Enter the
letter for the criteria typically used to
determine when bath additions are
necessary.
[S] - Statistical process control
[P] - Panel square feet processed
[C] - Chemical testing
[T] - Time
[O] - Other
b Method of Chemical Addition to Tank - Enter the letter for
the method typically used to add chemicals to the tanks.
[PR] - Poured
[P] - Pumped manually [O] - Other
c Duration of BailolS oi^A?fififii»n - Enter the elapsed time
from the retrieval of the chemical stock through the completion
of the addition of all chemicals. For bailout, enter the time
required to bailout the bath prior to making additions.
d Personal Protective Equipment - Enter the letters of all the
protective equipment used by the workers who physically replace the
spent bath.
E] - Eye protection
A] - Apron
L] - Lab coat/Sleeved garmerHlnt
-------
3.13 Chemical Bath Replacement — Nickel/Gold
Complete the chart below by providing information on the process of replacing, treating, and disposing of a spent chemical bath.
Bath Type
Criteria
for Replacement a
Replacement
F requencyb
Method of Spent
Bath Removalc
Tank
Cleaning Method d
Duration of
Replacement
Procedure e
Personal
Protective
Equipmentf
Cleaner/Conditioner
min.
Microetch
min.
Catalyst
min.
Acid Dip
min.
Activator
min.
Electroles Nickel
min.
Immersion Gold
min.
Other (specify)
min.
a Criteria for Replacement -
[S] - Statistical process control
P] - Panel square feet processed
[C - Chemical testing
T] - Time
[0] - Other (specify)
b Frequency - Enter the average amount of time
elapsed, or number of square feet processed, between
bath replacements. Clearly specify units (e.g., hours,
sq.ft.).
c Methods of Spent Bath Removal-
IP] - Pump spent bath from tank
S] - Siphon spent bath from tank
ID] - Drain spent bath from tank
[0] - Other (specify)
d Tank Cleaning Method -
[C] - Chemical flush
[W] - Water rinse
H] - Hand scrub
[0] - Other (specify)
e Duration of Replacement - Enter the
elapsed time from the beginning of bath
removal until the replacement bath is
finished.
f Personal Protective Equip. - Enter the letters
of all the protective equipment used by the
workers who physically replace the spent bath.
|E] - Eye protection
G - Gloves
L] - Lab coat/sleeved garment
[A - Apron
[R] - Respiratory protection
B - Boots
Z] - All except respiratory protection
[N] - None
A-20
-------
3.14 Process Waste Disposal — Nickel/Gold
Bath Type
Annual Volume
Treated or Disposed a
Method of Treatment
or Disposalb
RCRA Waste
Code (if applicable)
Container
Type
Cleaner/Conditi
oner
Microetch
Catalyst
Acid Dip
Activator
Electroless
Nickel
Immersion Gold
Other (specify):
11 Annual Volume Treated or
Disposed - Enter the yearly
amount of the specific bath
treated or disposed. Be sure to
consider the volume treated
from both bath change outs
and bailout before entering the
total
b Methods of Treatment or Disposal-
P] - Precipitation pretreatment on-site
1ST] - pH neutralization pretreatment on-site
S] - Disposed directly to sewer with no treatment
D] - Drummed for off-site treatment or disposal
llN] - Recycled on-site
RF] - Recycled off-site
0] - Other (specify)
Container Type -
Indicate the type of
container used for disposal
of bath wastes
OH]- Open-head drum
CH]- Closed-head drum
T]- Chemical tote
0]- Other (specify)
A-21
-------
Section 4. Electroless Nickel/Electroless Palladium/Immersion Gold Process
4.1 Process Schematic: Nickel/Palladium/Golcl
Fill in the figure below for your electroless nickel/ electroless palladium/immersion gold surface finishing processses. Using the key at the bottoi
of the page, identify which letter corresponds with the first step in your process and write that letter in the first box (see example). Continue usin
the key to fill in boxes for each step until your entire nickel/palladium/gold process is represented. If a particular process step is not represented
the key below, complete the figure by writing in the name of the process step in your particular surface finishing line in the corresponding boxeO
Finish by responding to the questions at the bottom of the page.
A-22
-------
4.2 General Data—Nickel/Palladium/Gold
Number of days the nickel/palladium/gold
line is in operation:
days/y
r
Number of hours per day the
nickel/palladium/gold line is in operation:
hrs/day
Estimated scrap rate (% of defective
product) for the nickel/palladium/gold
process:
%
Total of PWB surface square feet
processed by the nickel/palladium/gold line
per year:
ssf/yr
4.3 Process Area Employees—Nickel/Palladium/Gold
Complete the following table by indicating the number of employees of each type that perform work duties in the
same process room as the nickel/palladium/gold line, and for what length of time. Consider only workers who have
regularly scheduled responsibilities that require them to be physically within the process room. Specify "other" entry.
Enter "N/A" in any category that is not applicable.
Type of Surface Finish
Area Worker
Number of Employees
in Surface Finish Process Area
Average Hours per Week per
Employee in Surface Finish
Process Area
Line Operators
hrs
Lab Technicians
hrs
Maintenance Workers
hrs
Wastewater Treatment Operators
hrs
Supervisory Personnel
hrs
Other (specify):
hrs
4.4 Physical Settings—Nickel/Palladium/Gold
Size of the room containing the
surface finish process:
sq. ft.
Height of room:
ft.
Are the overall process areas/rooms
ventilated (circle one)?
Yes
No
Air flow rate:
cu. ft./min.
Do you have local vents (circle one)?
Yes
No
Local vent air flow rate:
cu. ft./min.
Overall surface finishing process line dimensions
Length (ft.): Width (ft.):
Height (ft.):
4.5 Rack Dimensions—Nickel/Palladium/Gold
Average number of panels per rack:
Average space between panels in rack:
in.
Average size of panel in rack:
Lengthen.): Width (in.):
Do you purposely slow the withdraw rate of your panels from process baths
to reduce drag-out? (Circle one)
Yes No
A-23
-------
4.6 Rinse Bath Water Usage—Nickel/Palladium/Gold
Consult the process schematic in section 2.1 to obtain the process step numbers associated with each of the water
rinse baths present in your nickel/palladium/gold process. Enter, in the table below, the process step number along
with the flow control method and flow rate data requested for each water rinse bath. If the water rinse bath is part
of a cascade, you need only report the daily water flow rate of one bath in the cascade.
Total volume of water used by the surface finish line when operating:
gal./day
Process Step
Numbera
Flow Controlb
Daily Water
Flow Rate c
Cascade Water
Process Steps d
Example: 8
R
2,400 gal./day
8-»6
gal./day
gal./day
gal./day
gal./day
gal./day
gal./day
a Process step number - Consult the process schematic in question 2.1 and
enter the process step number of the specific water rinse tank.
b Flow control - Consult key at right and enter the letter for the flow control
method used for that specific rinse bath.
c Daily water flow rate - Enter the average daily flow rate for the specific
water rinse tank.
d Cascade water process steps - Use the step numbers for rinses that are
cascaded together.
Fl<
T]
V
H
N
0
>w Control Methods Kev
- Conductivity Meter
- pH Meter
- Operator Control Valve
- Flow Restricter
- None (continuous flow)
- Other (explain)
4.7 Filter Replacement—Nickel/Palladium/Gold
Not Applicable
~
Bath(s) filtered
(enter process step # from flow diagram in 2.1)
Frequency of replacement:
Duration of replacement process:
Personal protective equipment (see key):
Personal Protective Equipment Key:
[E] - Eye Protection [G] - Gloves
[L] - Lab coat/Sleeved garment [A] - Apron
[R] - Respiratory Protection [B] - Boots
[Z] - All except Respiratory Protection
[N] - None
A-24
-------
4.8
Rack or Conveyor Cleaning—Nickel/Palladium/Gold
Rack Cleaning Method:
[C]-Chemical bath on SF process line
[D]-Chemical bath on another line
[T]-Temporary chemical bath
[S]-Manual scrubbing with chemical
[M]-Non-chemical cleaning
[N]-None
[O]-Continuous cleaning
Conveyor Cleaning Method:
[C]-Chemical rinsing or soaking
[S]-Manual scrubbing with chemical
[M]-Non-chemical cleaning
[N]-None
[O]-Continuous cleaning
Personal Protective Equipment:
[E]-Eye Protection [G]-Gloves
[L]-Lab coat/Sleeved garment [A]-Apron
[R]-Respiratory Protection [B]-Boots
[O]-Continuous Cleaning [N]-None
[Z]-A11 except Respiratory Protection
4.9 Chemical Bath Sampling —Nickel/Palladium/Gold
Bath Type
Type of
Sampling a
F requencyb
Duration of
Sampling c
Protective
Equipmentd
Method of
Sampling e
Example:
A
3 per day
5 min
E, G, A
P
Cleaner/
Conditioner
Microetch
Catalyst
Acid Dip
Acivator
Electroless
Nickel
Electroless
Palladium
Immersion Gold
Other (specify):
- Tvrte of Sampling
[A] - Automated
[M] - Manual
[N] - None
b Frequency: Enter the average
time elapsed or number of panel sq.
ft. processed between samples.
Clearly specify units (e.g., hours, sq.
ft.). *
- Duration of Sampling: Enter the a
verage time required to manually take
a sample from the tank.
- Protective Equipment: Consult
the key for the above table and enter
the letters for all protective
equipment used by the person
performing the chemical sampling.
- Method of Sampling:
[D] - Dram or spigot
[P] - Pipette
{L] - Ladle
[0] - Other (specify)
Not Applicable Q
Rack Cleaning Method (see key): OR
Conveyor Cleaning Method (see key):
Frequency of rack or conveyor cleaning:
Number of personnel involved:
Personal protective equipment (see key):
Average time required to clean:
min.
A-25
-------
4.10 Physical Data and Operating Conditions—Nickel/Palladium/Gold
Complete the tables below by entering the data requested for each specific type of chemical bath listed. If two tanks of the same type are used within the process,
list the data for each tank separately.
Average cycle time for a panel to complete entire surface finish process
(includes cleaning and post cleaning steps, if any):
mm.
Bath
Physical Data
Process Data
Operating Conditions
Length
(inches)
Width
(inches)
Nominal
Volume
(gal)
Immersion
Time a
(seconds)
DripbTime
(seconds)
Temp
(°F)
Agitation
(see key)
Vapor Control
(see key)
Cleaner/Conditioner
in.
in.
gal.
sec.
sec.
°F
Microetch
in.
in.
gal.
sec.
sec.
°F
Catalyst
in.
in.
gal.
sec.
sec.
°F
Acid Dip
in.
in.
gal.
sec.
sec.
°F
Activator
in.
in.
gal.
sec.
sec.
°F
Electroless Nickel
in.
in.
gal.
sec.
sec.
°F
Electroless Palladium
in.
in.
gal.
sec.
sec.
°F
Immersion Gold
in.
in.
gal.
sec.
sec.
°F
Other (specify);
in.
in.
gal.
sec.
sec.
°F
a Immersion Time - Enter the average elapsed time a rack of panels is immersed in
the specific process bath.
b Drip Time - Enter the average elapsed time that a rack of panels is allowed to hang
above the specific process bath to allow drainage from panels.
Agitation Methods Key:
Vapor Control Methods Kev:
PA] - Panel agitation
CP" - Circulation pump
AS] - Air sparge
0] - Other (explain)
BC] - Bath cover
EE] - Fully enclosed
VO] - Vent to outside
VC] - Vent to control
PP] - Push pull
0] - Other (explain)
A-26
-------
4.11 Initial Chemical Bath Make-Up Composition --Nickel/Palladium/Gold
Complete the chart below for each chemical component of the bath type listed. Provide the manufacturer name if the chemical used is known only by trade name. If more
room is needed nlease attach anot
her sheet with the additional information
f two tanks of the same tvne are used within the
Bath
Chemical Product Name
Manufacturer (if annlicahlei
Annual Ouantitv Used a Oallonst
Cleaner
1.
2.
3.
4.
Microetch
1.
2.
3.
4.
Catalyst
1.
2.
3.
4.
Acid Dip
1.
2.
3.
4.
Activator
1.
2.
3.
4.
Electroless Nickel
1.
2.
3.
4.
Elect roless
Palladium
1.
2.
3.
4.
Immersion Gold
1.
2.
3.
4.
Other (specify)
1.
2.
3.
4.
a Annual Quantity Used - If the amount of a particular chemical used is measured by weight (i.e., crystalline chemicals) instead of volume, enter the weight in
pounds and clearly specify the units (lbs).
A-27
-------
4.12 Chemical Bath Bailout and Additions—Nickel/Palladium/Gold
Complete the following chart detailing the typical bath bailout and chemical additions that are made to maintain the chemical balance of each specific process
bath. If more than three chemicals are added to a specific bath, attach another sheet with the additional information. If chemical additions to a bath are made
automatically, do not complete the last three columns for that bath. If two tanks of the same type are used within the process, list the data for a single tank only.
Bath Type
Bailout
Frequency
Bailout
Durationc
(minutes)
Bailout
Quantity
Personal
Protective
Eauirnnent d
Chemical Products Added
Criteria for
Addition"
Method of
Chemical
Addition to Tankb
Duration of
Addition0
(minutes )
Cleaner/
Conditioner
min.
1
min.
2
3
Microetch
min.
1
min.
2
3
Catalyst
min.
1
min.
2
3
Acid Dip
min.
1
min.
2
3
Activator
min.
1
min.
2
3
Electroless
Nickel
min.
1
min.
2
3
Electroless
Palladium
min.
1
2
3
Immersion
Gold
min.
1
min.
2
3
Other
(specify)
min.
1
min.
2
3
" Criteria for Additions - Enter the
letter for the criteria typically used to
determine when bath additions are
necessary.
[S] - Statistical process control
[P] - Panel square feet processed
[C] - Chemical testing
[T] - Time
[O] - Other
b Method of Chemical Addition to Tank - Enter the letter for
the method typically used to add chemicals to the tanks.
[PR] - Poured
[P] - Pumped manually [O] - Other
c Duration (if Bai- Enter the elapsed time from
the retrieval of the chemical stock through the completion of the
addition of all chemicals. For bailout, enter the time required to
bailout the bath prior to making additions.
d Personal Protective Equipment - Enter the letters of all the
protective equipment used by the workers who physically replace the
spent bath.
E] - Eye protection
A] - Apron
L] - Lab coat/Sleeved garTnera!^,,
R] - Respiratory proteftion
Z] - All except Respiratory Protection
1ST] - None
TGI - Gloves
A-28
-------
4.13 Chemical Bath Replacement — Nickel/Palladium/Gold
Complete the chart below by providing information on the process of replacing, treating, and disposing of a spent chemical bath.
Bath Type
Criteria
for Replacement a
Replacement
F requencyb
Method of Spent
Bath Removalc
Tank
Cleaning Method d
Duration of
Replacement
Procedure e
Personal
Protective
Equipmentf
Cleaner/Conditioner
min.
Microetch
min.
Catalyst
min.
Acid Dip
min.
Activator
min.
Electroless Nickel
min.
Electroless Palladium
min.
Immersion Gold
min.
Other (specify)
min.
a Criteria for Replacement -
[S] - Statistical process control
P] - Panel square feet processed
[C - Chemical testing
T] - Time
[0] - Other (specify)
b Frequency - Enter the average amount of time
elapsed, or number of square feet processed, between
bath replacements. Clearly specify units (e.g., hours,
sq.ft.).
c Methods of Spent Bath Removal-
IP] - Pump spent bath from tank
S] - Siphon spent bath from tank
ID] - Drain spent bath from tank
[0] - Other (specify)
d Tank Cleaning Method -
[C] - Chemical flush
[W] - Water rinse
H] - Hand scrub
[0] - Other (specify)
e Duration of Replacement - Enter the
elapsed time from the beginning of bath
removal until the replacement bath is
finished.
f Personal Protective Equip. - Enter the letters
of all the protective equipment used by the
workers who physically replace the spent bath.
|E] - Eye protection
G - Gloves
L] - Lab coat/sleeved garment
[A - Apron
[R] - Respiratory protection
B* - Boots
[Z] - All except respiratory protection
[N] - None
A-29
-------
4.14 Process Waste Disposal — Nickel/Palladium/Gold
Bath Type
Annual Volume
Treated or Disposed a
Method of Treatment
or Disposalb
RCRA Waste
Code (if applicable)
Container
Type
Cleaner/
Conditioner
Microetch
Catalyst
Acid Dip
Activator
Electroless
Nickel
Electroless
Palladium
Immersion Gold
Other (specify):
11 Annual Volume Treated or
Disposed - Enter the yearly
amount of the specific bath
treated or disposed. Be sure to
consider the volume treated
from both bath change outs
and bailout before entering the
total
b Methods of Treatment or Disposal-
P] - Precipitation pretreatment on-site
1ST] - pH neutralization pretreatment on-site
S] - Disposed directly to sewer with no treatment
ID] - Drummed for off-site treatment or disposal
llN] - Recycled on-site
RF] - Recycled off-site
0] - Other (specify)
Container Type -
Indicate the type of
container used for disposal
of bath wastes
OH]- Open-head drum
CH]- Closed-head drum
T]- Chemical tote
0]- Other (specify)
A-30
-------
Section 5. Organic Solder Preservative (OSP) Process
5.1 Process Schematic: OSP
Fill in the figure below for your OSP surface finishing process. Using the key at the bottom of the page, identify which letter corresponds with ti
first step in your process and write that letter in the first box (see example). Continue using the key to fill in boxes for each step until your entir
process is represented. If a particular step is not represented by the key below, complete the figure by writing in the name of the process step in
your particular surface finishing line in the corresponding box(es). Finish by responding to the questions at the bottom of the page.
11.
12.
13.
14.
15.
Is the entire OSP process, as described in the chart above, co-locatec^
in the same room:
Yes No
* If no (process steps performed in more than one room), please
circle the steps above that are in a separate room.
Type of Process Automation for the OSP line: (circle one)
Conveyorized Automated non-conveyorized Manually-controlled hoist
Manual (no automation) Other (specify):
OSP Process Step Key
[A] - Cleaner
[B] - Microetch
[C] - Predip
[D] - OSP
[E] - Water Rinse
[F] - Air Knife
[G] - Other (Specify in the appropriate box)
A-31
-------
5.2 General Data—OSP
Number of days the OSP line is in
operation:
days/yr
Number of hours per day the OSP line is in
operation:
hrs/day
Estimated scrap rate (% of defective
product) for the OSP process:
%
Total of PWB surface square feet
processed by the OSP line per year:
ssf/yr
5.3 Process Area Employees—OSP
Complete the following table by indicating the number of employees of each type that perform work duties in the
same process room as the OSP line, and for what length of time. Consider only workers who have regularly
scheduled responsibilities that require them to be physically within the process room. Specify "other" entry. Enter
"N/A" in any category that is not applicable.
Type of Surface Finish
Area Worker
Number of Employees
in Surface Finish Process Area
Average Hours per Week per
Employee in Surface Finish
Process Area
Line Operators
hrs
Lab Technicians
hrs
Maintenance Workers
hrs
Wastewater Treatment Operators
hrs
Supervisory Personnel
hrs
Other (specify):
hrs
5.4 Physical Settings—OSP
Size of the room containing the
surface finish process:
sq. ft.
Height of room:
ft.
Are the overall process areas/rooms
ventilated (circle one)?
Yes
No
Air flow rate:
cu. ft./min.
Do you have local vents (circle one)?
Yes
No
Local vent air flow rate:
cu. ft./min.
Overall surface finishing process line dimensions
Length (ft.): Width (ft.):
Height (ft.):
5.5 Rack Dimensions—OSP
Average number of panels per rack:
Average space between panels in rack:
in.
Average size of panel in rack:
Lengthen.): Width (in.):
Do you purposely slow the withdraw rate of your panels from process baths
to reduce drag-out? (Circle one)
Yes No
A-32
-------
5.6 Rinse Bath Water Usage—OSP
Consult the process schematic in section 2.1 to obtain the process step numbers associated with each of the water
rinse baths present in your OSP process. Enter, in the table below, the process step number along with the flow
control method and flow rate data requested for each water rinse bath. If the water rinse bath is part of a cascade,
you need only report the daily water flow rate of one bath in the cascade.
Total volume of water used by the surface finish line when operating:
gal./day
Process Step
Numbera
Flow Controlb
Daily Water
Flow Rate c
Cascade Water
Process Steps d
Example: 8
R
2,400 gal./day
8-»6
gal./day
gal./day
gal./day
gal./day
gal./day
gal./day
a Process step number - Consult the process schematic in question 2.1 and
enter the process step number of the specific water rinse tank.
b Flow control - Consult key at right and enter the letter for the flow control
method used for that specific rinse bath.
c Daily water flow rate - Enter the average daily flow rate for the specific
water rinse tank.
d Cascade water process steps - Use the step numbers for rinses that are
cascaded together.
Flow Control Methods Kev
C] - Conductivity Meter
P] - pH Meter
V] - Operator Control Valve
ll] - Flow Restricter
N] - None (continuous flow)
0] - Other (explain)
5.7 Filter Replacement—OSP
Not Applicable
~
Bath(s) filtered
(enter process step # from flow diagram in 2.1)
Frequency of replacement:
Duration of replacement process:
Personal protective equipment (see key):
Personal Protective Equipment Key:
[E] - Eye Protection [G] - Gloves
[L] - Lab coat/Sleeved garment [A] - Apron
[R] - Respiratory Protection [B] - Boots
[Z] - All except Respiratory Protection
[N] - None
A-33
-------
5.8 Rack or Conveyor Cleaning—OSP
Rack Cleaning Method:
[C]-Chemical bath on SF process line
[D]-Chemical bath on another line
[T]-Temporary chemical bath
[S]-Manual scrubbing with chemical
[M]-Non-chemical cleaning
[N]-None
[O]-Continuous cleaning
Conveyor Cleaning Method:
[C]-Chemical rinsing or soaking
[S]-Manual scrubbing with chemical
[M]-Non-chemical cleaning
[N]-None
[O]-Continuous cleaning
Personal Protective Equipment:
[E]-Eye Protection [G]-Gloves
[L]-Lab coat/Sleeved garment [A]-Apron
[R]-Respiratory Protection [B]-Boots
[O]-Continuous Cleaning [N]-None
[Z]-A11 except Respiratory Protection
5.9 Chemical Bath Sampling --OSP
Bath Type
Type of
Sampling a
F requencyb
Duration of
Sampling c
Protective
Equipmentd
Method of
Sampling e
Example:
A
3 per day
5 min
E, G, A
P
Cleaner
Microetch
Other (specify):
- TvDe of Sampling
[A] - Automated
[M] - Manual
[N] - None
b Frequency: Enter the average
time elapsed or number of panel sq.
ft. processed between samples.
Clearly specify units (e.g., hours, sq.
ft.).
- Duration of Samnlinn: Enter the a
verage time required to manually take
a sample from the tank.
- Protective Equipment: Consult
the key for the above table and enter
the letters for all protective
equipment used by the person
performing the chemical sampling.
- Method of Sampling:
[D] - Drain or spigot
[P] - Pipette
{L] - Ladle
[0] - Other (specify)
Not Applicable Q
Rack Cleaning Method (see key): OR
Conveyor Cleaning Method (see key):
Frequency of rack or conveyor cleaning:
Number of personnel involved:
Personal protective equipment (see key):
Average time required to clean:
min.
A-34
-------
5.10 Physical Data and Operating Conditions—OSP
Complete the tables below by entering the data requested for each specific type of chemical bath listed. If two tanks of the same type are used within the process,
list the data for each tank separately.
Average cycle time for a panel to complete entire OSP process
(includes cleaning and post cleaning steps, if any):
Bath
Physical Data
Process Data
Operating Conditions
Length
(inches)
Width
(inches)
Nominal
Volume
(gal)
Immersion
Time a
(seconds)
DripbTime
(seconds)
Temp
(°F)
Agitation
(see key)
Vapor Control
(see key)
Cleaner
in.
in.
gal.
sec.
sec.
°F
Microetch
in.
in.
gal.
sec.
sec.
°F
Flux
in.
in.
gal.
sec.
sec.
°F
Solder
in.
in.
gal.
sec.
sec.
°F
Post-Clean
in.
in.
gal.
sec.
sec.
°F
Other (specify);
in.
in.
gal.
sec.
sec.
°F
a Immersion Time - Enter the average elapsed time a rack of panels is immersed in
the specific process bath.
b Drip Time - Enter the average elapsed time that a rack of panels is allowed to hang
above the specific process bath to allow drainage from panels.
Agitation Methods Kev:
VaDor Control Methods Kev:
PA] - Panel agitation
CP] - Circulation pump
AS] - Air sparge
0] - Other (explain)
BC] - Bath cover
FE] - Fully enclosed
VO] - Vent to outside
VC] - Vent to control
PP] - Push pull
0] - Other (explain)
A-35
-------
5.11 Initial Chemical Bath Make-Up Composition -OSP
Complete the chart below for each chemical component of the bath type listed. Provide the manufacturer name if the chemical used is known only by trade name. If more
room is nppdpd rilpasp attach anot
ipr shppt with thp additional information
f two tanks of thp samp tvnp art' lisprl within thp
irorpss list thp data for a sinolt' tank onlv
Bath
Chemical Product Name
Manufacturer (if annlicablei
Annual Ouantitv Used a (gallons'*
Cleaner
1.
2.
3.
4.
Microetch
1.
2.
3.
4.
Flux
1.
2.
3.
4.
Solder
1.
2.
3.
4.
Post-Clean
1.
2.
3.
4.
Other (specify)
1.
2.
3.
4.
a Annual Quantity Used - If the amount of a particular chemical used is measured by weight (i.e., crystalline chemicals) instead of volume, enter the weight in
pounds and clearly specify the units (lbs).
A-36
-------
5.12 Chemical Bath Bailout and Additions—OSP
Complete the following chart detailing the typical bath bailout and chemical additions that are made to maintain the chemical balance of each specific process
bath. If more than three chemicals are added to a specific bath, attach another sheet with the additional information. If chemical additions to a bath are made
automatically, do not complete the last three columns for that bath. If two tanks of the same type are used within the process, list the data for a single tank only.
Bath Type
Bailout
Frequency
Bailout
Durationc
(minutes)
Bailout
Quantity
Personal
Protective
EauiDment d
Chemical Products Added
Criteria for
Addition"
Method of
Chemical
Addition to Tankb
Duration of
Addition0
(minutes )
Cleaner
min.
1
min.
2
3
Microetch
min.
1
min.
2
3
Flux
min.
1
min.
2
3
Solder
min.
1
min.
2
3
Post-Clean
min.
1
min.
2
3
Other
(specify)
min.
1
min.
2
3
" Criteria for Additions - Enter the
letter for the criteria typically used to
determine when bath additions are
necessary.
[S] - Statistical process control
[P] - Panel square feet processed
[C] - Chemical testing
[T] - Time
[O] - Other
b Method of Chemical Addition to Tank - Enter the letter for
the method typically used to add chemicals to the tanks.
[PR] - Poured
[P] - Pumped manually [O] - Other
c Duration (if BaioifyWftJllffhn - Enter the elapsed time from
the retrieval of the chemical stock through the completion of the
addition of all chemicals. For bailout, enter the time required to
bailout the bath prior to making additions.
d Personal Protective Equipment - Enter the letters of all the
protective equipment used by the workers who physically replace the
spent bath.
E] - Eye protection
A] - Apron
L] - Lab coat/Sleeved garmerHlnt
-------
5.13 Chemical Bath Replacement — OSP
Complete the chart below by providing information on the process of replacing, treating, and disposing of a spent chemical bath.
Bath Type
Criteria
for Replacement a
Replacement
F requencyb
Method of Spent
Bath Removalc
Tank
Cleaning Method d
Duration of
Replacement
Procedure e
Personal
Protective
Equipmentf
Cleaner
min.
Microetch
min.
Flux
min.
Solder
min.
Post-Clean
min.
Other (specify)
min.
a Criteria for Replacement -
[S] - Statistical process control
P] - Panel square feet processed
[C - Chemical testing
T] - Time
[0] - Other (specify)
b Frequency - Enter the average amount of time
elapsed, or number of square feet processed, between
bath replacements. Clearly specify units (e.g., hours,
sq.ft.).
c Methods of Spent Bath Removal-
IP] - Pump spent bath from tank
S] - Siphon spent bath from tank
ID] - Drain spent bath from tank
[0] - Other (specify)
d Tank Cleaning Method -
[C] - Chemical flush
[W] - Water rinse
H] - Hand scrub
[0] - Other (specify)
e Duration of Replacement - Enter the
elapsed time from the beginning of bath
removal until the replacement bath is
finished.
f Personal Protective Equip. - Enter the letters
of all the protective equipment used by the
workers who physically replace the spent bath.
[E] - Eye protection
[G - Gloves
[L] - Lab coat/sleeved garment
A - Apron
[R] - Respiratory protection
B - Boots
[Z] - All except respiratory protection
[N] - None
A-38
-------
5.14 Process Waste Disposal — OSP
Bath Type
Annual Volume
Treated or Disposed a
Method of Treatment
or Disposalb
RCRA Waste
Code (if applicable)
Container
Type
Cleaner
Microetch
Flux
Solder
Post-Clean
Other (specify):
11 Annual Volume Treated or
Disposed - Enter the yearly
amount of the specific bath
treated or disposed. Be sure to
consider the volume treated
from both bath change outs
and bailout before entering the
total
b Methods of Treatment or Disposal-
P] - Precipitation pretreatment on-site
TM] - pH neutralization pretreatment on-site
S] - Disposed directly to sewer with no treatment
ID] - Drummed for off-site treatment or disposal
llN] - Recycled on-site
RF] - Recycled off-site
0] - Other (specify)
Container Type -
Indicate the type of
container used for disposal
of bath wastes
OH]- Open-head drum
CH]- Closed-head drum
T]- Chemical tote
0]- Other (specify)
A-39
-------
Section 6. Immersion Silver Process
6.1 Process Schematic: Immersion Silver
Fill in the figure below for your immersion silver surface finishing process. Using the key at the bottom of the page, dentify which letter
corresponds with the first step in your process and write that letter in the first box (see example). Continue using the key to fill in boxes for each
step until your entire immersion silver process is represented. If a particular process step is not represented by the key below, complete the figu
by writing in the name of the process step in your particular surface finishing line in the corresponding bbox(es) . Finish by responding to the
questions at the bottom of the page.
A-40
-------
6.2
General Data—Immersion Silver
Number of days the immersion silver
line is in operation:
days/yr
Number of hours per day the immersion
silver line is in operation:
hrs/day
Estimated scrap rate (% of defective
product) for the immersion silver
process:
%
Total of PWB surface square feet
processed by the immersion silver line per
year:
ssf/yr
6.3 Process Area Employees—Immersion Silver
Complete the following table by indicating the number of employees of each type that perform work duties in the
same process room as the immersion silver line, and for what length of time. Consider only workers who have
regularly scheduled responsibilities that require them to be physically within the process room. Specify "other" entry.
Enter "N/A" in any category that is not applicable.
Type of Surface Finish
Area Worker
Number of Employees
in Surface Finish Process Area
Average Hours per Week per
Employee in Surface Finish
Process Area
Line Operators
hrs
Lab Technicians
hrs
Maintenance Workers
hrs
Wastewater Treatment Operators
hrs
Supervisory Personnel
hrs
Other (specify):
hrs
6.4 Physical Settings—Immersion Silver
Size of the room containing the
surface finish process:
sq. ft.
Height of room:
ft.
Are the overall process areas/rooms
ventilated (circle one)?
Yes
No
Air flow rate:
cu. ft./min.
Do you have local vents (circle one)?
Yes
No
Local vent air flow rate:
cu. ft./min.
Overall surface finishing process line dimensions
Length (ft.): Width (ft.):
Height (ft.):
6.5 Rack Dimensions—Immersion Silver
Average number of panels per rack:
Average space between panels in rack:
in.
Average size of panel in rack:
Lengthen.): Width (in.):
Do you purposely slow the withdraw rate of your panels from process baths
to reduce drag-out? (Circle one)
Yes No
A-41
-------
6.6 Rinse Bath Water Usage—Immersion Silver
Consult the process schematic in section 2.1 to obtain the process step numbers associated with each of the water
rinse baths present in your nickel/gold process. Enter, in the table below, the process step number along with the
flow control method and flow rate data requested for each water rinse bath. If the water rinse bath is part of a
cascade, you need only report the daily water flow rate of one bath in the cascade.
Total volume of water used by the surface finish line when operating:
gal./day
Process Step
Numbera
Flow Controlb
Daily Water
Flow Rate c
Cascade Water
Process Steps d
Example: 8
R
2,400 gal./day
8-»6
gal./day
gal./day
gal./day
gal./day
gal./day
gal./day
a Process step number - Consult the process schematic in question 2.1 and
enter the process step number of the specific water rinse tank.
b Flow control - Consult key at right and enter the letter for the flow control
method used for that specific rinse bath.
c Daily water flow rate - Enter the average daily flow rate for the specific
water rinse tank.
d Cascade water process steps - Use the step numbers for rinses that are
cascaded together.
Flow Control Methods Kev
C] - Conductivity Meter
P] - pH Meter
V] - Operator Control Valve
R] - Flow Restricter
N] - None (continuous flow)
0] - Other (explain)
6.7 Filter Replacement—Immersion Silver
Not Applicable
~
Bath(s) filtered
(enter process step # from flow diagram in 2.1)
Frequency of replacement:
Duration of replacement process:
Personal protective equipment (see key):
Personal Protective Equipment Key:
[E] - Eye Protection [G] - Gloves
[L] - Lab coat/Sleeved garment [A] - Apron
[R] - Respiratory Protection [B] - Boots
[Z] - All except Respiratory Protection
[N] - None
A-42
-------
6.8
Rack or Conveyor Cleaning—Immersion Silver
Rack Cleaning Method:
[C]-Chemical bath on SF process line
[D]-Chemical bath on another line
[T]-Temporary chemical bath
[S]-Manual scrubbing with chemical
[M]-Non-chemical cleaning
[N]-None
[O]-Continuous cleaning
Conveyor Cleaning Method:
[C]-Chemical rinsing or soaking
[S]-Manual scrubbing with chemical
[M]-Non-chemical cleaning
[N]-None
[O]-Continuous cleaning
Personal Protective Equipment:
[E]-Eye Protection [G]-Gloves
[L]-Lab coat/Sleeved garment [A]-Apron
[R]-Respiratory Protection [B]-Boots
[O]-Continuous Cleaning [N]-None
[Z]-A11 except Respiratory Protection
6.9 Chemical Bath Sampling —Immersion Silver
Bath Type
Type of
Sampling a
F requencyb
Duration of
Sampling c
Protective
Equipmentd
Method of
Sampling e
Example:
A
3 per day
5 min
E, G, A
P
Pre-Cleaner
Microetch
Pre-Conditioner
Immersion
Silver
Other (specify):
- Tvrte of Sampling
[A] - Automated
[M] - Manual
[N] - None
b Frequency: Enter the average
time elapsed or number of panel sq.
ft. processed between samples.
Clearly specify units (e.g., hours, sq.
ft.). *
- Duration of Sampling: Enter the a
verage time required to manually take
a sample from the tank.
- Protective Eauipment: Consult
the key for the above table and enter
the letters for all protective
equipment used by the person
performing the chemical sampling.
- Method of Sampling:
[D] - Dram or spigot
[P] - Pipette
{L] - Ladle
[0] - Other (specify)
Not Applicable Q
Rack Cleaning Method (see key): OR
Conveyor Cleaning Method (see key):
Frequency of rack or conveyor cleaning:
Number of personnel involved:
Personal protective equipment (see key):
Average time required to clean:
min.
A-43
-------
6.10 Physical Data and Operating Conditions—Immersion Silver
Complete the tables below by entering the data requested for each specific type of chemical bath listed. If two tanks of the same type are used within the process,
list the data for each tank separately.
Average cycle time for a panel to complete entire immersion silver process
(includes cleaning and post cleaning steps, if any):
Bath
Physical Data
Process Data
Operating Conditions
Length
(inches)
Width
(inches)
Nominal
Volume
(gal)
Immersion
Time a
(seconds)
DripbTime
(seconds)
Temp
(°F)
Agitation
(see key)
Vapor Control
(see key)
P re-Cleaner
in.
in.
gal.
sec.
sec.
°F
Microetch
in.
in.
gal.
sec.
sec.
°F
Pre-Conditioner
in.
in.
gal.
sec.
sec.
°F
Immersion Silver
in.
in.
gal.
sec.
sec.
°F
Other (specify):
in.
in.
gal.
sec.
sec.
°F
a Immersion Time - Enter the average elapsed time a rack of panels is immersed in
the specific process bath.
b Drip Time - Enter the average elapsed time that a rack of panels is allowed to hang
above the specific process bath to allow drainage from panels.
Agitation Methods Kev:
Vapor Control Methods Kev:
PA] - Panel agitation
CP] - Circulation pump
AS] - Air sparge
0] - Other (explain)
BC] - Bath cover
EE] - Fully enclosed
VO] - Vent to outside
VC] - Vent to control
PP] - Push pull
0] - Other (explain)
A-44
-------
6.11 Initial Chemical Bath Make-Up Composition —Immersion Silver
Complete the chart below for each chemical component of the bath type listed. Provide the manufacturer name if the chemical used is known only by trade name. If more
room is needed, please attach another sheet with the additional information. If two tanks of the same type are used within the process, list the data for a single tank only.
Bath
Chemical Product Name
Manufacturer (if annlicablet
Annual Ouantitv Used a (gallons'*
Pre-Cleaner
1.
2.
3.
4.
Microetch
1.
2.
3.
4.
Pre-Conditioner
1.
2.
3.
4.
Immersion Silver
1.
2.
3.
4.
Other (specify)
1.
2.
3.
4.
a Annual Quantity Used - If the amount of a particular chemical used is measured by weight (i.e., crystalline chemicals) instead of volume, enter the weight in
pounds and clearly specify the units (lbs).
A-45
-------
6.12 Chemical Bath Bailout and Additions—Immersion Silver
Complete the following chart detailing the typical bath bailout and chemical additions that are made to maintain the chemical balance of each specific process
bath. If more than three chemicals are added to a specific bath, attach another sheet with the additional information. If chemical additions to a bath are made
automatically, do not complete the last three columns for that bath. If two tanks of the same type are used within the process, list the data for a single tank only.
Bath Type
Bailout
Frequency
Bailout
Durationc
(minutes)
Bailout
Quantity
Personal
Protective
Eauirnnent d
Chemical Products Added
Criteria for
Addition"
Method of
Chemical
Addition to Tankb
Duration of
Addition0
(minutes )
Pre-Cleaner
min.
1
min.
2
3
Microetch
min.
1
min.
2
3
Pre-
Conditioner
min.
1
min.
2
3
Immersion
Silver
min.
1
min.
2
3
Other
(specify)
min.
1
min.
2
3
min.
1
min.
2
3
" Criteria for Additions - Enter the
letter for the criteria typically used to
determine when bath additions are
necessary.
[S] - Statistical process control
[P] - Panel square feet processed
[C] - Chemical testing
[T] - Time
[O] - Other
b Method of Chemical Addition to Tank - Enter the letter for
the method typically used to add chemicals to the tanks.
[PR] - Poured
[P] - Pumped manually [O] - Other
c Duration of BailolS oi^A?RBfri»n - Enter the elapsed time from
the retrieval of the chemical stock through the completion of the
addition of all chemicals. For bailout, enter the time required to
bailout the bath prior to making additions.
d Personal Protective Equipment - Enter the letters of all the
protective equipment used by the workers who physically replace the
spent bath.
E] - Eye protection
A] - Apron
L] - Lab coat/Sleeved garTnera!^,,
R] - Respiratory proteftion
Z] - All except Respiratory Protection
N] - None
TGI - Gloves
A-46
-------
6.13 Chemical Bath Replacement —Immersion Silver
Complete the chart below by providing information on the process of replacing, treating, and disposing of a spent chemical bath.
Bath Type
Criteria
for Replacement a
Replacement
F requencyb
Method of Spent
Bath Removalc
Tank
Cleaning Method d
Duration of
Replacement
Procedure e
Personal
Protective
Equipmentf
Pre-Cleaner
min.
Microetch
min.
Pre-Conditioner
min.
Immersion Silver
min.
Other (specify)
min.
a Criteria for Replacement -
[S] - Statistical process control
P] - Panel square feet processed
[C - Chemical testing
T] - Time
[0] - Other (specify)
b Frequency - Enter the average amount of time
elapsed, or number of square feet processed, between
bath replacements. Clearly specify units (e.g., hours,
sq.ft.).
c Methods of Spent Bath Removal-
IP] - Pump spent bath from tank
S] - Siphon spent bath from tank
[D] - Drain spent bath from tank
[0] - Other (specify)
d Tank Cleaning Method -
[C] - Chemical flush
W] - Water rinse
H] - Hand scrub
[0] - Other (specify)
e Duration of Replacement - Enter the
elapsed time from the beginning of bath
removal until the replacement bath is
finished.
f Personal Protective Equip. - Enter the letters
of all the protective equipment used by the
workers who physically replace the spent bath.
[E] - Eye protection
[G - Gloves
[L] - Lab coat/sleeved garment
A - Apron
[R] - Respiratory protection
B - Boots
Z] - All except respiratory protection
[N] - None
A-47
-------
6.14 Process Waste Disposal — Immersion Silver
Bath Type
Annual Volume
Treated or Disposed a
Method of Treatment
or Disposalb
RCRA Waste
Code (if applicable)
Container
Type
Pre-Cleaner
Microetch
Pre-Conditioner
Immersion
Silver
Other (specify):
11 Annual Volume Treated or
Disposed - Enter the yearly
amount of the specific bath
treated or disposed. Be sure to
consider the volume treated
from both bath change outs
and bailout before entering the
total
b Methods of Treatment or Disposal-
P] - Precipitation pretreatment on-site
TST] - pH neutralization pretreatment on-site
S] - Disposed directly to sewer with no treatment
ID] - Drummed for off-site treatment or disposal
llN] - Recycled on-site
RF] - Recycled off-site
0] - Other (specify)
Container Type -
Indicate the type of
container used for disposal
of bath wastes
OH]- Open-head drum
CH]- Closed-head drum
T]- Chemical tote
0]- Other (specify)
A-48
-------
Section 7. Immersion Tin Process
7.1 Process Schematic: Immersion Tin
Fill in the figure below for your immersion tin surface finishing processses. Using the key at the bottom of the page, dentify which letter
corresponds with the first step in your process and write that letter in the first box (see example). Continue using the key to fill in boxes for each
step intil your entire immersion tin process is represented. If a particular process step is not represented by the key below, complete the figure b
writing in the name of the process step in your particular surface finishing line in the corresponding boxe(s). Finish Dy responding to the
questions at the bottom of the page.
Type of Process
6.
11.
2.
7.
12.
Process
Ex.
Step Letter '——
(see key below)
^ A
3.
8.
13.
Chemical Supplier:
Process Line Installation Date:
4.
9.
14.
5.
10.
15.
Is the entire immersion tin process, as described in the chart above,
co-located in the same room:
Yes No
* If no (process steps performed in more than one room), please
circle the steps above that are in a separate room.
Type of Process Automation for the immersion tin line: (circle one)
Conveyorized Automated non-conveyorized Manually-controlled hoist
Manual (no automation) Other (specify):
Immersion Tin Process Step Key
[A] - Cleaner
[B] - Microetch
[C] - Predip
[D] - Immersion Tin
[E] - Water Rinse
[F] - Dry
[G] - Other (Specify in the appropriate box)
A-49
-------
7.2
General Data—Immersion Tin
Number of days the immersion tin line
is in operation:
days/yr
Number of hours per day the immersion tin
line is in operation:
hrs/day
Estimated scrap rate (% of defective
product) for the immersion tin
process:
%
Total of PWB surface square feet
processed by the immersion tin line per
year:
ssf/yr
7.3 Process Area Employees—Immersion Tin
Complete the following table by indicating the number of employees of each type that perform work duties in the
same process room as the immersion tin line, and for what length of time. Consider only workers who have regularly
scheduled responsibilities that require them to be physically within the process room. Specify "other" entry. Enter
"N/A" in any category that is not applicable.
Type of Surface Finish
Area Worker
Number of Employees
in Surface Finish Process Area
Average Hours per Week per
Employee in Surface Finish
Process Area
Line Operators
hrs
Lab Technicians
hrs
Maintenance Workers
hrs
Wastewater Treatment Operators
hrs
Supervisory Personnel
hrs
Other (specify):
hrs
7.4 Physical Settings—Immersion Tin
Size of the room containing the
surface finish process:
sq. ft.
Height of room:
ft.
Are the overall process areas/rooms
ventilated (circle one)?
Yes
No
Air flow rate:
cu. ft./min.
Do you have local vents (circle one)?
Yes
No
Local vent air flow rate:
cu. ft./min.
Overall surface finishing process line dimensions
Length (ft.): Width (ft.):
Height (ft.):
7.5 Rack Dimensions—Immersion Tin
Average number of panels per rack:
Average space between panels in rack:
in.
Average size of panel in rack:
Lengthen.): Width (in.):
Do you purposely slow the withdraw rate of your panels from process baths
to reduce drag-out? (Circle one)
Yes No
A-50
-------
7.6 Rinse Bath Water Usage—Immersion Tin
Consult the process schematic in section 2.1 to obtain the process step numbers associated with each of the water
rinse baths present in your immersion tin process. Enter, in the table below, the process step number along with the
flow control method and flow rate data requested for each water rinse bath. If the water rinse bath is part of a
cascade, you need only report the daily water flow rate of one bath in the cascade.
Total volume of water used by the surface finish line when operating:
gal./day
Process Step
Numbera
Flow Controlb
Daily Water
Flow Rate c
Cascade Water
Process Steps d
Example: 8
R
2,400 gal./day
8-»6
gal./day
gal./day
gal./day
gal./day
gal./day
gal./day
a Process step number - Consult the process schematic in question 2.1 and
enter the process step number of the specific water rinse tank.
b Flow control - Consult key at right and enter the letter for the flow control
method used for that specific rinse bath.
c Daily water flow rate - Enter the average daily flow rate for the specific
water rinse tank.
d Cascade water process steps - Use the step numbers for rinses that are
cascaded together.
Flow Control Methods Kev
C] - Conductivity Meter
P] - pH Meter
V] - Operator Control Valve
R] - Flow Restricter
N] - None (continuous flow)
0] - Other (explain)
7.7 Filter Replacement—Immersion Tin
Not Applicable
~
Bath(s) filtered
(enter process step # from flow diagram in 2.1)
Frequency of replacement:
Duration of replacement process:
Personal protective equipment (see key):
Personal Protective Equipment Kev:
[E] - Eye Protection [G] - Gloves
[L] - Lab coat/Sleeved garment [A] - Apron
[R] - Respiratory Protection [B] - Boots
[Z] - All except Respiratory Protection
[N] - None
A-51
-------
7.8
Rack or Conveyor Cleaning—Immersion Tin
Rack Cleaning Method:
[C]-Chemical bath on SF process line
[D]-Chemical bath on another line
[T]-Temporary chemical bath
[S]-Manual scrubbing with chemical
[M]-Non-chemical cleaning
[N]-None
[0]-Continuous cleaning
Conveyor Qeaning Method:
[C]-Chemical rinsing or soaking
[S]-Manual scrubbing with chemical
[M]-Non-chemical cleaning
[N]-None
[0]-Continuous cleaning
Personal Protective Equipment:
[E]-Eye Protection [G]-Gloves
[L]-Lab coat/Sleeved garment [A]-Apron
[R]-Respiratory Protection [B]-Boots
[0]-Continuous Cleaning [N]-None
[Z]-A11 except Respiratory Protection
7.9 Chemical Bath Sampling -Immersion Tin
Bath Type
Type of
Sampling a
F requencyb
Duration of
Sampling c
Protective
Equipmentd
Method of
Sampling e
Example:
A
3 per day
5 min
E, G, A
P
Cleaner
Microetch
Predip
Immersion Tin
Other (specify):
- Tvrte of Sampling
- Duration of Sampling: Enter the a
- Method of Sampling:
[A] - Automated
M] - Manual
[N] - None
b Frequency: Enter the average
time elapsed or number of panel sq.
ft. processed between samples.
Clearly specify units (e.g., hours, sq.
ft.).
verage time required to manually take
a sample from the tank.
- Protective Equipment: Consult
the key for the above table and enter
the letters for all protective
equipment used by the person
performing the chemical sampling.
[D] - Drain or spigot
[P] - Pipette
{L] - Ladle
[0] - Other (specify)
Not Applicable Q
Rack Cleaning Method (see key): OR
Conveyor Cleaning Method (see key):
Frequency of rack or conveyor cleaning:
Number of personnel involved:
Personal protective equipment (see key):
Average time required to clean:
min.
A-52
-------
7.10 Physical Data and Operating Conditions—Immersion Tin
Complete the tables below by entering the data requested for each specific type of chemical bath listed. If two tanks of the same type are used within the process,
list the data for each tank separately.
Average cycle time for a panel to complete entire immersion tin process
(includes cleaning and post cleaning steps, if any):
Bath
Physical Data
Process Data
Operating Conditions
Length
(inches)
Width
(inches)
Nominal
Volume
(gal)
Immersion
Time a
(seconds)
DripbTime
(seconds)
Temp
(°F)
Agitation
(see key)
Vapor Control
(see key)
Cleaner
in.
in.
gal.
sec.
sec.
°F
Microetch
in.
in.
gal.
sec.
sec.
°F
Predip
in.
in.
gal.
sec.
sec.
°F
Immersion Tin
in.
in.
gal.
sec.
sec.
°F
Other (specify):
in.
in.
gal.
sec.
sec.
°F
a Immersion Time - Enter the average elapsed time a rack of panels is immersed in
the specific process bath.
b Drip Time - Enter the average elapsed time that a rack of panels is allowed to hang
above the specific process bath to allow drainage from panels.
Agitation Methods Kev:
Vapor Control Methods Kev:
PA] - Panel agitation
CP] - Circulation pump
AS] - Air sparge
0] - Other (explain)
BC] - Bath cover
EE] - Fully enclosed
VO] - Vent to outside
VC] - Vent to control
PP] - Push pull
0] - Other (explain)
A-53
-------
7.11 Initial Chemical Bath Make-Up Composition —Immersion Tin
Complete the chart below for each chemical component of the bath type listed. Provide the manufacturer name if the chemical used is known only by trade name. If more
room is needed, please attach another sheet with the additional information. If two tanks of the same type are used within the process, list the data for a single tank only.
Bath
Chemical Product Name
Manufacturer (if annlicablet
Annual Ouantitv Used a (gallons'*
Cleaner
1.
2.
3.
4.
Microetch
1.
2.
3.
4.
Predip
1.
2.
3.
4.
Immersion Tin
1.
2.
3.
4.
Other (specify)
1.
2.
3.
4.
a Annual Quantity Used - If the amount of a particular chemical used is measured by weight (i.e., crystalline chemicals) instead of volume, enter the weight in
pounds and clearly specify the units (lbs).
A-54
-------
7.12 Chemical Bath Bailout and Additions—Immersion Tin
Complete the following chart detailing the typical bath bailout and chemical additions that are made to maintain the chemical balance of each specific process
bath. If more than three chemicals are added to a specific bath, attach another sheet with the additional information. If chemical additions to a bath are made
automatically, do not complete the last three columns for that bath. If two tanks of the same type are used within the process, list the data for a single tank only.
Bath Type
Bailout
Frequency
Bailout
Durationc
(minutes)
Bailout
Quantity
Personal
Protective
Eauirnnent d
Chemical Products Added
Criteria for
Addition"
Method of
Chemical
Addition to Tankb
Duration of
Addition0
(minutes )
Cleaner
min.
1
min.
2
3
Microetch
min.
1
min.
2
3
Predip
min.
1
min.
2
3
Immersion
Tin
min.
1
min.
2
3
Other
(specify)
min.
1
min.
2
3
min.
1
min.
2
3
" Criteria for Additions - Enter the
letter for the criteria typically used to
determine when bath additions are
necessary.
[S] - Statistical process control
[P] - Panel square feet processed
[C] - Chemical testing
[T] - Time
[O] - Other
bMethod of Chemical Addition to Tank - Enter the letter for the
method typically used to add chemicals to the tanks.
[PR] - Poured
[P] - Pumped manually [O] - Other
c Duration of BailolS oi^A?RBfii»n - Enter the elapsed time
from the retrieval of the chemical stock through the completion
of the addition of all chemicals. For bailout, enter the time
required to bailout the bath prior to making additions.
d Personal Protective Equipment - Enter the letters of all the
protective equipment used by the workers who physically replace the
spent bath.
E] - Eye protection
A] - Apron
L] - Lab coat/Sleeved garTnera!^,,
R] - Respiratory proteftion
Z] - All except Respiratory Protection
N] - None
TGI - Gloves
A-55
-------
7.13 Chemical Bath Replacement — Immersion Tin
Complete the chart below by providing information on the process of replacing, treating, and disposing of a spent chemical bath.
Bath Type
Criteria
for Replacement a
Replacement
F requencyb
Method of Spent
Bath Removalc
Tank
Cleaning Method d
Duration of
Replacement
Procedure e
Personal
Protective
Equipmentf
Cleaner
min.
Microetch
min.
Predip
min.
Immersion Tin
min.
Other (specify)
min.
a Criteria for Replacement -
[S] - Statistical process control
[P] - Panel square feet processed
[C - Chemical testing
T] - Time
[0] - Other (specify)
b Frequency - Enter the average amount of time
elapsed, or number of square feet processed, between
bath replacements. Clearly specify units (e.g., hours,
sq.ft.).
c Methods of Spent Bath Removal-
IP] - Pump spent bath from tank
[S] - Siphon spent bath from tank
ID] - Drain spent bath from tank
[0] - Other (specify)
d Tank Cleaning Method -
[C] - Chemical flush
W] - Water rinse
[H] - Hand scrub
[0] - Other (specify)
e Duration of Replacement - Enter the
elapsed time from the beginning of bath
removal until the replacement bath is
finished.
f Personal Protective Equip. - Enter the letters
of all the protective equipment used by the
workers who physically replace the spent bath.
|E] - Eye protection
[G - Gloves
[L] - Lab coat/sleeved garment
[A - Apron
[R] - Respiratory protection
B* - Boots
[Z] - All except respiratory protection
[N] - None
A-56
-------
7.14 Process Waste Disposal — Immersion Tin
Bath Type
Annual Volume
Treated or Disposed a
Method of Treatment
or Disposalb
RCRA Waste
Code (if applicable)
Container
Type
Cleaner
Microetch
Predip
Immersion Tin
Other (specify):
11 Annual Volume Treated or
Disposed - Enter the yearly
amount of the specific bath
treated or disposed. Be sure to
consider the volume treated
from both bath change outs
and bailout before entering the
total
b Methods of Treatment or Disposal-
P] - Precipitation pretreatment on-site
TM] - pH neutralization pretreatment on-site
S] - Disposed directly to sewer with no treatment
ID] - Drummed for off-site treatment or disposal
llN] - Recycled on-site
RF] - Recycled off-site
0] - Other (specify)
Container Type -
Indicate the type of
container used for disposal
of bath wastes
OH]- Open-head drum
CH]- Closed-head drum
T]- Chemical tote
0]- Other (specify)
A-57
-------
Facility Background Information
Design
for the
Environment
Printed Wiring Board Project
Performance Demonstration Questionnaire
Please complete this questionnaire, make a copy for
your records, and send the original to:
Ellen Moore
Abt Associates
55 Wheeler St.
Cambridge, MA 02138
Fax: (617) 349-2660
Note: The completed questionnaire must be returned PRIOR TO the
scheduled site visit.
FACILITY AND CONTACT INFORMATION
^arilitv Identifies
tinn-
Company
Name:
Site Name:
Street Address:
City:
State: Zip:
"'nntart TH
pntifirfltinn Fnter the names nf the nersnns wV
n ran he rnntarterl reoarrlinp this snrvev
Name:
Title:
Phone:
Fax:
E-Mail:
A-58
-------
Section 1. Facility Characterization
Estimate manufacturing data for the previous 12 month period or other convenient time period of 12
consecutive months (e.g., FY96). Only consider the portion of the facility dedicated to PWB
manufacturing when entering employee and facility size data.
1.1 General Information
Size of portion of facility used for
manufacturing PWBs.
Sq. Ft.
Number of days Surface Finish line is
in operation:
days/yr
Size of portion of facility used for
surface finishing.
Sq. Ft.
1.2 Process Type
Estimate the percentage of PWBs manufactured at your facility using the following methods for surface
finishing (SF). Specify "other" entry.
Type of PWB process
Percent of total
Type of PWB process
Percent of Total
HASL
%
Electroless Palladium
%
OSP-Thick
%
Electroless Nickel/Immersion Gold
%
OSP-Thin
%
Other:
%
Immersion Tin
%
Other:
%
Immersion Silver
%
TOTAL
100%
1.3 General Process Line Data
Process Data
Hours
Number of hours the Surface Finishing line is in operation per day:
1.4 Process Area Employees
Complete the following table by indicating the number of employees of each type that perform work
duties in the same process room as the Surface Finishing line and for what length of time. Report the
number of hours per employee. Consider only workers who have regularly scheduled responsibilities
physically within the process room. Specify "other" entry. Enter "N/A" in any category not applicable
Type of Process
Area Worker
Number of Employees
in Process Area
Average Hours per Week per
Employee in Process Area
Line Operators
Hrs.
Lab Technicians
Hrs.
Maintenance Workers
Hrs.
Wastewater Treatment Operators
Hrs.
Supervisory Personnel
Hrs.
Other:
Hrs.
Other:
Hrs.
A-59
-------
1.5 Wastewater Discharge and Sludge Data
Wastewater discharge type (check one) Direct Indirect
Zero
Annual weight (quantity in pounds) of sludge generated:
Is sludge dewatered prior to disposal?
% water content prior to dewatering:
% water content after dewatering:
Section 2. Process Description: Immersion Tin
2.1 Process Schematic
Fill in the following table by identifying what type of surface finishing process (e.g., HASL) your facility
uses. Then, using the proper key at the bottom of the page, identify which letter corresponds with the first
step in your process and write that letter in the first box (see example). Continue using the key to fill in
boxes for each step in your process until your entire surface finishing process is represented. If your
process is not represented by a key below, complete the chart by writing in the name of each process step
in your particular surface finishing line.
A-60
-------
Name of Process:
Process
Step Letter
(see key below)
Immersion Tin Process Step Key
[A] - Cleaner [D] - Immersion Tin
[B] - Microetch [E] - Water Rinse
[C] - Predip [F] - Other (specify step)
A
10.
15.
-------
2.2 Rinse Bath Water Usage
Consult the process schematic in section 2.1 to obtain the process step numbers associated with each of
the water rinse baths present. Enter, in the table below, the process step number along with the flow
control method and flow rate data requested for each water rinse bath. If the water rinse bath is part of
a cascade, you need only report the daily water flow rate of one bath in the cascade.
Amount of water used by the surface finishing line when operating:
gal/day
Process Step Number a
Flow Controlb
Daily Water Flow
Rate c
Cascade Water Process Steps d
Example: 8
R
2,400 gal./day
86
gal./day
gal./day
gal./day
gal./day
gal/, day
gal./day
gal./day
gal./day
a Process step number - Consult the process schematic in question 2.1 and
enter the process step number of the specific water rinse tank.
b Flow control - Consult key at right and enter the letter for the flow control
method used for that specific rinse bath.
c Daily water flow rate - Enter the average daily flow rate for the specific
water rinse tank.
d Cascade water process steps - Use the step numbers for rinses that are
cascaded together.
Flow Control Methods Kev
[C] - Conductivity Meter
[P] - pH Meter
[V] - Operator Control Valve
[R] - Flow Restricter
[N] - None (continuous flow)
[0] - Other (explain)
2.3 Process Parameters
Size of the room containing the process
sq. ft.
Height of room
Are the overall process areas (not tank vent) ventilated? (Circle one)
No
Air flow rate:
cu.ft.min.
Do you have local vents?
No
Local vent air flow rate:
cu. Ft./min.
Type of process automation for surface finishing line: (circle one)
Automated non-conveyorized Automated conveyorized Manually controlled hoise
Manual (no automation) Other, specify:
A-62
-------
2.4 Physical, Process, and Operating Conditions
Complete the table below by entering the data requested for each specific type of chemical bath listed. If
two tanks of the same type are used within the process, list the data for a single tank only.
BATH
LENGTH (inches)
WIDTH (inches)
NOMINAL VOLUME
Acid cleaner
in.
in..
gal.
Microetch
in.
in..
gal.
Acid predip
in.
in..
gal.
Immersion tin
in.
in..
gal.
Other (specify)
in.
in..
gal.
in.
in..
gal.
in.
in..
gal.
in.
in..
gal.
A-63
-------
2.5 Initial Chemical Bath Make-Up Composition
Complete the chart below for each chemical component of the bath type listed. Provide the manufacturer name if the chemical used is
known only by trade name. If more room is needed, please attach another sheet with the additional information. If two tanks of the
same type are used within the process, list the data for a single tank only.
BATH
CHEMICAL PRODUCT NAME
MANUFACTURER
(if applicable)
ANNUAL QUANTITY USED3
(gallons)
CLEANER
1.
2.
3.
4.
MICROETCH
1.
2.
3.
4.
ACID PREDIP
1.
2.
3.
4.
IMMERSION
TIN
1.
2.
3.
4.
OTHER
(specify)
1.
2.
3.
4.
a Annual Quantity Used - If the amount of a particular chemical used is measured by weight (i.e., crystalline chemicals) instead of
volume, enter the weight in pounds and clearly specify the units (lbs).
A-64
-------
2.6 Chemical Bath Replacement
Complete the chart below by providing information on the process of replacing, treating, and disposing of a spent chemical bath.
Bath Type
Criteria
for
Replacement
Frequency
Tank
Cleaning
Methodc
Duration of
Replacement
Procedured
Personal
Protective
Equipment'
Method of
Treatment or
Disposalf
Annual
Volume
Treated or
Disposedg
ACID CLEANER
mm.
MICROETCH
mm.
ACID PREDIP
mm.
IMMERSION
TIN
mm.
Criteria for Replacement -
iiicua iui rvepiaeeiiiem -
- Statistical process control
- Panel square feet processed
- Chemical testing
- Time
- Other (specify)
S
P'
C
T
:oj
b Frequency - Enter the average amount
of time elapsed, or number of square feet
processed, between bath replacements.
Clearly specify units (e.g., hours, sq.ft.,
etc.)
cTank Cleaning Method
C] - Chemical Flush
W] - Water Rinse
- Hand Scrub
Other (specify)
d Duration of Replacement-
Enter the elapsed time from the beginning
of bath removal until the replacement bath
is finished.
f Personal Protective Equip. -
Enter the letters of all the protective
equipment used by the workers who
physically replace the spent bath.
E ~ ' ¦"
G
L
A
R
B
Z
[N]
- Eye protection
- Gloves
- Lab coat/sleeved garment
- Apron
- Respiratory protection
- Boots
- All except respiratory protection
- None
f Methods of Spent Bath Removal -
P] - Precipitation Pretreatment on-site
N] - PH Neutralization Pretreatment on-site
S] - Disposed directly to sewer with no treatment
D] - Drummed for off-site treatment or disposal
RN] - Recycled on-site
RF] - Recycled off-site
O] - Other (specify)
g Annual Vol. Treat. Or Disp. -
Enter the yearly amount of the specific bath treated or
disposed. Needed only if water testing is not done.
A-65
-------
2.7 Chemical Bath Additions
Complete the following chart detailing the typical chemical additions that are made to maintain the chemical balance of each specific process bath.
If more than four chemicals are added to a specific bath, attach another sheet with the additional information. If chemical additions to a bath are
made automatically, do not complete the last three columns for that bath. If two tanks of the same type are used within the process, list the data for
Bath Type
Chemical Products
Added
Criteria for
Replacement3
Method of Chemical
Addition to Tankb
Duration of
Addition0 (minutes)
Personal Protective
Equipment"1
CLEANER
1.
2.
3.
4.
MICROETCH
1.
2.
3.
4.
ACID PREDIP
1.
2.
3.
4.
IMMERSION
TIN
1.
2.
3.
4.
OTHER (specify):
1.
2.
3.
4.
'"Criteria for Replacement -
Enter the letter for the criteria typically used to determine when bath
replacement is necessary.
[S] - Statistical Process Control
[P] - Panel Square Feet Processed
[C] - Chemical Testing
[T\ - Time
[O] - Other
"Method of Chemical Addition to Tank -
Enter the letters for the method typically used to add chemicals to
the tanks.
[P] - Pumped Manually
PR] - Poured
[S] - Scooped
[O] - Other
'Duration of Addition - Enter the average elapsed time from the
retrieval of the chemical stock through the completion of the
addition of all chemicals
"Pt
pre
the
[E]
[G
[L
[A
[R
[B
[Z
[N
rsonal Protective Equipment - Enter the letters of all the
tective equipment worn by the workers physically replacing
spent batn.
- Eye protection
- Gloves
- Labcoat/Sleeved garment
- Apron
- Respiratory protection
- Boots
- All except Respiratory Protection
- None
A-66
-------
Observer Data Sheet
Observer Data Sheet
DfE PWB Performance Demonstrations
Facility name and location:
Surface finishing process type and name: Installation date:
Date: Contact Name:
Test Panel Run
Overall Surface Finishing process line dimensions
Length (ft.): Width (ft.):
Height (ft.):
Average number of panels per rack:
Average space between panels in rack:
Average size of panel in rack: Length(in):
Width (in.):
At what % of capacity is the line currently
running?
At what % of capacity is the line typically
running?
What is the overall throughout? surface sq.ft./year
How is it calculated:
Estimated yield for surface finishing line:
Number of thermal cycles the finished board can withstand:
Note any unusual storage conditions or oxidation.
Load system with layer 4 facing up or toward the operator.
While running the test panels, verify each process step and complete the table on the next page.
Test Panel Serial Numbers
Test Board
Serial #
Test Board
Serial #
Test Board
Serial #
1.
3.
5.
2.
4.
6.
A-67
-------
Test Panel Run
Bath Name
(from schematic)
Equipment3
Bath
Temp
Immersion
Time
Drip
Time
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
Overall System Time:
a List Number, type of
Agitation: Vapor Control: Filter Type: Heater Control: Water Rinses:
[PA] - Panel agitation [ BC] - Bath Cover [BF] - Bag [TH] - Thermostat [CN] - Continuous
[CP] - Circulation Pump []FE} - Fully Enclosed [CF] - Cartridge [TM] - Tinier [DP] - Continuous During Process
[AS] - Air Sparge [ VO] - Vent to Outside [PR] - Programmed [PP] - Partial During Process
[VC] - Vent to Control
A-68
-------
Ycrificsilion of l*:irt A (niiirk siny chnn^os on working copy of I'sirl A):
Ventilation:
Verify the type of ventilation as recorded in the Questionnaire:
Tank Volumes:
Verify the length, width, and volume of each tank, as recorded in the Questionnaire:
Water use:
Verify water use data, for each tank: .—.
Daily water flow rate verified I—I
Cascade process steps verified | |
Pollution Prevention:
Have you used any other pollution prevention techniques on the surface finishing line (e.g., covered
tanks to reduce evaporation, measures to reduce dragout, changes to conserve water, etc.)?
If yes, describe and quantify results (note: if results have not been quantified, please provide an
estimate):
If your throughput changed during the time new pollution prevention techniques were
implemented, estimate how much (if any) of the pollution reductions are due to the throughput
changes:
A-69
-------
Filter Replacement
Bath(s) filtered (enter process step #)
Frequency of replacement:
Duration of replacement process:
Personal protective equipment (see key):
Pe
[E]
[L
[R
rsonal Protective Equipment Key:
- Eye Protection [G] - Gloves [Z] - All except Respiratory Protection
- Labcoat/Sleeved garment [A] - Apron [N] - None
- Respiratory Protection [B] - Boots
Equipment Maintenance
Estimate the maintenance requirements (excluding filter changes and bath changes) of the surface
finishing process equipment for both outside services calls (maintenance by vendor or service
company) and in-house maintenance (by facility personnel).
Describe the typical maintenance activities associated with the surface finishing process line (e.g.,
motor repair/replacement, conveyor repairs, valve leaks, etc.)
Average time spent per week:
Average downtime:
If there a recurring maintenance problem?
If yes, describe:
A-70
-------
Rack or Conveyor Cleaning Not Applicable Q
Frequency of rack or conveyor cleaning:
Rack Cleaning Method (see key): OR
Conveyor Cleaning Method (see key):
Number of personnel involved:
Personal protective equipment (see key):
Average time required to clean:
Rack Cleaning Method:
C] - Chemical bath on SF process line
D] - Chemical bath on another line
T] - Temporary chemical bath
S] - Manual scrubbing with chemical
M] - Non-chemical cleaning
N1 - None
<1-
O] - Continuous cleaning
Conveyor Cleaning Method:
rC] - Chemical rinsing or soaking
S] - Manual scrubbing with chemical
Ml - Non-chemical cleaning
NJ - None
O] - Continuous cleaning
Personal Protective Equipment:
'E] - Eye Protection
G1 - Gloves
3J"
LJ - Labcoat/Sleeved garment
R] - Respiratory Protection
O] - Continuous Cleaning
Z] - All except Respiratory Protection
A] - Apron
13] - Boots
N] - None
Chemical Bath Sampling
Bath Type
Type of
Sampling"
Frequency b
Duration of
Sampling c
Protective
Equipmentd
Method of
Sampling e
Cleaner
Microetch
Flux
Solder
Post Clean
Other
(specify)
Other
(specify)
a Type of Sampling c Duration of Sampling: e Method of Obtaining Samples:
[A] - Automated Enter the average time for manually [D] - Drain or spigot
[M] - Manual taking a sample from the tank [p] - Pipette
[N] - None [L] - Ladle
[O] - Other (specify)
b Frequency: (1 Protective Equipment:
Enter the average time elapsed Consult the key for the above table
or number of panel sq. ft. processed and enter the letters for all protective
between samples. Clearly specify equipment worn by the person performing
units (e.g., hours, sq. ft., etc.) the chemical sampling.
A-71
-------
Process Description
Process Schematic
Fill in the table below by identifying what type of alternative surface finishing process (e.g., immersion tin) your company uses. Then, using the key at the bottom left of the
page, identify which letter corresponds with the first bath step in your process and write that letter in the first box (see example). Continue using the key to fill in boxes for each
step in your process until your entire alternative surface finishing process is represented. If your process step is not represented by the key below, complete the chart by writing in
the name of the process step in your particular surface finishing fine.
Process Automation
Letter (see key below right)
Type of Process
(write in process name)
Process Steps of
Your Facility
(begin here)
2.
1.
6.
7.
9.
11.
14.
16.
Standard Bath Types
G] - Accelerator
H] - Enhancer
J] - Electroless Nickel
K] - Electroless Gold
L] - Electroless Palladium
M] - Immersion
Palladium
[N] - Immersion Gold
P] - Immersion Tin
Q] - Immersion Silver
R] - OSP
S] - Anti-tamish
W] - Water rinse
O] - Other (specify step)
[AJ - Center
[B] - Conditioner
[C] - Micro Etch
[D] - Pre-dip
E] - Catalyst
[F] - Activator
Process Automation
Please list all the process types with which the above process may be operated in:
Process Automation Key
PJ - Automated on-conveyorized [S] - Manually controlled hoist [V] - Other (specify)
Q] - Automated conveyorized [T] - Manual (no information)
R] - Partially automated [A] - All of the above
A-72
-------
C 0111 p:i i':i I i vc K\ :t I u :t I ion:
ll'llic l;ici111> has s\\ ildieJ li'om ;i |iiv\ ions s\ slcni In llie cui'ivnl s\ slem. toni|ilclc Ihis |\ilv
Product Quality:
What, if any, changes were noticed in the quality of the boards produced? (Yield change?)
Installation:
How long was the debug period when this system was installed?
What were the types of problems encountered:
Manufacturing Process Changes: How did you change your upstream or downstream processes
when this system was installed (e.g., did you have to make changes in your solder mask)?
Waste Treatment:
Have any ofyour waste treatment methods or volumes changed due to the installation of this system
(not associated with volume changes due to throughput changes)?
If yes, describe the change(s) and attach quantitative information, if available:
Process Safety:
Have any additional OSHA-related procedures or issues arisen as a result of changing to the present
system (e.g., machinery lock-outs while cleaning, etc)? If so, describe:
Customer Acceptance:
Have customers accepted the new process? Why or why not:
Other:
Describe any other issues that have arisen as a result of the new process.
A-73
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Supplier Data Sheet
DfE Printed Wiring Board Project
Alternative Technologies for Surface Finishing
Manufacturer/Supplier Product Data Sheet
Manufacturer N ame:
Address:
Contact:
Phone:
Fax:
How many alternative making holes conductive product lines will you submit for testing?
Please complete a Data Sheet for each product line you wish to submit for testing. In addition,
if you have not already done so, please submit the material safety data sheets (MSDS), product
literature, and the standard manufacturer instructions for each product line submitted.
Product Line Name: Category:"
* Categories of Product Lines:
A. HASL
B. Immersion Tin
C. Immersion Palladium
D. Electroless Nickel/Immersion Gold
E. Nickel/Palladium/Immersion Gold
F. OSP - (Thin)
G. OSP-(Thick)
For the product line listed above, please identify one or two facilities that are currently using the
product line at which you would like your product demonstrated. Also, identify the location of the
site (city, state) and whether the site is 1) a customer production site, 2) a customer test site, or 3)
your own supplier testing site.
Facility 1 Name and Location:
Type of Site:
Facility Contact:
May we contact the facility at this time (yes or no):
Facility 2 Name and Location:
Type of Site:
Facility Contact Phone:
May we contact the facility at this time (yes or no):
A-74
-------
Kncr»v I sago
For each piece of equipment in the surface finishing line using energy, complete the table below:
Equipment Type
Tank or
Station #a
Power Rating
(from nameplate)
Load
(1% capacity in use)
Equipment
Cost
Period of Usage
Machine Control
_ continuous
_ continuous during process cycle
_ partial during process cycle. If partial, record
how often:
_ other:
_ timer
_ program
_ operator/manual
_ other:
_ continuous
_ continuous during process cycle
_ partial during process cycle. If partial, record
how often:
_ other:
_ timer
_ program
_ operator/manual
_ other:
_ continuous
_ continuous during process cycle
_ partial during process cycle. If partial, record
how often:
_ other:
_ timer
_ program
_ operator/manual
_ other:
_ continuous
_ continuous during process cycle
_ partial during process cycle. If partial, record
how often:
_ other:
_ timer
_ program
_ operator/manual
_ other:
_ continuous
_ continuous during process cycle
_ partial during process cycle. If partial, record
how often:
_ other:
_ timer
_ program
_ operator/manual
_ other:
a Specify whether tank number of process flow diagram step numbers are used.
A-75
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Special Product Characteristics
1. Does the process operate as a vertical process, horizontal process, or either?
2. Average number of thermal excursions the finished board can withstand?
3. Most likely process step preceding the beginning of the surface finish application?
4. Should the application of solder mask occur after the application of the surface finish, or before?
5. Which of the following technologies is the surface finish compatible with?
(Circle all applicable choices.)
A. SMT D. Gold Wire Bonding
B. Flip Chip E. Aluminum Wire Bonding
C. BGA F. Other, Explain:
6. Please state cycle time of surface finish process line.
7. Please describe any special process equipment recommended (e.g., high pressure rinse, air knife, dryer,
aging equipment, etc.).
Product Line Constraints
1. Please list any substrate incompatibilities (e.g., BT, cyanate ester, Teflon, Kevlar, copper invar copper,
polyethylene, other [specify])
2. Please list compatibilities with solder masks.
3. Are there any special requirements needed for the soldering process (e.g., type of flux, etc.)?
4. Average shelf-life of finished boards?
5. Other general comments about the product line (include any known impacts on other process
steps).
A-76
-------
Bath Life
Please fill in the following table (for bath listings, please refer back to your process description on page
2).
Bath
Recommended
T reatment/Disposal
Methoda
Criteria for Dumping
Bath
(e.g., time, surface sq ft of
panel processed,
concentration, etc.)
Recommended Bath
Life
(in terms of criteria listed
at left)
1.
2.
3.
4.
5.
6.
7.
8.
a Attach and reference materials, if necessary.
A-77
-------
Costs:
Chemical Cost
Please provide the cost per gallon (or pound) of chemical for each chemical product required to operate
this alternative surface finishing product line. It is recognized that the cost of chemicals is, in part,
dependant on the amount of chemical purchased (i.e., volume discounts) and may vary accordingly. If
cost would decrease, please write decreased cost in margin along with volume of chemical required for
pricing discount.
lialli Name
Product Name
Chemical Cos!
(S/«al or S/lb)
1.
A.
B.
C.
2.
A.
B.
C.
3.
A.
B.
C.
4.
A.
B.
C.
5.
A.
B.
C.
6.
A.
B.
C.
7.
A.
B.
C.
A-78
-------
Equipment Cost
Do you recommend or suggest any specific equipment manufacturers to customers for obtaining process
equipment to operate this surface finish line? If so, why? Please provide the contact information for
equipment manufacturer below.
Equipment Company # 1
Company Name:
Contact Name:
Phone number:
Equipment Type:
Equipment Company # 2
Company Name:
Contact Name:
Phone number:
Equipment Type:
Do either of the companies listed above manufacture equipment specifically designed for your product
line? Which one?
If so, what is special or different about the equipment design?
A-79
-------
Appendix B
Bath Chemistry Data
-------
Contents
Table B-l. Bath Concentrations for the HASL Technology
Table B-2. Bath Concentrations for the Electroless Nickel/Immersion Gold Technology
Table B-3. Bath Concentrations for the Electroless Nickel/Electroless Palladium/Immersion
Gold Technology
Table B-4. Bath Concentrations for the OSP Technology
Table B-5. Bath Concentrations for the Immersion Silver Technology
Table B-6. Bath Concentrations for the Immersion Tin Technology
-------
Table B-l. Bath Concentrations for the HASL Technology
Bath
Chemicals
Concentration in Bath (g/1)
Cleaner
Alkylphenolpolyethoxyethanol
Ethylene glycol monobutyl ether
Fluoboric acid
Phosphoric acid
Sulfuric acid
*9 other confidential chemicals
18.00
22.90
12.33
61.11
110.40
Microetch
1,4-Butenediol
Copper sulfate pentahydrate
Hydrogen peroxide
Sodium hydroxide
Sulfuric acid
*7 other confidential chemicals
12.72
45.00
50.73
0.170
103.50
Table B-2. Bath Concentrations for the Electroless Nickel/Immersion Gold Technology
Bath
Chemicals
Concentration in Bath (g/1)
Cleaner
Phosphoric acid
Sulfuric acid
Hydrochloric acid
Alkylphenolpolyethoxyethanol
*Two other confidential chemicals
50.8
138
17.85
18.00
Microetch
Sodium hydroxide
Hydrogen peroxide
Copper sulfate pentahydrate
Sulfuric acid
*Two other confidential chemicals
0.170
35.88
45.00
87.40
Catalyst
Hydrochloric acid
*Four other confidential chemicals
55.80
Acid Dip
*Two confidential chemicals
Electroless Nickel
Nickel sulfate
*13 other confidential chemicals
37.24
Immersion Gold
Potassium gold cyanide
*Four other confidential chemicals
2.999
B-l
-------
Table B-3. Bath Concentrations for the Electroless Nickel/Electroless
Palladium/Immersion Gold Technology
Bath
Chemical
Concentration in Bath (g/1)
Cleaner
Phosphoric acid
*2 other confidential chemicals
50.80
Microetch
Sodium hydroxide
Hydrogen peroxide
Copper sulfate pentahydrate
Sulfuric acid
* 1 other confidential chemical
0.17
35.88
45.00
156.40
Catalyst
*4 confidential chemicals
Acid Dip
* 1 confidential chemical
Electroless Nickel
Nickel sulfate
*10 other confidential chemicals
58.65
Preinitiator
*4 confidential chemicals
Electroless Palladium
Ethylenediamine
Propionic acid
Maleic acid
*6 other confidential chemicals
4.45
7.30
2.00
Immersion Gold
Potassium gold cyanide
*4 other confidential chemicals
3.00
Table I
1-4. Bath Concentrations for the OSP Technology
Bath
Chemical
Concentration in Bath (g/1)
Cleaner
Phosphoric acid
Sulfuric acid
*3 other confidential chemicals
50.80
9.20
Microetch
Sodium hydroxide
Hydrogen peroxide
Copper sulfate pentahydrate
Sulfuric acid
*6 other confidential chemicals
0.170
18.165
45.00
250.70
OSP
Copper ion
*5 other confidential chemicals
50.50
B-2
-------
Table B-5. Bath Concentrations for the Immersion Silver Technology
Bath
Chemical
Concentration in Bath (g/1)
Cleaner
Phosphoric acid
122.90
Microetch
1,4-Butenediol
Sulfuric acid
Hydrogen peroxide
12.72
4.60
113.00
Predip
Sodium hydroxide
*4 other confidential chemicals
29.36
Immersion Silver
Sodium hydroxide
*5 other confidential chemicals
26.43
Table B-6. I
ath Concentrations for the Immersion Tin Technology
Bath
Chemical
Concentration in Bath (g/1)
Cleaner
Ethylene glycol monobutyl ether
Fluoboric acid
Sulfuric acid
Phosphoric acid
*6 other confidential chemicals
22.90
12.33
184.00
30.25
Microetch
Sulfuric acid
* 1 other confidential chemical
18.40
Predip
Methane sulfonic acid
Sulfuric acid
*10 other confidential chemicals
337.50
0.0092
Immersion Tin
Sulfuric acid
Urea
1,3 -Diethylthiourea
Tin chloride
Methane sulfonic acid
Stannous methane sulfonic acid
*14 other confidential chemicals
92.18
90.00
20.00
13.98
69.17
111.80
B-3
-------
Appendix C
Chemical Properties Data
-------
Contents
1.3-Diethylthioure a C-l
1.4-Butenedio l C-3
Acetic Acid C-4
Branched Octylphenol, Ethoxylated C-8
Ammonium Chloride C-9
Ammonium Hydroxide C-l2
Sodium Citrate (citric acid) C-l4
Cupric Sulfate (copper ion) C-l6
Cupric Acetate (copper sulfate pentahydrate) C-l8
Ethylenediamine C-20
Ethylene Glycol C-22
Ethylene Glycol Monobutyl Ether C-24
Fluoroboric Acid (fluoride) C-25
Hydrochloric Acid C-30
Hydrogen Peroxide C-32
Lead C-34
Mai eic Acid C-3 5
Malic Acid C-37
Methanesulfonic Acid C-3 9
Nickel Sulfate C-41
Palladium Chloride C-43
Phosphoric Acid C-45
Potassium Aurocyanide C-47
Potassium Peroxymonosulfate C-49
Propionic Acid C-51
Silver Nitrate C-54
Sodium Hydroxide C-56
Sodium Hypophosphite and Sodium Hypophosphite Monohydrate C-58
Stannous Methanesulfonic Acid C-61
Sulfuric Acid C-63
Thiourea C-65
Tin C-67
Tin Chloride C-68
Urea C-70
References C-72
-------
CHEMICAL SUMMARY FOR 1,3-DIETHYLTHIOUREA
This summary is based on information retrieved from a systematic search limited to secondary sources. The only
exception is summaries of studies from unpublished TSCA submissions that may have been included. These sources
include online databases, unpublished EPA information, government publications, review documents, and standard
reference materials. No attempt has been made to verify information in these databases and secondary sources.
I. CHEMICAL IDENTITY AND PHYSICAL/CHEMICAL PROPERTIES
The chemical identity and physical/chemical properties of 1,3-diethylthiourea are summarized in Table 1.
TABLE 1. CHEMICAL IDENTITY AND CHEMICAL/PHYSICAL PROPERTIES OF 1,3-DIETHYLTHIOUREA
Characteristic/Property
Data
Reference
CAS No.
105-55-5
Lide(1995)
Common Synonyms
N,N-diethylthiourea
Lide(1995)
Molecular Formula
C5H12N2S
Lide(1995)
Chemical Structure
c2h5nhcsnhc2h5
Lewis (1993)
Physical State
buff solid
Lewis (1993)
Molecular Weight
132.32
Lide(1995)
Melting Point
78 °C
Lide(1995)
Boiling Point
decomposes
Lide(1995)
Water Solubility
4.56 g/L
PHYSPROP (1998)
Density
1.11 mg/m3
Ohm (1997)
Vapor Density (air =1)
no data
Koc
49 (estimated)
HSDB (1998)
Log Kow
0.57
PHYSPROP (1998)
Vapor Pressure
0.240 mm Fig at 25 °C (estimated)
PHYSPROP (1998)
Reactivity
no data
Flammability
no data
Flash Point
no data
Dissociation Constant
no data
Molecular Dif&sivity Constant
no data
Air Dif&sivity Constant
no data
Flenry's Law Constant
6.9x10"8 atm m3/mole (estimated)
PHYSPROP (1998)
Fish Bioconcentration Constant
2 (estimated)
HSDB (1998)
Odor Threshold
no data
IL ENVIRONMENTAL FATE
A. Aquatic Fate
If released into aquatic waters, 1,3-diethylthiourea is not expected to adsorb to suspended solids and sediments in
water based upon an estimated Koc of 49 (HSDB, 1998; Swann et al., 1983), determined from a log Kow of 0.57
(Govers et al., 1986, as cited in PHYSPROP, 1998) and a regression-derived equation (Lyman et al., 1990).
Volatilization from the water column to the atmosphere is not expected to occur (Lyman et al., 1990) based on an
estimated Henry's Law constant of 6.9xl0"8 atm-m3/mole (PHYSPROP, 1998; SRC, 1998). Since thiourea, a
structurally similar compound, was found to be stable to hydrolysis and photolysis (Schmidt-Bleek et al., 1982, as
cited in HSDB, 1998), 1,3-diethylthiourea is also expected to be stable to both hydrolysis and photolysis. According
C-l
-------
to a classification scheme (Franke et al., 1994), an estimated BCF of 2 (HSDB, 1998; Lyman et al., 1990) suggests
that the potential for bioconcentration in aquatic organisms is low.
B. Atmospheric Fate
According to a model of gas/particle partitioning of semivolatile organic compounds in the atmosphere (Bidleman,
1988), 1,3-diethylthiourea, which has an estimated vapor pressure of 0.24 mm Hg at 25 ° C (PHYSPROP, 1998;
SRC, 1998), should exist solely as a vapor in the ambient atmosphere. The predominant removal process of 1,3-
diethylthiourea from the atmosphere is reaction with photochemically-produced hydroxyl radicals; the half-life for
this reaction in air is estimated to be 4 hours (Atkinson, 1988). 1,3-diethylthiourea, which has a high estimated water
solubility of 4.56 g/L (PHYSPROP, 1998; SRC, 1998), is expected to adsorb onto atmospheric particulate material;
the small amount of 1,3-diethylthiourea deposited onto particulate material may be physically removed by wet and dry
deposition (HSDB, 1998).
C. Terrestrial Fate
Based on a classification scheme (Swann et al., 1983), an estimated Koc of 49 (HSDB, 1998), determined from a log
Kow of 0.57 (Govers et al., 1986, as cited in PHYSPROP, 1998) and a regression-derived equation (Lyman et al.,
1990), indicates that 1,3-diethylthiourea is expected to have very high mobility in soil. Volatilization of 1,3-
diethylthiourea from moist soil surfaces is not expected to be important (Lyman et al., 1990) given an estimated
Henry's Law constant of 6.9xl0"8 atm-m3/mole (PHYSPROP, 1998). In addition, 1,3-diethylthiourea is not expected
to volatilize from dry soil given its estimated vapor pressure of 0.24 mm Hg (PHYSPROP, 1998; SRC, 1998).
D. Summary
If released to air, an estimated vapor pressure of 0.24 mm Hg at 25 ° C indicates that 1,3-diethylthiourea should exist
solely as a vapor in the ambient atmosphere. Gas-phase 1,3-diethylthiourea will be degraded in the atmosphere by
reaction with photochemically-produced hydroxyl radicals; the half-life for this reaction in air is estimated to be 4
hours. 1,3-Diethylthiourea is not expected to adsorb to suspended solids and sediments in water. An estimated BCF
of 2 suggests the potential for bioconcentration in aquatic organisms is low. If released to soil, 1,3-diethylthiourea is
expected to have very high mobility based upon an estimated Koc of 49, and, therefore, it has the potential to leach to
groundwater. Volatilization from water and from moist soil surfaces is not expected to be an important fate process
based upon a Henry's Law constant of 6.9xl0"8 atm-m3/mole. Volatilization from dry soil surfaces is not expected to
occur based upon the vapor pressure of this compound.
C-2
-------
SUMMARY FOR 1,4-BUTENEDIOL
This summary is based on information retrieved from a systematic search limited to secondary sources. The only
exception is summaries of studies from unpublished TSCA submissions that may have been included. These sources
include online databases, unpublished EPA information, government publications, review documents, and standard
reference materials. No attempt has been made to verify information in these databases and secondary sources.
I. CHEMICAL IDENTITY AND PHYSICAL/CHEMICAL PROPERTIES
The chemical identity and physical/chemical properties of 1,4-butenediol are summarized in Table 1.
TABLE 1. CHEMICAL IDENTITY AND CHEMICAL/PHYSICAL PROPERTIES OF 1,4-BUTENEDIOL
Characteristic/Property
Data
Reference
CAS No.
110-64-5
Grafje et al. (1985)
Common Synonyms
2-butene-l,4-diol (mixed isomers)
Grafje et al. (1985)
Molecular Formula
c4h8o2
Grafje etal. (1985)
Chemical Structure
hoch2ch=chch2oh
Grafje etal. (1985)
Physical State
pale, yellow liquid
Grafje etal. (1985)
Molecular Weight
88.1
Grafje etal. (1985)
Melting Point
4 °C (cis); 25 °C (trans)
Flo ward and Meylan (1997)
Boiling Point
235 °C (cis); 135 °C @ 12 mm Hg (trans)
Flo ward and Meylan (1997)
Water Solubility
soluble; estimated to be >lxl03 g/1
Grafje et al. (1985); SRC (1998)
Density
specific gravity = 1.07 @ 25 °C (liquid)
Weiss (1986)
Vapor Density (air =1)
no data
Koc
8.6 (estimated)
Lyman et al. (1990)
Log Kow
-0.81
Flansch etal. (1995)
Vapor Pressure
4.7x10"3 mm Fig @ 25 °C (extrapolated)
Grafje etal. (1985)
Reactivity
no data
Flammability
not flammable: flash point>100 °F
Cote (1997)
Flash Point
263 °F (Cleveland open cup)
Flick (1991)
Dissociation Constant
no data
Molecular Dif&sivity Constant
no data
Air Dif&sivity Constant
no data
Flenry's Law Constant
1,54xl0"lc atm m3/mole (estimated)
Meylan and Flo ward (1991)
Fish Bioconcentration Constant
0.14 (estimated)
Boethling et al. (1994)
Odor Threshold
no data
IL ENVIRONMENTAL FATE
A. Aquatic Fate
An estimated Koc of 8.6, determined from a log Kow of -0.81 (Hansch et al., 1995) and a regression-derived
equation (Lyman et al., 1990), indicates that 1,4-butenediol is not expected to adsorb to suspended solids and
sediment in water. Also, an estimated Henry's Law constant of 1.54xlO"10 atm m3/mole at 25 °C(Meylanand
Howard, 1991) indicates that 1,4-butenediol is not expected to volatilize from water surfaces (Lyman et al., 1990).
Hydrolysis is not expected to be an important fate process for 1,4-butenediol due to the lack of hydrolyzable
functional groups (Lyman et al., 1990). No data were available in the scientific literature for the biodegradation of
1,4-butenediol in aquatic media under aerobic or anaerobic conditions. However, using a structure estimation
C-3
-------
method (Boethling et al., 1994), aerobic biodegradation is expected to be rapid (days to weeks). According to a
classification scheme (Franke et al., 1994), an estimated BCF of 0.14 (Lyman et al., 1990), obtained from the log
Kow, suggests the potential for bioconcentration of 1,4-butenediol in aquatic organisms is low.
B. Atmospheric Fate
According to a model of gas/particle partitioning of semivolatile organic compounds in the atmosphere (Bidleman,
1988), 1,4-butenediol, which has an extrapolated vapor pressure of 4.7xl0"3 mm Hg at 25 ° C (Grafje et al., 1985), is
expected to exist solely as a gas in the ambient atmosphere. Gas-phase 1,4-butenediol is degraded in the atmosphere
by reaction with photochemically-produced hydroxyl radicals; the half-life for this reaction in air is estimated to be 5-
6 hours, depending upon the isomer (Meylan and Howard, 1993). The half-life for the reaction of 1,4-butenediol
with ozone in the atmosphere is estimated to be 1-2 hours, depending upon the isomer (Meylan and Howard, 1993).
1,4-Butenediol is not expected to directly photolyze in the atmosphere due to the lack of absorption in the
environmental UV spectrum greater than 290 nm (Lyman et al., 1990). Because 1,4-butenediol is miscible with
water, physical removal from the atmosphere by wet deposition may occur.
C. Terrestrial Fate
An estimated Koc of 8.6 (Lyman, 1990), determined from a log Kow of -0.81 (Hansch et al., 1995), indicates that
1,4-butenediol is expected to have very high mobility in soil (Swann et al., 1983). Volatilization of 1,4-butenediol
from moist soil surfaces is not expected to be important (Lyman et al., 1990) given an estimated Henry's Law
constant of 1.54xlO"10 atm nfVmolc (Meylan and Howard, 1991). In addition, an extrapolated vapor pressure of
4.7xl0~3 mm Hg (Grafje et al., 1985) indicates that 1,4-butenediol is not expected to volatilize from dry soil surfaces.
No data were available in the scientific literature for the biodegradation of 1,4-butenediol in soil under aerobic or
anaerobic conditions. However, using a structure estimation method (Boethling et al., 1994), aerobic biodegradation
is expected to be rapid (days to weeks).
D. Summary
1,4-Butenediol exists as a mixture of the cis and trans isomers that are expected to behave similarly in the
environment. If released to air, an extrapolated vapor pressure of 4.7xl0~3 mm Hg at 25 ° C indicates 1,4-butenediol
should exist solely as a gas in the ambient atmosphere. Gas-phase 1,4-butenediol will be degraded in the atmosphere
by reaction with photochemically-produced hydroxyl radicals; the half-life for this reaction in air is estimated to be 5-
6 hours, depending upon the isomer. The gas phase reactions of 1,4-butenediol with photochemically produced
ozone corresponds to a half-life of 1-2 hours. Physical removal of gas-phase 1,4-butenediol from the atmosphere
may also occur via wet deposition processes based on the miscibility of this compound with water. If released to soil,
1,4-butenediol is expected to have very high mobility and is not expected to adsorb to soil surfaces. Volatilization
from water and moist soil surfaces is not expected to be an important fate process based upon an estimated Henry's
Law constant of 1.54xlO"10 atm m3/mole. In addition, volatilization from dry soil surfaces is not expected to occur
based upon the vapor pressure of 1,4-butenediol. Biodegradation data were not available from the scientific
literature; however, a computer model estimates that aerobic biodegradation in both soil and water may occur within
days to weeks. In water, 1,4-butenediol is not expected to bioconcentrate in fish and aquatic organisms based on its
estimated BCF of 0.14.
C-4
-------
CHEMICAL SUMMARY FOR ACETIC ACID
This summary is based on information retrieved from a systematic search limited to secondary sources. The only
exception is summaries of studies from unpublished TSCA submissions that may have been included. These sources
include online databases, unpublished EPA information, government publications, review documents, and standard
reference materials. No attempt has been made to verify information in these databases and secondary sources.
I. CHEMICAL IDENTITY AND PHYSICAL/CHEMICAL PROPERTIES
The chemical identity and physical/chemical properties of acetic acid are summarized in Table 1.
TABLE 1. CHEMICAL IDENTITY AND CHEMICAL/PHYSICAL PROPERTIES OF ACETIC ACID
Characteristic/Property
Data
Reference
CAS No.
64-19-7
Flo ward and Neal (1992)
Common Synonyms
ethanoic acid; vinegar acid
Flo ward and Neal (1992)
Molecular Formula
c2h4o2
Budavari et al. (1996)
Chemical Structure
ch3cooh
Budavari et al. (1996)
Physical State
clear liquid
Budavari et al. (1996)
Molecular Weight
60.05
Budavari et al. (1996)
Melting Point
16.7 °C
Budavari et al. (1996)
Boiling Point
118 °C
Budavari et al. (1996)
Water Solubility
1x10s g/1, 25 °C
U.S. EPA (1981)
Density
d25'25, 1.049
Budavari et al. (1996)
Vapor Density (air =1)
no data
Koc
6.5-228
Sansone et al. (1987)
Log Kow
-0.17
Flansch etal. (1995)
Vapor Pressure
15.7 mm Fig @ 25 °C
Daubert and Danner (1985)
Reactivity
corrosive, particularly when dilute
Weiss (1986)
Flammability
flammable
Budavari et al. (1996)
Flash Point
103 °F (39 °C), closed cup
Budavari et al. (1996)
Dissociation Constant
pKa = 4.76
Serjeant and Dempsey (1979)
Molecular Dif&sivity Constant
no data
Air Diffiisivity Constant
no data
Flenry's Law Constant
1.00x10"' atm m3/mole @ 25 °C
Gaffney et al. (1987)
Fish Bioconcentration Factor
<1 (calculated)
Lyman et al. (1990)
Odor Threshold
no data
IL ENVIRONMENTAL FATE
A. Aquatic Fate
The dominant environmental fate process for acetic acid in water is expected to be biodegradation. A large number of
biological screening studies have determined that acetic acid biodegrades readily under both aerobic (Zahn and
Wellens, 1980; Dore et al., 1975; Price et al., 1974; Placak and Ruchhoft, 1947 as cited in HSDB, 1998) and
anaerobic (Kameya et al., 1995; Mawson et al., 1991; Swindoll et al., 1988 as cited in HSDB, 1998) conditions.
Two aqueous adsorption studies found that acetic acid exists primarily in the water column and not in sediment
(Hemphill and Swanson, 1964; Gordon and Millero, 1985 as cited in HSDB, 1998). In general, organic ions are not
expected to volatilize from water to adsorb to particulate matter in water to the degree that would be predicted for
C-5
-------
their neutral counterparts. Volatilization from the water column to the atmosphere is not expected to occur (Lyman
et al., 1990 as cited in HSDB, 1998) based on a Henry's Law constant of lxlO"9 atm-m3/mole at pH 7 (Gaffney et al.,
1987 as cited in HSDB, 1998). According to a classification scheme (Franke et al., 1994 as cited in HSDB, 1998),
an estimated BCF of <1 (Lyman, 1990 as cited in HSDB, 1998), calculated from a log Kow of -0.17 (Hansch et al.,
1995 as cited in HSDB, 1998), suggests that the potential for bioconcentration in aquatic organisms is low.
B. Atmospheric Fate
According to a model of gas/particle partitioning of semivolatile organic compounds in the atmosphere (Bidleman,
1988 as cited in HSDB, 1998), acetic acid, which has a vapor pressure of 15.7 mm Hg at 25 ° C (Daubert and Danner,
1989 as cited in HSDB, 1998), should exist solely as a gas in the ambient atmosphere. This is consistent with a study
in which over 91% of the total measured acetic acid in an air sample was found to be in the gas phase (Khwaja, 1995
as cited in HSDB, 1998). Acetic acid has been identified as one of the major sources of free acidity in precipitation
from remote regions of the world (Keene and Galloway, 1984 as cited in HSDB, 1998), indicating that physical
removal by wet deposition is an important fate process (Hartmann et al., 1989 as cited in HSDB, 1998). Another
important removal process of acetic acid from the atmosphere is reaction with photochemically-produced hydroxyl
radicals; the half-life for this reaction in air is estimated to be 22 days (Atkinson, 1989 as cited in HSDB, 1998).
Acetic acid has also been detected adsorbed to atmospheric particulate material as the acetate (Gregory et al., 1986;
Khwaja, 1995 as cited in HSDB, 1998); the small amount of acetic acid associated with particulate material may be
physically removed by wet and dry deposition (Grosjean, 1992).
C. Terrestrial Fate
The major environmental fate process for acetic acid in soil is expected to be biodegradation. A large number of
biological screening studies have determined that acetic acid biodegrades readily under both aerobic ,Zahn and
Wellens, 1980; Dore et al., 1975; Price et al., 1974; Placak and Ruchhoft, 1947 as cited in HSDB, 1998) and
anaerobic (Kameya et al., 1995; Mawson et al., 1991; Swindoll et al., 1988 as cited in HSDB, 1998) conditions.
Based on a classification scheme (Swann et al., 1983 as cited in HSDB, 1998), Koc values of 6.5 to 228 (Sansone et
al., 1987 as cited in HSDB, 1998) indicate that acetic acid is expected to have moderate to very high mobility in soil.
This is consistent with a study in which no sorption was reported for three different soils/sediments (Von Oepen et al.,
1991 as cited in HSDB, 1998). Volatilization of acetic acid from moist soil surfaces is not expected to be important
(Lyman et al., 1990, as cited in HSDB, 1998) given a Henry's Law constant of lxlO"9 atm-m3/mole (Gaffney et al.,
1987 as cited in HSDB, 1998) and because acetic acid will exist predominantly as the acetate at environmental pH's.
However, the potential for volatilization of acetic acid from dry soil surfaces may exist based on it's vapor pressure
of 15.7 mm Hg (Daubert and Danner, 1989 as cited in HSDB, 1998). Volatilization will be attenuated depending
upon pH and the amount of acetic acid dissociated.
D. Summary
Acetic acid occurs throughout nature as a normal metabolite of both plants and animals. Consequently, acetic acid's
fate in the environment will, in part, be dependent on its participation in natural cycles. With a pKa of 4.76, acetic
acid and its conjugate base will exist in environmental media in varying proportions that are pH dependent; under
typical environmental conditions (pHs of 5 to 9), acetic acid will exist almost entirely in the ionized (dissociated)
form. If released to air, a vapor pressure of 15.7 mm Hg at 25 ° C indicates that acetic acid should exist solely as a
gas in the ambient atmosphere. Gas-phase acetic acid will be degraded in the atmosphere by reaction with
photochemically-produced hydroxyl radicals; the half-life for this reaction in air is estimated to be 22 days. Physical
removal of vapor-phase acetic acid from the atmosphere may occur via wet deposition processes based on its
miscibility with water. An estimated BCF of <1 suggests the potential for bioconcentration on aquatic organisms is
low. Adsorption studies indicate that acetic acid is not expected to adsorb to suspended solids and sediments in water.
If released to soil, acetic acid is expected to have very high to moderate mobility based upon measured Koc values
ranging from 6.5 to 228 and, therefore, it has the potential to leach to groundwater. If released to soil in high
concentrations, such as those encountered in a spill, acetic acid may travel through soil and reach groundwater.
Volatilization from water and from moist soil surfaces is not expected to be an important fate process based upon a
Henry's Law constant of lxlO"9 atm-m3/mole. Yet, volatilization from dry soil surfaces may occur based upon the
vapor pressure of this compound. However, volatilization of acetic acid will be pH dependent; if acetic acid is
C-6
-------
dissociated, very little (about 1%) will be available for volatilization. Biodegradation is expected to be rapid and may
be the dominant fate process in both soil and water under non-spill conditions; a large number of biological screening
studies have determined that acetic acid biodegrades readily under both aerobic and anaerobic conditions.
C-7
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CHEMICAL SUMMARY FOR BRANCHED OCTYLPHENOL, ETHOXYLATED1
(alkylphenol polyethoxyethanol)
This summary is based on information retrieved from a systematic search limited to secondary sources. The only
exception is summaries of studies from unpublished TSCA submissions that may have been included. These sources
include online databases, unpublished EPA information, government publications, review documents, and standard
reference materials. No attempt has been made to verify information in these databases and secondary sources. The
search identified sources of information for branched octylphenol, ethoxylated.
I. CHEMICAL IDENTITY AND PHYSICAL/CHEMICAL PROPERTIES
The chemical identity and physical/chemical properties of branched octylphenol, ethoxylated1 are summarized in Table
1.
TABLE 1. CHEMICAL IDENTITY AND CHEMICAL/PHYSICAL PROPERTIES OF BRANCHED
OCTYLPHENOL, ETHOXYLATED1
Characteristic/Property
Data
Reference
CAS No.
9036-19-5, 9002-93-1
Floward and Neal (1992)
Common Synonyms
Triton X-1001, OPIOSP
Flo ward and Neal (1992)
Molecular Formula
C14H22O.(C2H4O)100
Floward and Neal (1992)
Chemical Structure
(C8H17)C6H4O(C2H4O)100
Floward and Neal (1992)
Physical State
Clear viscous liquid
MSDS
Molecular Weight
polymer, >4000
Floward and Neal (1992)
Melting Point
7.2°C
MSDS
Boiling Point
271°C
MSDS
Water Solubility
Dispersible, >100 g/L
MSDS
Density
d25, 1.07
MSDS
Vapor Density (air =1)
>1
MSDS
Koc
No data
Log Kow
No data
Vapor Pressure
<0.001 torr
MSDS
Reactivity
No data
Flammability
No data
Flash Point
288°C
MSDS
Dissociation Constant
No data
Molecular Diffusivity Constant
No data
Air Diffusivity Constant
No data
Flenry's Law Constant
No data
Fish Bioconcentration Constant
No data
Odor Threshold
No data
1 The properties are given for TritonXlOO (manufacturer Rohm and Haas).
C-8
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CHEMICAL SUMMARY FOR AMMONIUM CHLORIDE
This summary is based on information retrieved from a systematic search limited to secondary sources. The only
exception is summaries of studies from unpublished TSCA submissions that may have been included. These sources
include online databases, unpublished EPA information, government publications, review documents, and standard
reference materials. No attempt has been made to verify information in these databases and secondary sources.
I. CHEMICAL IDENTITY AND PHYSICAL/CHEMICAL PROPERTIES
The chemical identity and physical/chemical properties of ammonium chloride are summarized in Table 1.
TABLE 1. CHEMICAL IDENTITY AND CHEMICAL/PHYSICAL PROPERTIES OF AMMONIUM CHLORIDE
Characteristic/Property Data Reference
CAS No.
Common Synonyms
Molecular Formula
Chemical Structure
Physical State
Molecular Weight
Melting Point
Boiling Point
Water Solubility
Density
Vapor Density (air =1)
Koc
Log Kow
Vapor Pressure
Reactivity
Flammability
Flash Point
Dissociation Constant
Molecular Dif&sivity Constant
Air Dif&sivity Constant
Flenry's Law Constant
Fish Bioconcentration Constant
Odor Threshold
12125-02-9
Ammonium muriate
C1H4N
NH4C1
colorless cubic crystals
53.492
sublimes at 350°C
no data
approximately 300 g/L1
1.519 g/cm3
no data
no data; expected to be < 10
no data; expected to be < 1
1.84X10"12 mm Fig at 25 °C (extrapolated)
no data
not flammable
not flammable
dissociates to NH4+ and CI"
no data
no data
no data; expected to be < lxlO"8
no data
odorless
CAS (1998)
Budavari et al. (1996)
Budavari et al. (1996)
Budavari et al. (1996)
Lide(1995)
Lide(1995)
Lewis (1993)
Estimated
Lide(1995)
Estimated
Estimated
Daubert and Danner (1992)
Weiss (1986)
Weiss (1986)
Bodek et al. (1988)
Estimated
Weiss (1986)
1 Estimated from a reported solubility of 37 parts in 100 parts water at 20°C (Dean 1985).
IL ENVIRONMENTAL FATE
A.
Aquatic Fate
If ammonium chloride is released into water, it is expected to dissociate into ammonium (NH4+) and chloride (CI )
ions (Bodek et al., 1988). The counter ion associated with the NH4+ will vary depending on the concentration and
type of ions available and the pH in the receiving water. In addition, NH4+ and NH3 (ammonia) are in equilibrium in
the environment and since the pKa of the ammonium ion, NH4+, is 9.26, most ammonia in water is present as the
protonated form rather than as NH3 (Manahan, 1991). Ammonia is, however, present in the equilibrium and will
volatilize to the atmosphere (based upon its Henry's Law constant of 1.6X10"5 atm nfVmolc [Betterton, 1992 as cited
in PHYSPROP, 1998]); the rate of volatilization will increase with increasing pH and, to a lesser degree, temperature
C-9
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(ATSDR, 1990). In the aquatic environment, ammonium can undergo sequential transformation by the nitrification
and denitrification processes of the nitrogen cycle; within this process, ionic nitrogen compounds are formed
(ATSDR, 1990). In addition, ammonium can be taken up by aquatic plants as a source of nutrition, and the uptake of
ammonium by fish has also been documented (ATSDR, 1990). Adsorption of ammonium to sediment should
increase with increasing organic content, increased metal content, and decreasing pH; however, ammonium can be
produced in, and subsequently released from, sediment (ATSDR, 1990). The dissociation of ammonium chloride into
its component ions indicates that ammonium chloride is not expected to bioconcentrate in aquatic organisms.
Ammonium ions may be adsorbed by negatively charged surfaces of sediment in the water column, however
ammonium ions are expected to be replaced by other cations present in natural waters (Evans, 1989). The chloride
ion may complex with heavy metals, thereby increasing their solubility (Bodek et al., 1988). Adsorption of the
chloride ion to suspended solids and sediment in the water column is not expected to be an important fate process.
B. Atmospheric Fate
If ammonium chloride is released to the atmosphere, this compound's low vapor pressure (Daubert and Danner,
1992) indicates it will exist as a particulate in the ambient atmosphere. Ammonium chloride is expected to undergo
wet deposition (ATSDR, 1990) in rain, snow, or fog based upon its high water solubility (Dean, 1985). Dry
deposition of ammonium chloride is expected to be an important fate process in the atmosphere (ATSDR, 1990). The
rate of dry deposition will depend on the prevailing winds and particle size (Bodek et al., 1988). In addition, NH4+
and NH3 (ammonia) are in equilibrium. The gas-phase reactions of ammonia with photochemically produced
hydroxyl radicals has been reported to be 1.6xl0"13 cm3/molc-sec, with a calculated half-life of approximately 100
days; this process contributes approximately 10% to the removal of atmospheric ammonia (ATSDR, 1990).
C. Terrestrial Fate
If ammonium chloride is released to soil, it is expected to dissociate into its component ions in moist soils. As noted
above, NH4+ and NH3 (ammonia) are in equilibrium in the environment and since the pKa of the ammonium ion,
NH4+, is 9.26, most ammonia in water is present as the protonated form rather than as NH3 (Manahan, 1991). The
low vapor pressure and Henry's Law constant expected for an ionic salt indicates that ammonium chloride will not
volatilize from either dry or moist soil surfaces. Nonetheless, ammonia is present in the equilibrium and will
volatilize to the atmosphere (based upon its Henry's Law constant of 1.6X10"5 atm nfVmolc [Betterton, 1992 as cited
in PHYSPROP, 1998]); the rate of volatilization will increase with increasing pH and, to a lesser degree, temperature
(ATSDR, 1990). The mobility of ammonium ions through soil may be attenuated by attraction to negatively charged
surfaces of soil particles, however ammonium ions are expected to be replaced by other cations present in soil (Evans,
1989). In soil, ammonium will serve as a source of nutrient taken up by plants and other organisms and converted to
organic-nitrogen compounds. Ammonium can be converted to nitrate by microbial populations through nitrification;
the nitrate formed will either leach through soil or be taken up by plants and other organisms. It has been determined
that minerals and dry soils can rapidly and effectively adsorb ammonia from air. Chloride is extremely mobile in soils
(Bodek et al., 1988). The chloride ion may complex with heavy metals, thereby increasing their solubility (Bodek et
al., 1988) and potential for leaching into groundwater.
D. Summary
If released into water, ammonium chloride is expected to dissociate into ammonium and chloride ions. The
dissociation of ammonium chloride into its component ions indicates that ammonium chloride is not expected to
bioconcentration in aquatic organisms. Ammonium, however, will be used as a nutrient source by microorganisms
and plants, and rapid uptake is anticipated. Ammonium is in equilibrium with ammonia, but the majority will be in
the ammonium form under most environmental pHs. When present, ammonia's Henry's Law constant indicates that
volatilization from water surfaces may occur. If released to soil, ammonium chloride is expected to dissociate into
its component ions in moist soils and will be used as a nutrient by microorganisms and plants. The dissociation of
ammonium chloride into its component ions in moist soils indicates that volatilization of ammonium from moist soil
surfaces is not expected to occur. The mobility of ammonium ions in soil is expected to be attenuated by cation
exchange processes. The low vapor pressure expected for an ionic salt indicates that ammonium chloride is not
expected to volatilize from dry soil surfaces, however, when ammonia is present in equilibrium, volatilization may
C-10
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occur. If released to the atmosphere, ammonium chloride's low vapor pressure indicates this compound will exist as
a particulate. Wet and dry deposition will be the dominant fate processes in the atmosphere. The rate of dry
deposition will depend on the prevailing wind patterns and particle size. Some atmospheric oxidation may occur.
C-ll
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CHEMICAL SUMMARY FOR AMMONIUM HYDROXIDE
This summary is based on information retrieved from a systematic search limited to secondary sources. The only
exception is summaries of studies from unpublished TSCA submissions that may have been included. These sources
include online databases, unpublished EPA information, government publications, review documents, and standard
reference materials. No attempt has been made to verify information in these databases and secondary sources.
I. CHEMICAL IDENTITY AND PHYSICAL/CHEMICAL PROPERTIES
The chemical identity and physical/chemical properties of ammonium hydroxide are summarized in Table 1.
TABLE 1. CHEMICAL IDENTITY AND CHEMICAL/PHYSICAL PROPERTIES OF AMMONIUM
HYDROXIDE
Characteristic/Property Data Reference
CAS No.
Common Synonyms
Molecular Formula
Chemical Structure
Physical State
Molecular Weight
Melting Point
Boiling Point
Water Solubility
Density
Vapor Density (air =1)
Koc
Log Kow
Vapor Pressure
Reactivity
Flammability
Flash Point
Dissociation Constant
Molecular Diffusivity Constant
Air Diffusivity Constant
Flenry's Law Constant
Fish Bioconcentration Constant
Odor Threshold
1336-21-6
ammonia solution; aqua ammonia; ammonium hydrate
H5NO
nh4oh
colorless liquid
35.05
no data
no data
soluble in water
no data
no data
no data; estimated to be < 10
no data; estimated to be < 1
no data
incompatible w/ HC1, F1N03, Ag compounds
not flammable
no data; estimated to be > 350 °C
9.26 (water solution)
no data
no data
no data1
no data
no data
Lide(1995)
Lewis (1993)
PHYSPROP (1998)
Lide(1995)
Lewis (1993)
Lide(1995)
Sax(1984)
Estimated
Estimated
Sax (1984)
Weiss (1986)
Estimated
Manahan (1991)
1 In the environment, ammonium ion is expected to predominate in the ammonia-ammonium ion equilibrium; however, this equilibrium is
highly dependent on both pFl and temperature (ATSDR, 1990). Ammonia is expected to have a very high Flenry's Law constant, while
ammonium is expected to have a negligible Flenry's Law constant (SRC, 1998).
IL ENVIRONMENTAL FATE
A.
Aquatic Fate
If released into the water column at low concentrations, ammonia or ammonium hydroxide will volatilize to the
atmosphere; the rate of volatilization will increase with increasing pH and, to a lesser degree, temperature (ATSDR,
1990). Since the pKa of the ammonia is 9.26, most ammonia in most environmental waters is present as the
protonated, NH4+, form rather than as NH3 (Manahan, 1991). In the aquatic environment, ammonia can undergo
C-12
-------
sequential transformation by the nitrification and denitrification processes of the nitrogen cycle; within this process,
ionic nitrogen compounds are formed (ATSDR, 1990). In addition, ammonia can be taken up by aquatic plants as a
source of nutrition, and the uptake of ammonia by fish has also been documented (ATSDR, 1990). Adsorption of
ammonia to sediment should increase with increasing organic content, increased metal content, and decreasing pH;
however, ammonia can be produced in, and subsequently released from sediment (ATSDR, 1990). Large releases of
the concentrated base into water, such as may result from a spill, will result in an increase of the pH (ATSDR, 1990).
B. Atmospheric Fate
If ammonia is released to the atmosphere, its vapor pressure indicates it will exist as a vapor in the ambient
atmosphere. If ammonium hydroxide is released to the atmosphere, it is anticipated that the dominant form will be as
a particulate, but during equilibrium between ammonium and ammonia, the ammonia will rapidly leave the particle as
a vapor. The dominant fate process for the removal of ammonia from the atmosphere is the reaction with acid air
pollutants to form ammonium compounds (e.g., ammonium sulfate, ammonium nitrate); these ammonium
compounds can then be removed by wet or dry deposition (ATSDR, 1990). In addition, gas-phase reactions of
ammonia with photochemically produced hydroxyl radicals has been reported to be 1.6xl0"13 cm3/molc-sec, with a
calculated half-life of approximately 100 days; this process contributes approximately 10% to the removal of
atmospheric ammonia (ATSDR, 1990).
C. Terrestrial Fate
If ammonia or ammonium hydroxide is released to soil, it will serve as a source of nutrient taken up by plants and
other organisms and converted to organic-nitrogen compounds. Ammonia can be converted to nitrate by microbial
populations through nitrification; the nitrate formed will either leach through soil or be taken up by plants and other
organisms. It has been determined that minerals and dry soils can rapidly and effectively adsorb ammonia from air.
Specifically, ammonia may be either bound to soil or undergo volatilization to the atmosphere. (ATSDR, 1990)
D. Summary
Ammonia is a base, and as such, the environmental fate of ammonia is pH and temperature dependent. If released into
water, ammonia and ammonium hydroxide will volatilize to the atmosphere, depending on the pH. At high pHs,
where the equilibrium more favors ammonia, volatilization will become increasingly important. At low pHs,
volatilization will be less important. Adsorption of ammonia to sediment and suspended organic material can be
important under proper conditions (i.e., organic matter content, metal content, and pH). In addition, ammonia will be
taken up by aquatic organisms and plants as a source of nutrition. The dominant fate of ammonia in water will be its
participation in the nitrogen cycle. The predominant removal process of ammonia and ammonium hydroxide from the
atmosphere is expected to be wet and dry deposition. To a lesser extent, reactions with photochemically-produced
hydroxyl radicals will occur. If released to soil, ammonia is expected to be taken up by plants and other organisms
and converted to organic-nitrogen compounds. These compounds will either be taken up by plants or other organisms
or leach through the soil. Volatilization of ammonia from soil surfaces is expected to occur.
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CHEMICAL SUMMARY FOR SODIUM CITRATE (citric acid)
This summary is based on information retrieved from a systematic search limited to secondary sources. The only
exception is summaries of studies from unpublished TSCA submissions that may have been included. These sources
include online databases, unpublished EPA information, government publications, review documents, and standard
reference materials. No attempt has been made to verify information in these databases and secondary sources.
I. CHEMICAL IDENTITY AND PHYSICAL/CHEMICAL PROPERTIES
The chemical identity and physical/chemical properties of sodium citrate are summarized in Table 1.
TABLE 1. CHEMICAL IDENTITY AND CHEMICAL/PHYSICAL PROPERTIES OF SODIUM CITRATE
Characteristic/Property
Data
Reference
CAS No.
Common Synonyms
Molecular Formula
Chemical Structure
Physical State
Molecular Weight
Melting Point
Boiling Point
Water Solubility
Density
Vapor Density (air =1)
Koc
Log KqW
Vapor Pressure
Reactivity
Flammability
Flash Point
Dissociation Constant
Flenry's Law Constant
Molecular Diffusivity Coefficient
Air Diffusivity Coefficient
Fish Bioconcentration Factor
Odor Threshold
Conversion Factors
68-04-2
trisodium citrate; sodium citrate anhydrous; 2-hydroxy-1,2,3-
propanetricarboxylic acid, trisodium salt
C6H5Na307
CH2(COONa)C(OH)(COONa)CH2COONa
dihydrate, white crystals, granules, or powder; pentahydrate,
relatively large, colorless crystals or white granules
258.07
150°C (-2 H20)
decomposed at red heat
72 g/100 mL at25°C (dihydrate)
1.9
no data
no data
no data
no data
0 (nonreactive, NFPA classification);
aqueous solution slightly acid to litmus
1 (slightly combustible, NFPA classification);
no data
no data
no data
no data
no data
no data
no data; odorless
no data
Lockheed Martin 1991
Budavari et al. 1989
Osol 1980
Budavari et al. 1989
Budavari et al. 1989
Fisher Scientific 1985
Lewis 1993
Weast 1983-1984
Fisher Scientific 1985
Lockheed Martin 1991
Osol, 1980
Lockheed Martin 1991
Lewis 1993
IL ENVIRONMENTAL FATE
A. Environmental Release
Sodium citrate is a solid with a cool, saline taste that is soluble in water (Fisher Scientific 1985). It is used in soft
drinks, frozen desserts, meat products, cheeses, and as a nutrient for cultured buttermilk; in photography; in
detergents; as a sequestrant and buffer; as an anticoagulant for blood withdrawn from the body; and in the removal of
sulfur dioxide from smelter waste gases (Lewis 1993). Medicinally, sodium citrate is used as expectorant and
C-14
-------
systemic alkalizer. Sodium citrate is a chelating agent and has been used to facilitate elimination of lead from the
body (Osol 1980).
No data were found on the environmental releases of sodium citrate. The chemical is not listed on U.S. EPA's Toxics
Release Inventory, requiring certain U.S. industries to report on chemical releases to the environment (TRI93 1995).
The chemical could potentially enter the environment when used for the removal of sulfur dioxide from smelter waste
gases.
B. Transport
No data were found on the environmental transport of sodium citrate in the secondary sources searched. Its water
solubility suggests that the sodium citrate would remain in the water phase.
C. Transformation/Persistence
No data were found on the transformation/persistence of potassium bisulfate in the secondary sources searched.
C-15
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CHEMICAL SUMMARY FOR CUPRIC SULFATE (copper ion)
This summary is based on information retrieved from a systematic search limited to secondary sources. The only
exception is summaries of studies from unpublished TSCA submissions that may have been included. These sources
include online databases, unpublished EPA information, government publications, review documents, and standard
reference materials. No attempt has been made to verify information in these databases and secondary sources.
I. CHEMICAL IDENTITY AND PHYSICAL/CHEMICAL PROPERTIES
The chemical identity and physical/chemical properties of cupric sulfate are summarized in Table 1.
TABLE 1. CHEMICAL IDENTITY AND CHEMICAL/PHYSICAL PROPERTIES OF CUPRIC SULFATE
Characteristic/Property
Data
Reference
CAS No.
7758-99-8
Lide(1995)
Common Synonyms
cupric sulfate pentahydrate; blue Vitriol
Budavari et al. (1996)
Molecular Formula
Cu04S-5H20
ATSDR (1990)
Chemical Structure
CuS04-5H20
Lide(1995)
Physical State
large, blue, triclinic crystals; blue powder
Budavari et al. (1996)
Molecular Weight
249.68
Lide(1995)
Melting Point
decomposes @ 110°C
Lide(1995)
Boiling Point
decomposes to CuO @ 650°C
ATSDR (1990)
Water Solubility
316 g/L @ 0°C
Weast et al. (1985)
Density
2.286 g/cm3
Lide(1995)
Vapor Density (air =1)
no data
Koc
no data
Log Kow
no data
Vapor Pressure
no data
Reactivity
reacts with Mg to produce Cu20, MgS04, and Fl2
U.S. Air Force (1990)
Reactivity
reacts with NF^Cl producing (NF[4)2SC>4 and CuCl2;
reacts with alkali (R)OFl to produce Cu(OF1)2 and
RS04; reacts with excess aq. NH3 producing
Cu(NH3)22+ + OFT;decomposition products include
so2.
F1SDB (1998)
Flammability
non-flammable
F1SDB (1998)
Flash Point
non-flammable
F1SDB (1998)
Dissociation Constant
no data
Molecular Dif&sivity Constant
no data
Air Dif&sivity Constant
no data
Flenry's Law Constant
no data
Fish Bioconcentration Constant
10-100 for copper; 30,000 for copper in oysters
ATSDR (1990)
Odor Threshold no data
IL ENVIRONMENTAL FATE
A. Aquatic Fate
Copper (Cu) commonly exists in three valence states, Cu° (metal), Cu+ (cuprous), and Cu2+ (cupric). It can also be
oxidized to a Cu3+ state, but Cu3+ ions are rapidly reduced to Cu2+ in the environment (ATSDR, 1990). Copper in
solution is present almost exclusively as the Cu2+ valence state (U.S. EPA, 1987). Copper in the Cu2+ valence state
C-16
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forms compounds and complexes with a variety of organic and inorganic ligands binding to -NH2, -SH, and, to a
lesser extent, -OH groups (ATSDR, 1990). The predominant form of copper in aqueous solution is dependent on the
pH of the solution. Below pH 6, the cupric ion (Cu2+) predominates; copper complexes with carbonate usually
predominate above pH 6 (U.S. EPA, 1987; ATSDR, 1990). The association of copper with organic or inorganic
ligands also depends on the pH and on the CaC03 alkalinity. Most of the copper entering surface water is in the form
of particulate matter, which settles out, precipitates, or adsorbs to organic matter, hydrous iron and manganese oxides,
and clay; however, the predominating form can change with the amount of rain, pH, content of runoff, and the
availability of ligands (ATSDR, 1990). The processes of complexation, adsorption and precipitation limit the
concentration of copper (Cu2+) to very low values in most natural waters (ATSDR, 1990). Calculations of the
bioconcentration factor in fish for copper have ranged from 10 to 100; however, the majority of copper
measurements in fish tissues under environmental conditions have indicated little, if any, bioconcentration. Filter
feeding shellfish, especially oysters, however, were found to significantly concentrate copper with bioconcentration
factors as high as 30,000 (ATSDR, 1990).
B. Atmospheric Fate
Most of the copper in the air is in the form of particulate matter (dust) or is adsorbed to particulate matter. Larger
particles (>5 |im) are removed by gravitational settling, smaller particles are removed by other forms of dry and wet
deposition (ATSDR, 1990). Atmospheric copper resulting from combustion is associated with sub-micron particles
that can remain in the troposphere for an estimated 7-30 days and may be carried long distances (ATSDR, 1990).
C. Terrestrial Fate
Most of the copper deposited in the soil is strongly adsorbed primarily to organic matter, carbonate minerals, clay
minerals, and hydrous iron and manganese oxides. Movement through the soil is dependent on the presence of these
substances, the pH, and other physical and chemical parameters. The greatest potential for leaching is seen in sandy
soils with low pH (ATSDR, 1990). Laboratory experiments using controlled models and field experiments utilizing
core samples have shown that very little copper moves through the soil. Core samples showed that some movement
occurred as far as the 22.5-25 cm layer of soil, but little, if any, moved below this zone. The evidence indicates that
hazardous amounts of copper should not leach into groundwater from sludge, even from sandy soils (ATSDR, 1990).
D. Summary
Copper (Cu) commonly exists in three valence states, Cu° (metal), Cu+ (cuprous), and Cu2+ (cupric). It can also be
oxidized to a Cu3+ state, but there are no important industrial Cu3+ chemicals, and Cu3+ ions are rapidly reduced to
Cu2+ in the environment. If released to water, copper in solution will be present almost exclusively as the Cu2+
valence state. The predominant form of copper in aqueous solution is dependent on the pH of the solution. Most of
the copper entering surface water is in the form of particulate matter; however, the predominating form can change
with the amount of rain, pH, content of runoff, and the availability of ligands. Copper in the Cu2+ valence state will
form compounds and complexes with a variety of organic and inorganic ligands. Calculations of the bioconcentration
factor in fish for copper have ranged from 10 to 100; however, the majority of copper measurements in fish tissues
under environmental conditions have indicated little, if any, bioconcentration. If released to soil, the majority of
copper deposited in the soil is strongly adsorbed. Movement through the soil is dependent on the presence of organic
matter, carbonate minerals, clay minerals, hydrous iron and manganese oxides, the pH, and other physical and
chemical parameters. The greatest potential for leaching is seen in sandy soils with low pH. If released into the
atmosphere, copper is expected to exist as a dust particulate or adsorb to particulate matter. Studies have shown that
copper can remain in the atmosphere up to 30 days and be carried long distances.
C-17
-------
CHEMICAL SUMMARY FOR CUPRIC ACETATE (copper sulfate pentahydrate)
This summary is based on information retrieved from a systematic search limited to secondary sources. The only
exception is summaries of studies from unpublished TSCA submissions that may have been included. These sources
include online databases, unpublished EPA information, government publications, review documents, and standard
reference materials. No attempt has been made to verify information in these databases and secondary sources.
I. CHEMICAL IDENTITY AND PHYSICAL/CHEMICAL PROPERTIES
The chemical identity and physical/chemical properties of cupric acetate are summarized in Table 1.
TABLE 1. CHEMICAL IDENTITY AND CHEMICAL/PHYSICAL PROPERTIES OF COPPER ACETATE
Characteristic/Property
Data
Reference
CAS No.
6046-93-1
Lide(1995)
Common Synonyms
copper (II) acetate monohydrate
Lide(1995)
Molecular Formula
(CH3C02)2CuH20
Aldrich (1996)
Chemical Structure
Cu(C2H302 )2 h2o
Lide(1995)
Physical State
dark, green monoclinic crystals
Budavari et al. (1996)
Physical State
greenish-blue, fine powder
Lewis (1993)
Molecular Weight
199.65
Lide(1995)
Melting Point
115 °C
Lide(1995)
Boiling Point
decomposes at 240 °C
Lide(1995)
Water Solubility
72 g/L cold water; 200 g/L hot water
Weastet al. (1985)
Density
1.88 g/cm3
Lide(1995)
Vapor Density (air =1)
no data
Koc
no data
Log Kow
no data
Vapor Pressure
no data
Reactivity
stable
Weiss (1986)
Flammability
not flammable
Weiss (1986)
Flash Point
not flammable
Weiss (1986)
Dissociation Constant
no data
Molecular Dif&sivity Constant
no data
Air Dif&sivity Constant
no data
Flenry's Law Constant
no data
Fish Bioconcentration Constant
10-100 for copper; 30,000 for copper in oysters
ATSDR (1990)
Odor Threshold
no data
IL ENVIRONMENTAL FATE
A. Aquatic Fate
Copper (Cu) commonly exists in three valence states, Cu° (metal), Cu+ (cuprous), and Cu2+ (cupric). It can also be
oxidized to a Cu3+ state, but Cu3+ ions are rapidly reduced to Cu2+ in the environment (ATSDR, 1990). Copper in
solution is present almost exclusively as the Cu2+ valence state (U.S. EPA, 1987). Copper in the Cu2+ valence state
forms compounds and complexes with a variety of organic and inorganic ligands binding to -NH2, -SH, and, to a
lesser extent, -OH groups (ATSDR, 1990). The predominant form of copper in aqueous solution is dependent on the
pH of the solution. Below pH 6, the cupric ion (Cu2+) predominates; copper complexes with carbonate usually
C-18
-------
predominate above pH 6 (U.S. EPA, 1987; ATSDR, 1990). The association of copper with organic or inorganic
ligands also depends on the pH and on the CaC03 alkalinity. Most of the copper entering surface water is in the form
of particulate matter, which settles out, precipitates, or adsorbs to organic matter, hydrous iron and manganese oxides,
and clay; however, the predominating form can change with the amount of rain, pH, content of runoff, and the
availability of ligands (ATSDR, 1990). The processes of complexation, adsorption and precipitation limit the
concentration of copper (Cu2+) to very low values in most natural waters (ATSDR, 1990). Calculations of the
bioconcentration factor in fish for copper have ranged from 10 to 100; however, the majority of copper
measurements in fish tissues under environmental conditions have indicated little, if any, bioconcentration. Filter
feeding shellfish, especially oysters, however, were found to significantly concentrate copper with bioconcentration
factors as high as 30,000 (ATSDR, 1990).
B. Atmospheric Fate
Most of the copper in the air is in the form of particulate matter (dust) or is adsorbed to particulate matter. Larger
particles (>5 |im) are removed by gravitational settling, smaller particles are removed by other forms of dry and wet
deposition (ATSDR, 1990). Atmospheric copper resulting from combustion is associated with sub-micron particles
that can remain in the troposphere for an estimated 7-30 days and may be carried long distances (ATSDR, 1990).
C. Terrestrial Fate
Most of the copper deposited in the soil is strongly adsorbed primarily to organic matter, carbonate minerals, clay
minerals, and hydrous iron and manganese oxides. Movement through the soil is dependent on the presence of these
substances, the pH, and other physical and chemical parameters. The greatest potential for leaching is seen in sandy
soils with low pH (ATSDR, 1990). Laboratory experiments using controlled models and field experiments utilizing
core samples have shown that very little copper moves through the soil. Core samples showed that some movement
occurred as far as the 22.5-25 cm layer of soil, but little, if any, moved below this zone. The evidence indicates that
hazardous amounts of copper should not leach into groundwater from sludge, even from sandy soils (ATSDR, 1990).
D. Summary
Copper (Cu) commonly exists in three valence states, Cu° (metal), Cu+ (cuprous), and Cu2+ (cupric). It can also be
oxidized to a Cu3+ state, but there are no important industrial Cu3+ chemicals, and Cu3+ ions are rapidly reduced to
Cu2+ in the environment. If released to water, copper in solution will be present almost exclusively as the Cu2+
valence state. The predominant form of copper in aqueous solution is dependent on the pH of the solution. Most of
the copper entering surface water is in the form of particulate matter; however, the predominating form can change
with the amount of rain, pH, content of runoff, and the availability of ligands. Copper in the Cu2+ valence state will
form compounds and complexes with a variety of organic and inorganic ligands. Calculations of the bioconcentration
factor in fish for copper have ranged from 10 to 100; however, the majority of copper measurements in fish tissues
under environmental conditions have indicated little, if any, bioconcentration. If released to soil, the majority of
copper deposited in the soil is strongly adsorbed. Movement through the soil is dependent on the presence of organic
matter, carbonate minerals, clay minerals, hydrous iron and manganese oxides, the pH, and other physical and
chemical parameters. The greatest potential for leaching is seen in sandy soils with low pH. If released into the
atmosphere, copper is expected to exist as a dust particulate or adsorb to particulate matter. Studies have shown that
copper can remain in the atmosphere up to 30 days and be carried long distances.
C-19
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CHEMICAL SUMMARY FOR ETHYLENEDIAMINE
This summary is based on information retrieved from a systematic search limited to secondary sources. The only
exception is summaries of studies from unpublished TSCA submissions that may have been included. These sources
include online databases, unpublished EPA information, government publications, review documents, and standard
reference materials. No attempt has been made to verify information in these databases and secondary sources.
I. CHEMICAL IDENTITY AND PHYSICAL/CHEMICAL PROPERTIES
The chemical identity and physical/chemical properties of ethylene diamine are summarized in Table 1.
TABLE 1. CHEMICAL IDENTITY AND CHEMICAL/PHYSICAL PROPERTIES OF ETHYLENE DIAMINE
Characteristic/Property
Data
Reference
CAS No.
107-15-3
Flo ward and Neal (1992)
Common Synonyms
1,2-diamineethane; 1,2-ethanediamine
Budavari et al. (1996)
Molecular Formula
c2h8n2
Budavari et al. (1996)
Chemical Structure
h2nch2ch2nh2
Budavari et al. (1996)
Physical State
colorless, clear, thick, liquid
Budavari et al. (1996)
Molecular Weight
60.10
Budavari et al. (1996)
Melting Point
8.5 °C
Budavari et al. (1996)
Boiling Point
116-117 °C
Budavari et al. (1996)
Water Solubility
1x10s g/1 @ 25 °C
Riddick et al. (1986)
Density
d25'4, 0.898
Budavari et al. (1996)
Vapor Density (air =1)
no data
Koc
2 (calculated)
Lyman etal. (1990)
Log Kow
-2.04
Flansch etal. (1995)
Vapor Pressure
12.0 mm Fig @ 25 °C
Boublik et al. (1984)
Reactivity
volatile w/ steam; absorbs C02 from air
Budavari et al. (1996)
Flammability
flammable
Aldrich (1997)
Flash Point
110 °F(43 °C), closed cup
Budavari et al. (1996)
Dissociation Constant
pKaj = 9.92; pKa2 = 6.86
Perrin (1972)
Molecular Dif&sivity Constant
no data
Air Dif&sivity Constant
no data
Flenry's Law Constant
1.73x10"' atm m3/mole @ 25 °C
Fline and Mookerjee (1975)
Fish Bioconcentration Factor
0.02 (calculated)
Lyman etal. (1990)
Odor Threshold
100% recognizable @11.2 ppm
Verschueren (1996)
IL ENVIRONMENTAL FATE
A Aquatic Fate
The dominant environmental fate process for ethylenediamine in surface water is expected to be biodegradation. A
number of biological screening studies have determined that ethylenediamine biodegrades readily under aerobic
conditions (Price et al., 1974; Takemoto et al., 1981; Pitter, 1976 ; Mills and Stack, 1955, as cited in HSDB, 1998).
No data were available for the biodegradation of ethylenediamine under anaerobic conditions. An estimated Koc
value of 2, determined from an experimental log Kow of -2.04 (Hansch et al., 1995) and a regression-derived
equation (Lyman et al., 1990), indicates that ethylenediamine is not expected to adsorb to suspended solids and
sediment in water. In general, organic ions are not expected to volatilize from water or adsorb to particulate matter in
water to the degree that would be predicted for their neutral counterparts. Based on an estimated BCF of 0.02
C-20
-------
(Lyman et al., 1990) calculated from the log Kow, a classification scheme (Franke et al., 1994) suggests the potential
forbioconcentration in aquatic organisms is low. Ethylenediamine is not expected to volatilize from water surfaces
(Lyman et al., 1990) based upon an experimental Henry's Law constant of 1.73xl0"9 atm-m3/mole (Hine and
Mookeijee, 1975). However, volatilization of ethylenediamine will be pH dependent and attenuated if it is
protonated; very little, about 1%, will be available for volatilization. Hydrolysis of ethylenediamine is not expected
to occur due to the lack of hydrolyzable functional groups (Lyman et al., 1990).
B. Atmospheric Fate
According to a model of gas/particle partitioning of semivolatile organic compounds in the atmosphere (Bidleman,
1988), ethylenediamine, which has a vapor pressure of 12 mm Hg at 25 ° C (Boublik et al, 1984), should exist solely
as a gas in the ambient atmosphere. Gas-phase ethylenediamine is degraded in the atmosphere by reaction with
photochemically-produced hydroxyl radicals; the half-life for this reaction in air is estimated to be 6 hours (Meylan
and Howard, 1993). Due to its miscibility with water, ethylenediamine may also be removed physically from the
atmosphere by wet deposition. Ethylenediamine is not expected to directly photolyze in the atmosphere due to the
lack of absorption in the environmental UV spectrum (>290 nm) (Lyman et al., 1990).
C. Terrestrial Fate
The major environmental fate process for ethylenediamine in aerobic soils is expected to be biodegradation. A
number of biological screening studies have determined that ethylenediamine biodegrades readily under aerobic
conditions (Price et al., 1974; Takemoto et al., 1981; Pitter, 1976 ; Mills and Stack, 1955, as cited in HSDB, 1998).
No data on the biodegradation of ethylenediamine under anaerobic conditions were located in the available literature.
An estimated Koc value of 2 (Lyman et al., 1990), determined from an experimental log Kow of -2.04 (Hansch et al.,
1995), indicates that ethylenediamine is expected to have very high mobility in soil (Swann et al., 1983).
Volatilization of ethylenediamine from moist soil surfaces is not expected to be important (Lyman et al., 1990) given
an experimental Henry's Law constant of 1.73xl0"9 atm-m3/mole (Hine and Mookeijee, 1975), although it may
volatilize from dry soil surfaces based upon a vapor pressure of 12 mm Hg (Boublik et al., 1984). However, at
environmental pH's of 5-7, ethylenediamine will most likely be a salt and volatilization will be attenuated.
D. Summary
The dominant removal mechanisms of ethylenediamine from the environment are expected to be biodegradation on
the earth's surface and reaction with photochemically-produced hydroxyl radicals in the atmosphere. In both soil and
water, biodegradation is expected to be rapid; a large number of biological screening studies have determined that
ethylenediamine biodegrades readily under aerobic conditions. If released to air, a vapor pressure of 12 mm Hg
indicates ethylenediamine should exist solely as a gas in the ambient atmosphere. Gas-phase ethylenediamine will be
degraded in the atmosphere by reaction with photochemically-produced hydroxyl radicals; the half-life for this
reaction in air is estimated to be 6 hours. Physical removal of gas-phase ethylenediamine from the atmosphere may
also occur via wet deposition processes based on the miscibility of this compound with water. With a pKa, of 9.92,
ethylenediamine and its conjugate acid will exist in environmental media in varying proportions that are pH
dependent. If released to soil, ethylenediamine may display very high mobility based upon an estimated Koc of 2. If
released to soil in high concentrations, such as those encountered in a spill, ethylenediamine may travel through soil
and reach groundwater. Volatilization of ethylenediamine from water and moist soil surfaces is not expected to be an
important fate process based upon a Henry's Law constant of 1.73xl0"9 atm-m3/mole, although its vapor pressure
indicates that volatilization from dry soil surfaces may occur. However, at environmental pH's of 5-7,
ethylenediamine will most likely be a salt and volatilization will be attenuated. In water, ethylenediamine is not
expected to bioconcentrate in fish and aquatic organisms based on an estimated BCF of 0.02.
C-21
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CHEMICAL SUMMARY FOR ETHYLENE GLYCOL
This summary is based on information retrieved from a systematic search limited to secondary sources. The only
exception is summaries of studies from unpublished TSCA submissions that may have been included. These sources
include online databases, unpublished EPA information, government publications, review documents, and standard
reference materials. No attempt has been made to verify information in these databases and secondary sources.
I. CHEMICAL IDENTITY AND PHYSICAL/CHEMICAL PROPERTIES
The chemical identity and physical/chemical properties of ethylene glycol are summarized in Table 1.
TABLE 1. CHEMICAL IDENTITY AND CHEMICAL/PHYSICAL PROPERTIES OF ETHYLENE GLYCOL
Characteristic/Property
Data
Reference
CAS No.
107-21-1
Budavari et al. (1996)
Common Synonyms
1,2-ethanediol
Budavari et al. (1996)
Molecular Formula
c2h6o2
Budavari et al. (1996)
Chemical Structure
hoch2ch2oh
Budavari et al. (1996)
Physical State
slightly viscous liquid
Budavari et al. (1996)
Molecular Weight
62.07
Budavari et al. (1996)
Melting Point
-13 °C
Budavari et al. (1996)
Boiling Point
197.6 °C
Budavari et al. (1996)
Water Solubility
miscible (1,000 g/1)
Riddick et al (1986)
Density
1.11 g/cm3
Budavari et al. (1996)
Vapor Density (air =1)
2.1
Verschueren (1996)
Koc
4 (estimated)
SRC (1998)
Log Kow
-1.36
Flansch et al. (1995), as cited in F1SDB
(1998)
Vapor Pressure
0.092 mm Fig
Daubert and Danner (1989)
Reactivity
no data
no data
Flammability
combustible
Lewis (1993)
Flash Point
240 °F (115 °C)
Budavari et al. (1996)
Dissociation Constant
15.1
Flo ward and Meylan (1997)
Molecular Dif&sivity Constant
no data
Air Dif&sivity Constant
no data
Flenry's Law Constant
6.0x10"8 atm m3/mol
Flo ward and Meylan (1997)
Fish Bioconcentration Constant
10
HSDB (1998)
Odor Threshold
25 ppm
ECDIN (1998)
IL ENVIRONMENTAL FATE
A. Aquatic Fate
The dominant environmental fate process for ethylene glycol in water is expected to be biodegradation. A large
number of biological screening studies have determined that ethylene glycol biodegrades readily under both aerobic
and anaerobic conditions (Bridie et al. 1979; Pitter 1976; and Price et al. 1974, as cited in HSDB, 1998). Aerobic
degradation is essentially complete in <1-4 days, although 100% theoretical biological oxygen demand may not be
realized for several weeks (Bridie et al., 1979; Pitter 1976; and Price et al., 1974, as cited in HSDB, 1998).
Ethylene glycol is not expected to adsorb to suspended solids and sediments in water based upon an estimated Koc of
4 (Swann et al., 1983, as cited in HSDB, 1998), determined from a log Kow of -1.36 (Hansch et al., 1995, as cited in
C-22
-------
HSDB, 1998) and a regression-derived equation (Lyman et al., 1990, as cited in HSDB, 1998). Volatilization from
the water column to the atmosphere is not expected to occur (Lyman et al., 1990, as cited in HSDB, 1998) based on a
Henry's Law constant of 6.0xl0"8 atm-m3/mole (Butler and Ramchandani 1935, as cited in Howard and Meylan
1997). Ethylene glycol is expected to be stable to hydrolysis in the pH range of 5-9 typically encountered in the
environment (Lyman et al., 1990, as cited in HSDB, 1998). According to a classification scheme (Franke et al.,
1994), a BCF of 10 in golden ide fish (Freitag et al., 1985, as cited in HSDB, 1998) suggests that the potential for
bioconcentration in aquatic organisms is low.
B. Atmospheric Fate
According to a model of gas/particle partitioning of semivolatile organic compounds in the atmosphere (Bidleman
1989, as cited in HSDB, 1998), ethylene glycol, which has a vapor pressure of 0.092 mm Hg at 25 ° C (Daubert and
Danner 1989), should exist solely as a gas in the ambient atmosphere. Nonetheless, ethylene glycol has been detected
adsorbed onto atmospheric particulate material (Abdelghani et al., 1990, as cited in HSDB, 1998); the small amount
of ethylene glycol deposited onto particulate material may be physically removed by wet and dry deposition. The
predominant removal process of ethylene glycol from the atmosphere is reaction with photochemically-produced
hydroxyl radicals; the half-life for this reaction in air is estimated to be 50 hours (Atkinson 1989, as cited in HSDB,
1998). Ethylene glycol may undergo some degradation by direct photolysis; 12.1% of applied ethylene glycol was
degraded after 17 hours following irradiation by light > 290 nm (Freitag et al., 1985, as cited in HSDB, 1998).
C. Terrestrial Fate
The major environmental fate process for ethylene glycol in soil is expected to be biodegradation. A large number of
biological screening studies have determined that ethylene glycol biodegrades readily under both aerobic and
anaerobic conditions; complete biodegradation was shown in one soil within 2 days and 97% biodegradation in 12
days was reported for a second soil (McGahey and Bower 1992, as cited in HSDB, 1998). Based on a classification
scheme (Swann et al., 1983, as cited in HSDB, 1998), an estimated Koc of 4, determined from a log Kow of -1.36
(Hansch et al., 1995, as cited in HSDB, 1998) and a regression-derived equation (Lyman, 1990 et al., as cited in
HSDB, 1998), indicates that ethylene glycol is expected to have very high mobility in soil. Percent adsorption to 4
soils (2 clay and 2 sandy clay soils) ranged from 0-0.5% (Abdelghani et al 1990, as cited in HSDB, 1998).
Volatilization of ethylene glycol from moist soil surfaces is not expected to be important (Lyman et al., 1990, as cited
in HSDB, 1998) given a Henry's Law constant of 6.0xl0"8 atm-m3/mole (Butler and Ramchandani 1935, as cited in
Howard and Meylan 1997). Ethylene glycol may volatilize from dry soil given its vapor pressure of 0.092 mm Hg
(Daubert and Danner, 1989); this may be attenuated by hydrogen bonding to soil materials (SRC, 1998).
D. Summary
If released to air, a vapor pressure of 0.092 mm Hg at 25 ° C indicates that ethylene glycol should exist solely as a gas
in the ambient atmosphere; however, experimental results show that at least some ethylene glycol is associated with
atmospheric particulates. Gas-phase ethylene glycol will be degraded in the atmosphere by reaction with
photochemically-produced hydroxyl radicals; the half-life for this reaction in air is estimated to be 50 hours.
Adsorption studies indicate that ethylene glycol is not expected to adsorb to suspended solids and sediments in water.
A BCF of 10 in golden ide fish suggests the potential for bioconcentration in aquatic organisms is low. If released to
soil, ethylene glycol is expected to have very high mobility based upon an estimated Koc of 4, and, therefore, it has the
potential to leach to groundwater. Volatilization from water and from moist soil surfaces is not expected to be an
important fate process based upon a Henry's Law constant of 6.0xl0"8 atm-m3/mole. Volatilization from dry soil
surfaces may occur based upon the vapor pressure of this compound, although this may be attenuated by hydrogen
bonding to soil materials. Biodegradation is expected to be rapid and may be the dominant fate process in both soil
and water under non-spill conditions; a large number of biological screening studies have determined that ethylene
glycol biodegrades readily under both aerobic and anaerobic conditions.
C-23
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CHEMICAL SUMMARY FOR ETHYLENE GLYCOL MONOBUTYL ETHER
This summary is based on information retrieved from a systematic search limited to secondary sources. The only
exception is summaries of studies from unpublished TSCA submissions that may have been included. These sources
include online databases, unpublished EPA information, government publications, review documents, and standard
reference materials. No attempt has been made to verify information in these databases and secondary sources. The
search identified sources of information for ethylene glycol monobutyl ether.
I. CHEMICAL IDENTITY AND PHYSICAL/CHEMICAL PROPERTIES
The chemical identity and physical/chemical properties of ethylene glycol monobutyl ether are summarized in Table 1.
TABLE 1. CHEMICAL IDENTITY AND CHEMICAL/PHYSICAL PROPERTIES OF ETHYLENE GLYCOL
MONOBUTYL ETHER
Characteristic/Property Data Reference
CAS No.
Common Synonyms
Molecular Formula
Chemical Structure
Physical State
Molecular Weight
Melting Point
Boiling Point
Water Solubility
Density
Vapor Density (air =1)
Koc
Log Kow
Vapor Pressure
Reactivity
Flammability
Flash Point
Dissociation Constant
Molecular Diffusivity Constant
Air Diffusivity Constant
Flenry's Law Constant
Fish Bioconcentration Constant
Odor Threshold
111-76-2
BUCS, butoxyethanol, Dowanol EB
C6H1402
CH3(CH2)30CH2CH20H
Clear, colorless liquid
118.18
-70°C
171°C, 743 mm Hg
>1000 g/L, 25°C
d20'20, 0.9012
4.07
1
0.83
0.88 mm Hg @ 25°C
Inert
Combustible
60°C
No data
No data
No data
2.08x10"8 atm m3/mol
No data
No data
Floward and Neal (1992)
Floward and Neal (1992)
Floward and Neal (1992)
Floward and Neal (1992)
F1SDB (1998)
Floward and Neal (1992)
Budavari etal. (1996)
Budavari etal. (1996)
F1SDB (1998)
F1SDB (1998)
F1SDB (1998)
EPI
Floward and Meylan (1997)
Floward and Meylan (1997)
Sax and Lewis (1987)
Sax and Lewis (1987)
F1SDB (1998)
Floward and Meylan (1997)
C-24
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CHEMICAL SUMMARY FOR FLUOROBORIC ACID (fluoride)
This chemical was identified by one or more suppliers as a bath ingredient for the electroless copper and tin-palladium
processes. This summary is based on information retrieved from a systematic search limited to secondary sources.
The only exception is summaries of studies from unpublished TSCA submissions that may have been included. These
sources include online databases, unpublished EPA information, government publications, review documents, and
standard reference materials. No attempt has been made to verify information in these databases and secondary
sources. Very little information on the environmental fate and toxicity of fluoroboric acid or fluoroborates was
found in the available secondary sources. Supplemental information is provided for fluoride which may be a
degradation product and for sodium bifluoride.
I. CHEMICAL IDENTITY AND PHYSICAL/CHEMICAL PROPERTIES
The chemical identity and physical/chemical properties of fluoroboric acid are summarized in Table 1.
TABLE 1. CHEMICAL IDENTITY AND CHEMICAL/PHYSICAL PROPERTIES OF FLUOROBORIC ACID
Characteristic/Property
Data
Reference
CAS No.
Common Synonyms
Molecular Formula
Chemical Structure
Physical State
Molecular Weight
Melting Point
Boiling Point
Water Solubility
Density
Koc
Log KqW
Vapor Pressure
Vapor Density
Reactivity
Flammability
Flash Point
Dissociation Constant (-pK)
Flenry's Law Constant
Molecular Diffiisivity Coefficient
Air Diffusivity Coefficient
Fish Bioconcentration Factor
Odor Threshold
Conversion Factors
16872-11-0
hydrogen tetrafluoroborate
fluoboric acid
hydrofluoroboric acid
HBF4
b-f4-h
colorless liquid
87.82
-90 °C
130°C (decomposes)
miscible;
sol. in hot water
-1.84 g/mL
NA
NA
5.1 mm Fig at 20 ° C
3.0
strong acid; corrosive
NA
NA
-4.9
NA
NA
NA
NA
NA
Na
F1SDB (1995)
F1SDB (1995)
F1SDB (1995)
Fisher Scientific (1993)
F1SDB (1995)
F1SDB (1995)
Fisher Scientific (1993)
F1SDB (1995)
F1SDB (1995)
F1SDB (1995)
Fisher Scientific (1993)
Fisher Scientific (1993)
F1SDB (1995)
F1SDB (1995)
The chemical identity and physical/chemical properties of sodium tetrafluoroborate are summarized in Table 2.
C-25
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TABLE 2. CHEMICAL IDENTITY AND CHEMICAL/PHYSICAL PROPERTIES OF SODIUM
TETRAFLUOROBORATE
Characteristic/Property
Data
Reference
CAS No.
Common Synonyms
Molecular Formula
Chemical Structure
Physical State
Molecular Weight
Melting Point
Boiling Point
Water Solubility
Density
Koc
Log KqW
Vapor Pressure
Reactivity
Flammability
Flash Point
Dissociation Constant (-pK)
Flenry's Law Constant
Molecular Diffusivity Coefficient
Air Diffusivity Coefficient
Fish Bioconcentration Factor
Odor Threshold
Conversion Factors
013755-29-8
sodium fluoroborate
STB
sodium borfluoride
sodium boron tetrafluoride
NaNF„
Na-F„-B
white crystalline powder
109.82
384°C
108 g/100 mL at 26 ° C
210 g/100 mL at 100 °C
2.470
NA
NA
NA
reacts with strong oxidizing
agents; sensitive to moisture
noncombustible
NA
NA
NA
NA
NA
NA
Lockheed Martin (1994)
Lockheed Martin (1994)
Sigma-Aldrich (1992)
Budavari et al. (1989)
Budavari et al. (1989)
Budavari et al. (1989)
Sigma-Aldrich (1992)
Sigma-Aldrich (1992)
Lockheed Martin (1994)
The chemical identity and physical/chemical properties of sodium fluoride are summarized in Table 3.
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TABLE 3. CHEMICAL IDENTITY AND CHEMICAL/PHYSICAL PROPERTIES OF SODIUM FLUORIDE
Characteristic/Property
Data
Reference
CAS No.
7681-49-4
Common Synonyms
sodium hydrofluoride
sodium monfluoride
floridine
Molecular Formula
NaF
Chemical Structure
Na-F
Physical State
crystals
Budavari et al. (1989)
Molecular Weight
42.00
Budavari et al. (1989)
Melting Point
993-c
Budavari et al. (1989)
Boiling Point
1704°C
Budavari et al. (1989)
Water Solubility
4.0 g/100 mL at 15 ° C
4.3 g/100 mL at 25 °C
Budavari et al. (1989)
Density
2.78
Budavari et al. (1989)
Koc
NA
Log KqW
NA
Vapor Pressure
1 mm Hgatl077°C
Keith and Walters (1985)
Reactivity
stable under normal conditions
Keith and Walters (1985)
Flammability
nonflammable
Keith and Walters (1985)
Flash Point
Dissociation Constant (-pK)
Henry's Law Constant
Molecular Diffusivity Coefficient
Air Diffusivity Coefficient
Fish Bioconcentration Factor
Odor Threshold
Conversion Factors
The chemical identity and physical/chemical properties of sodium bifluoride are summarized in Table 4.
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TABLE 4. CHEMICAL IDENTITY AND CHEMICAL/PHYSICAL PROPERTIES OF SODIUM BIFLUORIDE
Characteristic/Property Data Reference
CAS No.
Common Synonyms
Molecular Formula
Chemical Structure
Physical State
Molecular Weight
Melting Point
Boiling Point
Water Solubility
Density
Koc
Log KqW
Vapor Pressure
Vapor Density
Reactivity
Flammability
Flash Point
Dissociation Constant (-pK)
Flenry's Law Constant
Molecular Diffusivity Coefficient
Air Diffusivity Coefficient
Fish Bioconcentration Factor
Odor Threshold
Conversion Factors
1333-83-1
sodium hydrogen difluoride
sodium hydrogen fluoride
sodium acid fluoride
NaHF2
F2-H-Na
white, crystalline powder
62.01
decomposes on heating
NA
soluble in cold and hot water
2.08
NA
NA
NA
NA
aqueous solution corrodes glass
slightly combustible
NA
NA
NA
NA
NA
NA
NA
NA
F1SDB (1995)
F1SDB (1995)
Lewis (1993)
F1SDB (1995)
Budavari et al. (1989)
Budavari et al. (1989)
Lewis (1993)
Lide (1991)
Lewis (1993)
Budavari et al. (1989)
Lockheed Martin (1990)
IL ENVIRONMENTAL FATE
A. Environmental Release
Fluoroboric acid may be released into the environment in emissions and effluents from facilities involved in its
manufacture or use. It is used primarily in industrial metal plating solutions (60%), in the synthesis of diazo salts
(20%), and in metal finishing (20%) (HSDB 1995). It is used in bright dipping solutions for Sn-Pb alloys in printed
circuits and other electrical components (HSDB 1995).
B. Transport
No information was found in the available secondary sources on the environmental transport of fluoroboric acid. Its
miscibility with water indicates that transport in aqueous systems is very likely.
C-28
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C. Transformation/Persistence
FLUOROBORIC ACID:
1. Air — No information was found in the available secondary sources on the transformation and persistence
of fluoroboric acid or fluoroborates in the atmosphere.
2. Soil — No information was found in the available secondary sources on the transformation and persistence
of fluoroboric acid or fluoroborates in soil. Fluoroboric acid may undergo limited hydrolysis in moist soils
(Budavari et al. 1989).
3. Water — Fluoroboric acid undergoes limited hydrolysis in water to form hydroxyfluoroborate ions, the
major product is BF3OH" (Budavari et al. 1989).
4. Biota — No information was found in the available secondary sources on the biotransformation or
bioconcentration of fluoroboric acid or fluoroborates. Rapid urinary excretion of tetrafluoroborates
suggests that these salts would not bioaccumulate.
FLUORIDES:
1. Air — Gaseous inorganic fluorides undergo hydrolysis in the atmosphere; however, particulate forms are
relatively stable and do not hydrolyze readily (ATSDR 1993).
2. Soil — Fluorides tend to persist in soils as fluorosilicate complexes under acidic conditions and as calcium
fluoride under alkaline conditions. Sandy acidic soils favor the formation of soluble forms (ATSDR 1993).
3. Water — In dilute solutions and at neutral pH, fluoride is generally present as dissolved fluoride ion. High
calcium carbonate levels may lead to precipitation as calcium fluoride (ATSDR 1993).
4. Biota — Fluorides have been shown to accumulate in some aquatic organisms (ATSDR 1993). Soluble
forms of fluoride are taken up by terrestrial plants and converted into fluoro-organic compounds (ATSDR
1993).
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CHEMICAL SUMMARY FOR HYDROCHLORIC ACID
This summary is based on information retrieved from a systematic search limited to secondary sources. The only
exception is summaries of studies from unpublished TSCA submissions that may have been included. These sources
include online databases, unpublished EPA information, government publications, review documents, and standard
reference materials. No attempt has been made to verify information in these databases and secondary sources.
I. CHEMICAL IDENTITY AND PHYSICAL/CHEMICAL PROPERTIES
The chemical identity and physical/chemical properties of hydrochloric acid are summarized in Table 1.
TABLE 1. CHEMICAL IDENTITY AND CHEMICAL/PHYSICAL PROPERTIES OF HYDROCHLORIC ACID
Characteristic/Property
Data
Reference
CAS No.
7647-01-0
Budavari et al. (1996)
Common Synonyms
muriatic acid
Budavari et al. (1996)
Molecular Formula
HC1
Budavari et al. (1996)
Chemical Structure
HC1
Budavari et al. (1996)
Physical State
fuming liquid
Lewis (1993)
Molecular Weight
36.46
Lide (1995)
Melting Point
-25.4 °C (39.17% soln)
Budavari etal. (1996)
Boiling Point
108.58 °C at 760 mm Hg
Budavari etal. (1996)
Water Solubility
479.1 g/1 (40% soln)
Weastetal. (1985)
Density
1.20 g/cm3 (39.11% soln)
Budavari et al. (1996)
Vapor Density (air =1)
1.639 g/1
Austin and Glowacki (1989)
Koc
expected to be < 50
SRC (1998)
Log Kow
expected to be < 1
SRC (1998)
Vapor Pressure
no data
Reactivity
toxic, corrosive fumes w/H20 or steam
Sax(1984)
Flammability
non-combustible
Lewis (1993)
Flash Point
no data
Dissociation Constant
~ -3
Bodek etal. (1988)
Molecular Dif&sivity Constant
no data
Air Dif&sivity Constant
no data
Flenry's Law Constant
no data
Fish Bioconcentration Constant no data
Odor Threshold no data
IL ENVIRONMENTAL FATE
A. Aquatic Fate
If hydrochloric acid is released into the water column at low concentrations, a pKa of ~ -3.00 (Bodek et al., 1988)
indicates it will dissociate completely into chloride (CI ) and hydrogen (H+) ions. The amount of gaseous
hydrochloric acid dissolved in water is affected by the pH of the solution. A higher pH allows more aqueous
hydrochloric acid to dissociate, thereby increasing the solubility of hydrochloric acid gas (Bodek et al., 1988). As a
result, dilute solutions of hydrochloric acid are not expected to volatilize from water surfaces or to bioconcentrate in
aquatic organisms. Chloride ions generally do not react with many species in water and are harmless at relatively low
concentrations (Manahan, 1991). Hydrochloric acid will protonate amines and other electron pair donators present in
C-30
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natural waters, forming salts; this will be dependent upon pH. Large releases of the concentrated acid into water, such
as may result from a spill, will result in a lowering of the pH (Bodek et al., 1988).
B. Atmospheric Fate
If hydrochloric acid is released to the atmosphere, its vapor pressure indicates it will exist as a vapor in the ambient
atmosphere. Wet deposition of hydrochloric acid in rain, snow, or fog is expected to be the dominant fate process in
the atmosphere based upon its high water solubility (Arimoto, 1989).
C. Terrestrial Fate
If hydrochloric acid is released to soil, it will dissociate into chloride and hydrogen ions in moist soils. Hydrochloric
acid will protonate amines and other electron pair donators present in soils, forming salts; this will be dependent upon
pH. The chloride ion is extremely mobile in soils and almost no soil retention occurs (Bodek et al., 1988). Chloride
is typically the predominant ion in saline soils and the second most abundant anion in sodic soils; thus, it is readily
available for the formation of metal complexes in soil (Bodek et al., 1988; SRC, 1998).
D. Summary
If released into water, hydrochloric acid will dissociate into chloride (CI ) and hydrogen (H+) ions. Therefore,
hydrochloric acid is not expected to adsorb to suspended solids or sediment in the water column, bioconcentrate in
aquatic organisms, nor volatilize from water surfaces. Chloride ions generally do not react with many species in
water and are harmless at relatively low concentrations. Hydrochloric acid will protonate amines and other electron
pair donators present in natural waters and soils, forming salts; this will be dependent upon pH. If released to soil,
hydrochloric acid is expected to dissociate into its component ions in moist soils. Because the chloride ion is
extremely mobile in soils, almost no soil retention occurs. Chloride is typically the predominant ion in saline soils
and the second most abundant anion in sodic soils; thus, it is readily available for the formation of metal complexes in
soil. Volatilization of hydrochloric acid from soil surfaces is not expected to occur. If released to the atmosphere,
hydrochloric acid is expected to exist as a gas. Hydrochloric acid is expected to be physically removed from the
atmosphere by wet deposition based upon its high water solubility.
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CHEMICAL SUMMARY FOR HYDROGEN PEROXIDE
This chemical was identified by one or more suppliers as a bath ingredient for the electroless copper, non-
formaldehyde electroless copper, and tin-palladium processes. This summary is based on information retrieved from
a systematic search limited to secondary sources (see Attachment C-l). These sources include online databases,
unpublished EPA information, government publications, review documents, and standard reference materials. No
attempt has been made to verify information in these databases and secondary sources.
I. CHEMICAL IDENTITY AND PHYSICAL/CHEMICAL PROPERTIES
The chemical identity and physical/chemical properties of hydrogen peroxide are summarized in Table 1.
TABLE 1. CHEMICAL IDENTITY AND CHEMICAL/PHYSICAL PROPERTIES OF HYDROGEN PEROXIDE
Characteristic/Property Data Reference
CAS No.
Common Synonyms
Molecular Formula
Chemical Structure
Physical State
Molecular Weight
Melting Point
Boiling Point
Water Solubility
Density
Vapor Density (air =1)
Koc
Log KqW
Vapor Pressure
Reactivity
Flammability
Flash Point
Dissociation Constant
Flenry's Law Constant
Molecular Diffusivity Coefficient
Air Diffusivity Coefficient
Fish Bioconcentration Factor
Odor Threshold
Conversion Factors
7722-84-1
hydrogen dioxide; hydroperoxide; albone; hioxyl
h2o2
h2o2
colorless, unstable liquid, bitter taste
34.02
-0.43 °C
152°C
miscible
1.463 @0°C
no data
no data
no data
1.97 mm Fig @ 25 ° C (measured)
strong oxidizer; may decompose violently if traces of
impurities are present
molecular additions, substitutions, oxidations,
reduction; can form free radicals
not flammable, but can cause spontaneous combustion
of flammable materials
no data
no data
no data
no data
no data
no data
odorless
1 ppm = 1.39 mg/m3
1 mg/m3 = 0.72 ppm
30% soln 1.1 kg/L
anhydrous 1.46 kg/L
Budavari et al. 1989
Budavari et al. 1989
IARC 1985
Budavari et al. 1989
Budavari et al. 1989
Budavari etal. 1989
Budavari etal. 1989
Budavari etal. 1989
Budavari etal. 1989
CHEMFATE 1995
Budavari etal. 1989
IARC 1985
HSDB 1995
Budavari etal. 1989
IARC 1985
Budavari et al. 1989
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IL ENVIRONMENTAL FATE
A. Environmental Release
No information was found in the secondary sources searched regarding the environmental release of hydrogen
peroxide. Solutions of hydrogen peroxide gradually deteriorate (Budavari et al., 1989). Hydrogen peroxide is a
naturally occurring substance. Gaseous hydrogen peroxide is recognized to be a key component and product of the
earth's lower atmospheric photochemical reactions, in both clean and polluted atmospheres. Atmospheric hydrogen
peroxide is also believed to be generated by gas-phase photochemical reactions in the remote troposphere (IARC,
1985)
B. Transport
No information was found in the secondary sources searched regarding the transport of hydrogen peroxide.
C. Transformation/Persistence
1. Air — Hydrogen peroxide may be removed from the atmosphere by photolysis giving rise to hydroxyl
radicals, by reaction with hydroxyl radicals, or by heterogenous loss processes such as rain-out (IARC,
1985).
2. Soil — No information was found in the secondary sources searched regarding the transformation or
persistence of hydrogen peroxide in soil, however, solutions of hydrogen peroxide gradually deteriorate
(Budavari et al., 1989).
3. Water — Hydrogen peroxide is a naturally occurring substance. Surface water concentrations of hydrogen
peroxide have been found to vary between 51-231 mg/L, increasing both with exposure to sunlight and the
presence of dissolved organic matter (IARC, 1985).
4. Biota — Hydrogen peroxide is a naturally occurring substance. Endogenous hydrogen peroxide has been
found in plant tissues at the following levels (mg/kg frozen weight): potato tubers, 7.6; green tomatoes, 3.5;
red tomatoes, 3.5; and castor beans in water, 4.7 (IARC, 1985).
C-33
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CHEMICAL SUMMARY FOR LEAD
This summary is based on information retrieved from a systematic search limited to secondary sources. The only
exception is summaries of studies from unpublished TSCA submissions that may have been included. These sources
include online databases, unpublished EPA information, government publications, review documents, and standard
reference materials. No attempt has been made to verify information in these databases and secondary sources. The
search identified sources of information for Lead.
I. CHEMICAL IDENTITY AND PHYSICAL/CHEMICAL PROPERTIES
The chemical identity and physical/chemical properties of Lead are summarized in Table 1.
TABLE 1. CHEMICAL IDENTITY AND CHEMICAL/PHYSICAL PROPERTIES OF LEAD
Characteristic/Property Data Reference
CAS No. 7439-92-1 Howard and Neal (1992)
Common Synonyms
Molecular Formula Pb Howard and Neal (1992)
Chemical Structure
N/A
Physical State
Metal
Weast (1983)
Molecular Weight
207.2
Weast (1983)
Melting Point
327.4°C
Weast (1983)
Boiling Point
1740°C
Weast (1983)
Water Solubility
Insoluble
Weast (1983)
Density
10.65
Budavari et al. (1996)
Vapor Density (air =1)
no data
Koc
no data
Log Kow
no data
Vapor Pressure
1.77 mm Hg @ 1000°C
Budavari et al. (1996)
Reactivity
Flammable solid
Flammability
no data
Flash Point
no data
Dissociation Constant
no data
Molecular Dif&sivity Constant
no data
Air Dif&sivity Constant
no data
Henry's Law Constant
no data
Fish Bioconcentration Constant
no data
Odor Threshold
no data
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CHEMICAL SUMMARY FOR MALEIC ACID
This summary is based on information retrieved from a systematic search limited to secondary sources. The only
exception is summaries of studies from unpublished TSCA submissions that may have been included. These sources
include online databases, unpublished EPA information, government publications, review documents, and standard
reference materials. No attempt has been made to verify information in these databases and secondary sources.
I. CHEMICAL IDENTITY AND PHYSICAL/CHEMICAL PROPERTIES
The chemical identity and physical/chemical properties of maleic acid are summarized in Table 1.
TABLE 1. CHEMICAL IDENTITY AND CHEMICAL/PHYSICAL PROPERTIES OF MALEIC ACID
Characteristic/Property
Data
Reference
CAS No.
110-16-7
Lide(1995)
Common Synonyms
(Z)-butenedioic acid; toxilic acid
Budavari et al. (1996)
Common Synonyms
cis-l,2-ethylenedicarboxylic acid
Budavari et al. (1996)
Common Synonyms
maleinic acid
Lewis (1993)
Molecular Formula
c4h4o4
Budavari et al. (1996)
Chemical Structure
HOOCCH=CHCOOH
Aldrich (1996)
Physical State
white crystals
Budavari et al. (1996)
Molecular Weight
116.07
Budavari et al. (1996)
Melting Point
130.5°C
Lide(1995)
Boiling Point
no data
Water Solubility
441 g/1 at 25 °C
PHYSPROP (1998)
Density
1.59 g/cm3 at 20 °C
Lide(1995)
Vapor Density (air =1)
no data
Koc
16 (estimated)
Lyman et al. (1990)
Log Kow
-0.34
Flansch etal. (1995)
Vapor Pressure
3.06x10"5 mm Fig at 25 °C
Daubert and Danner (1991)
Reactivity
stable
Weiss (1986)
Flammability
combustible
Lewis (1993)
Flash Point
not pertinent
Weiss (1986)
Dissociation Constant
pKj = 1.83; pK2 = 6.07
Howard (1989)
Molecular Dif&sivity Constant
no data
Air Dif&sivity Constant
no data
Flenry's Law Constant
no data; estimated to be < lxlO"8 atm m3/mol
Estimated
Fish Bioconcentration Constant
10-11
F1SDB (1998)
Odor Threshold
no data
IL ENVIRONMENTAL FATE
A. Aquatic Fate
If released into water, maleic acid is not expected to adsorb to suspended solids or sediments in water based upon an
estimated Koc of 16 (Swann et al., 1983), determined from a log Kow of -0.34 (Hansch et al., 1995) and a
regression-derived equation (Lyman et al., 1990). Volatilization from the water column to the atmosphere is not
expected to occur (Lyman et al., 1990) based on an estimated Henry's Law constant of <10"8 atm-m3/mole . Maleic
acid is expected to be stable to hydrolysis in the pH range of 5-9 typically encountered in the environment (Lyman et
C-35
-------
al., 1990). According to a classification scheme (Franke et al., 1994), a BCF of 10 in golden ide fish (Freitag, 1985,
as cited in HSDB, 1998) suggests that the potential for bioconcentration in aquatic organisms is low. Maleic acid
was determined to be readily degraded in biodegradation screening tests; however, no biodegradation studies were
available in environmental waters (Howard, 1989).
B. Atmospheric Fate
According to a model of gas/particle partitioning of semivolatile organic compounds in the atmosphere (Bidleman,
1988), maleic acid, which has a vapor pressure of 3.06xl0"5 mmHg at 25 °C (Daubert andDanner, 1991), is
expected to exist as both a particulate and vapor in the ambient atmosphere. Because maleic acid has pKa's of 1.83
and 6.07 (Howard, 1989), it is expected to exist in the dissociated form in the environment and form salts with
cations (HSDB, 1998). Removal of maleic acid from the atmosphere by reaction with photochemically-produced
hydroxyl radicals results in an estimated half-life of 2 days (Meylan and Howard, 1993). The reaction of maleic acid
with ozone in the atmosphere results in a gas-phase half-life ranging from 7-13 days (Meylan and Howard, 1993).
Maleic acid may undergo some degradation by direct photolysis; 17% of applied maleic acid was degraded after 17
hours following irradiation by light > 290 nm (Freitag et al., 1985, cited in HSDB, 1998). Wet deposition of maleic
in rain, snow, or fog is expected to be an important transport process in the atmosphere based upon its high water
solubility (Arimoto, 1989).
C. Terrestrial Fate
Based on a classification scheme (Swann et al., 1983), an estimated Koc of 16, determined from a log Kow of -0.34
(Hansch et al., 1995) and a regression-derived equation (Lyman et al., 1990), indicates that maleic acid is expected to
have very high mobility in soil. Volatilization of maleic acid from moist soil surfaces is not expected to be important
(Lyman et al., 1990) given an estimated Henry's Law constant of <10"8 atm-m3/mole. In addition, maleic acid is not
expected to volatilize from dry soil given its vapor pressure of 3.06xl0"5 mm Hg (Daubert and Danner, 1991). While
maleic acid is readily biodegradable in screening studies, no degradation data were available for soil systems
(Howard, 1989).
D. Summary
If released to air, a vapor pressure of 3,06xl0~5 mm Hg at 25 ° C indicates that maleic acid should exist as both a gas
and particulate in the ambient atmosphere. Gas-phase maleic acid will be degraded in the atmosphere by reaction with
photochemically-produced hydroxyl radicals; the half-life for this reaction in air is estimated to be 2 hours. The
reaction of maleic acid with ozone in the atmosphere results in a gas-phase half-life ranging from 7-13 days. Wet
deposition of maleic acid from the atmosphere is expected to be an important transport process. Screening studies
suggest that direct photolysis if maleic acid may occur. A BCF of 10 in golden ide fish suggests the potential for
bioconcentration in aquatic organisms is low. If released to soil, maleic acid is expected to have very high mobility
based upon an estimated Koc of 16, and, therefore, it has the potential to leach to groundwater. Volatilization from
water and from moist soil surfaces is not expected to be an important fate process based upon an estimated Henry's
Law constant of <10"8 atm-m3/mole. Volatilization from dry soil surfaces is not expected to occur based upon the
vapor pressure of this compound. Maleic acid was determined to be readily biodegraded in screening studies, although
no data were available for biodegradation in water or soil.
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CHEMICAL SUMMARY FOR MALIC ACID
This summary is based on information retrieved from a systematic search limited to secondary sources. The only
exception is summaries of studies from unpublished TSCA submissions that may have been included. These sources
include online databases, unpublished EPA information, government publications, review documents, and standard
reference materials. No attempt has been made to verify information in these databases and secondary sources.
I. CHEMICAL IDENTITY AND PHYSICAL/CHEMICAL PROPERTIES
The chemical identity and physical/chemical properties of malic acid are summarized in Table 1.
TABLE 1. CHEMICAL IDENTITY AND CHEMICAL/PHYSICAL PROPERTIES OF MALIC ACID
Characteristic/Property
Data
Reference
CAS No.
6915-15-7
Lewis (1993)
Common Synonyms
hydroxysuccinic acid; apple acid
Lewis (1993)
Molecular Formula
c4h6o5
Budavari et al. (1996)
Chemical Structure
COOHCH2CH(OH)COOH
Lewis (1993)
Physical State
colorless crystals
Lewis (1993)
Molecular Weight
134.09
Budavari et al. (1996)
Melting Point
O
O
O
O
Budavari et al. (1996)
Boiling Point
140 °C, decomposes
Budavari et al. (1996)
Water Solubility
592 g/1 at 25 °C
PHYSPROP (1998)
Density
1.6 g/cm3
Lewis (1993)
Vapor Density (air =1)
no data
Koc
5 (estimated)
Lyman et al. (1990)
Log Kow
-1.26
Flansch etal. (1995)
Vapor Pressure
3.28x10"8 mm Fig at 25 °C
Yaws (1994)
Reactivity
no data
Flammability
combustible
Lewis (1993)
Flash Point
no data
Dissociation Constant
3.40
PHYSPROP (1998)
Molecular Dif&sivity Constant
no data
Air Dif&sivity Constant
no data
Flenry's Law Constant
no data; expected to be < 10"8 atm m3/mol
Estimated
Fish Bioconcentration Constant
no data; expected to be <1
Estimated
Odor Threshold
no data
IL ENVIRONMENTAL FATE
A. Aquatic Fate
If released into aquatic waters, malic acid is not expected to adsorb to suspended solids and sediments in water based
upon an estimated Koc of 5 (Swann et al., 1983), determined from a log Kow of -1.26 (Hansch et al., 1995) and a
regression-derived equation (Lyman et al., 1990). Volatilization from the water column to the atmosphere is not
expected to occur (Lyman et al., 1990) based on an estimated Henry's Law constant of <10"8 atm-m3/mole . Malic
acid is expected to be stable to hydrolysis in the pH range of 5-9 typically encountered in the environment (Lyman et
al., 1990). According to a classification scheme (Franke et al., 1994), an estimated BCF of <1 suggests that the
potential for bioconcentration in aquatic organisms is low and not an important fate process. Results from a number
C-37
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of biological screening tests have shown that malic acid biodegrades relatively fast (Fischer et al., 1974; Malaney and
Gerhold, 1969; Heukelekian and Rand, 1955; as cited in HSDB, 1998).
B. Atmospheric Fate
According to a model of gas/particle partitioning of semivolatile organic compounds in the atmosphere (Bidleman,
1988), malic acid, which has a vapor pressure of 3.28xl0"8 mmHg at 25 °C(Yaws, 1994), should exist almost
entirely as a particulate in the ambient atmosphere. Removal of malic acid from the atmosphere by reaction with
photochemically-produced hydroxyl radicals results in an estimated half-life of 2 days (Meylan and Howard, 1993).
Wet deposition of malic acid in rain, snow, or fog is expected to be the dominant transport process in the atmosphere
based upon its high water solubility (Arimoto, 1989). Because carboxylic acids are generally resistant to hydrolysis,
malic acid is not expected to hydrolyze in environmental media (Lyman et al., 1990).
C. Terrestrial Fate
Based on a classification scheme (Swann et al., 1983), an estimated Koc of 5, determined from a log Kow of-1.26
(Hansch et al., 1995) and a regression-derived equation (Lyman et al., 1990), indicates that malic acid is expected to
have very high mobility in soil and may leach to groundwater. Volatilization of malic acid from moist soil surfaces is
not expected to be important (Lyman et al., 1990) given an estimated Henry's Law constant of <10"8 atm-m3/mole. In
addition, malic acid is not expected to volatilize from dry soil given its vapor pressure of 3,28xl0"8 mm Hg (Yaws,
1994). Biodegradation screening studies reveal that malic acid biodegrades relatively fast (Fischer et al., 1974;
Malaney and Gerhold, 1969; Heukelekian and Rand, 1955; as cited in HSDB, 1998).
D. Summary
If released to air, a vapor pressure of 3.28x10 s mm Hg at 25 ° C indicates that malic acid should exist as a particulate
in the ambient atmosphere. Removal of malic acid from the atmosphere by reaction with photochemically-produced
hydroxyl radicals results in an estimated half-life of 2 days. Wet deposition is expected to be the dominant transport
process of malic acid from the atmosphere. An estimated BCF of <1 suggests the potential for bioconcentration in
aquatic organisms is low. If released to soil, malic acid is expected to have very high mobility based upon an
estimated Koc of 5, and, therefore, it has the potential to leach to groundwater. Volatilization from water and from
moist soil surfaces is not expected to be an important fate process based upon an estimated Henry's Law constant of
<10"8 atm-m3/mole, also volatilization from dry soil surfaces is not expected to occur based upon the vapor pressure
of this compound. Hydrolysis of malic acid in environmental media is not expected to occur. Malic acid was
determined to be readily biodegraded in screening studies, although no data were available for biodegradation in water
or soil.
C-38
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CHEMICAL SUMMARY FOR METHANESULFONIC ACID
This summary is based on information retrieved from a systematic search limited to secondary sources. The only
exception is summaries of studies from unpublished TSCA submissions that may have been included. These sources
include online databases, unpublished EPA information, government publications, review documents, and standard
reference materials. No attempt has been made to verify information in these databases and secondary sources.
I. CHEMICAL IDENTITY AND PHYSICAL/CHEMICAL PROPERTIES
The chemical identity and physical/chemical properties of methanesulfonic acid are summarized in Table 1.
TABLE 1. CHEMICAL IDENTITY AND CHEMICAL/PHYSICAL PROPERTIES OF METHANESULFONIC
ACID
Characteristic/Property Data Reference
CAS No.
Common Synonyms
Molecular Formula
Chemical Structure
Physical State
Physical State
Molecular Weight
Melting Point
Boiling Point
Water Solubility
Density
Vapor Density (air =1)
Koc
Log Kow
Vapor Pressure
Reactivity
Flammability
Flash Point
Dissociation Constant
Molecular Diffusivity Constant
Air Diffusivity Constant
Flenry's Law Constant
Fish Bioconcentration Constant
Odor Threshold
75-75-2
methylsulfonic acid
ch4o3s
ch3so2oh
solid
liquid at room temperature
96.11
20 °C
200 °C; 167 °C at 10 mm Hg
l.OxlO3 g/L at 20 °C
1.48 g/cm3
no data
1 (estimated)
no data; estimated to be < 1
4.28x10"4 mm Fig at 25 °C
thermally stable at mod. elevated temps
no data
112 °C
-1.86
no data
no data
1.3x10"8 atm m3/mol (estimated)
3 (estimated)
no data
Lide(1995)
Budavari et al. (1996)
Budavari et al. (1996)
Budavari et al. (1996)
Budavari et al. (1996)
Lewis (1993)
Budavari et al. (1996)
Lide(1995)
Lewis (1993); Lide (1995)
PHYSPROP (1998)
Lide(1995)
F1SDB (1998)
Estimated
Daubert and Danner (1991)
Budavari et al. (1996)
ECDIN (1998)
Serjeant and Dempsey (1979)
Meylan and Flo ward (1991)
Meylan etal. (1997)
IL ENVIRONMENTAL FATE
A. Aquatic Fate
If released into aquatic waters, methanesulfonic acid is not expected to adsorb to suspended solids and sediments in
water based upon an estimated Koc of 1 (Swann et al., 1983), determined from a structure fragment estimation
method (Meylan et al., 1992). Volatilization from the water column to the atmosphere is not expected to occur
(Lyman et al., 1990) based on an estimated Henry's Law constant of 1.3xl0"8 atm-m3/mole (Meylan and Howard,
1991; SRC, 1998). Methanesulfonic acid is expected to be stable to hydrolysis in the pH range of 5-9 typically
C-39
-------
encountered in the environment (Lyman et al., 1990). According to a classification scheme (Franke et al., 1994), an
estimated BCF of 3 (Meylan et al., 1997) suggests that the potential for bioconcentration in aquatic organisms is low.
It was determined that many bacterial types can degrade methanesulfonic acid through diverse routes and at different
rates, although specifics were not given (Baker et al., 1991, as cited in HSDB, 1998). Because methanesulfonic acid
has pKaof -1.86 (Seijeant and Dempsey, 1979), it is expected to exist in the dissociated form in the environment.
B. Atmospheric Fate
According to a model of gas/particle partitioning of semivolatile organic compounds in the atmosphere (Bidleman,
1988), methanesulfonic acid, which has a vapor pressure of 4.28xl0"4 mmHg at 25 °C (Daubert andDanner, 1991),
has the potential to exist as both a vapor and particulate in the ambient atmosphere. Because methanesulfonic acid
has pKa of -1.86 (Seijeant and Dempsey, 1979), it is expected to exist in the dissociated form in the environment.
Removal of methanesulfonic acid from the atmosphere by reaction with photochemically- produced hydroxyl radicals
results in an estimated half-life of 58 days (Meylan and Howard, 1993). In the atmosphere, methanesulfonic acid is
concentrated in the smaller size particles, 0.25-2 um in diameter (Kolaitis et al., 1989, as cited in HSDB, 1998).
Removal of particulate methanesulfonic acid from the atmosphere can occur through wet and dry deposition (HSDB,
1998).
C. Terrestrial Fate
Based on a classification scheme (Swann et al., 1983), an estimated Koc of 1, determined from a structure fragment
estimation method (Meylan et al., 1992), indicates that methanesulfonic acid is expected to have very high mobility in
soil. Volatilization of methanesulfonic acid from moist soil surfaces is not expected to be important (Lyman et al.,
1990) given an estimated Henry's Law constant of 1.3xl0"8 atm-m3/mole (Meylan and Howard, 1991; SRC, 1998).
In addition, methanesulfonic acid is not expected to volatilize from dry soil given its vapor pressure of 4.28xl0"4 mm
Hg (Daubert and Danner, 1991). It was determined that many bacterial types can degrade methanesulfonic acid
through diverse routes and at different rates, although specifics were not given (Baker et al., 1991, as cited in HSDB,
1998).
D. Summary
If released to air, a vapor pressure of 4.28 x 10~4 mm Hg at 25 ° C indicates that methanesulfonic acid has the
potential to exist as both a vapor and particulate in the ambient atmosphere. Gas-phase methanesulfonic acid will be
degraded in the atmosphere by reaction with photochemically-produced hydroxyl radicals; the half-life for this
reaction in air is estimated to be 58 hours. Removal of particulate methanesulfonic acid from the atmosphere can
occur through wet and dry deposition. An estimated BCF of 3 suggests the potential for bioconcentration in aquatic
organisms is low. If released to soil, methanesulfonic acid is expected to have very high mobility based upon an
estimated Koc of 1, and, therefore, it has the potential to leach to groundwater. Volatilization from water and from
moist soil surfaces is not expected to be an important fate process based upon an estimated Henry's Law constant of
1.3xl0"8 atm-m3/mole. Hydrolysis of methanesulfonic acid is not expected to occur. Volatilization from dry soil
surfaces is not expected to occur based upon the vapor pressure of this compound. Methanesulfonic acid was
determined to be biodegraded by many bacterial types, although specifics were not given.
C-40
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CHEMICAL SUMMARY FOR NICKEL SULFATE
This summary is based on information retrieved from a systematic search limited to secondary sources. The only
exception is summaries of studies from unpublished TSCA submissions that may have been included. These sources
include online databases, unpublished EPA information, government publications, review documents, and standard
reference materials. No attempt has been made to verify information in these databases and secondary sources. The
search identified sources of information for nickel and soluble salts of nickel, including nickel sulfate and nickel
sulfate hexahydrate.
I. CHEMICAL IDENTITY AND PHYSICAL/CHEMICAL PROPERTIES
The chemical identity and physical/chemical properties of nickel sulfate are summarized in Table 1.
TABLE 1. CHEMICAL IDENTITY AND CHEMICAL/PHYSICAL PROPERTIES OF NICK F.I. SULFATE
Characteristic/Property Data Reference
CAS No.
Common Synonyms
Molecular Formula
Chemical Structure
Physical State
Molecular Weight
Melting Point
Boiling Point
Water Solubility
Density
Vapor Density (air =1)
Koc
Log Kow
Vapor Pressure
Reactivity
Flammability
Flash Point
Dissociation Constant
Molecular Dif&sivity Constant
Air Dif&sivity Constant
Flenry's Law Constant
Fish Bioconcentration Constant
Odor Threshold
7786-81-4
sulfuric acid, nickel (2+) salt
Ni04S
NiSQ,
green-yellow orthorhombic crystals
154.757
840 °C, decomposes
no data
293 g/LatO °C
4.01 g/cm3
no data
no data; expected to be < 10
no data; expected to be < 1
no data; expected to be <10-6 mm Fig at 25 C
no data
not flammable
no data; expected to be > 350 °C
no data
no data
no data
no data; expected to be < lxlO"8
no data
no data
Lide(1995)
Flo ward and Neal (1992)
Budavari et al. (1996)
Lide(1995)
Lide(1995)
Lide(1995)
Lide(1995)
Dean (1985)
Lide(1995)
SRC (1998)
SRC (1998)
Estimated
Prager (1995)
SRC (1998)
SRC (1998)
IL ENVIRONMENTAL FATE
A. Aquatic Fate
If released into water, nickel sulfate is expected to dissociate into nickel (Ni2+) and sulfate [(S04)2"] ions. The
dissociation of nickel sulfate into its component ions indicates that the compound nickel sulfate is not expected to
volatilize from water surfaces. In aqueous solutions, nickel exists as the hexaquonickel ion, [Ni(H20)62+]; this ion is
poorly absorbed by most living organisms (Sunderman and Oskarsson, 1991). In natural waters, nickel exists both in
the ionic form and as stable organic complexes (Sunderman and Oskarsson, 1991). Nickel compounds are generally
C-41
-------
soluble at pH values less than 6.5, but at pH values greater than 6.7 nickel exists predominantly as insoluble nickel
hydroxides (Sunderman and Oskarsson, 1991). Shellfish and Crustacea generally contain higher concentrations of
nickel in their flesh than do other species of fish (Sunderman and Oskarsson, 1991).
B. Atmospheric Fate
If released to the atmosphere, nickel sulfate's high melting point (Lide, 1995) and low vapor pressure (SRC, 1998)
indicate that it will exist as a particulate (Bidleman, 1988). Wet and dry deposition of nickel sulfate is expected to be
the dominant fate process in the atmosphere (Arimoto, 1989). The rate of dry deposition will depend on the
prevailing winds and particle size (Bodek et al., 1988). Nickel sulfate's high water solubility (Dean, 1985) indicates
that it is expected to undergo wet deposition in rain, snow, or fog.
C. Terrestrial Fate
If nickel sulfate is released to soil, it is expected to dissociate into Ni2+ and (S04)2" ions in the presence of moisture.
Iron and manganese oxides, clay minerals, and organic matter may be important sorbents of nickel (Bodek et al.,
1988) and will retard its migration through soil. Complexing ligands, such as organic acids, may reduce the sorption
of nickel (Bodek et al., 1988). Acid rain has a tendency to mobilize nickel from soil and increase leaching into
groundwater due to the high solubility of nickel compounds at pH values less than 6.5 (Sunderman and Oskarsson,
1991). The high melting point, low vapor pressure, and low Henry's Law constant expected for an ionic salt indicate
that nickel sulfate will not volatilize from either moist or dry soil surfaces (Bodek et al., 1988).
D. Summary
If released into water, nickel sulfate is expected to dissociate into nickel (Ni2+) and sulfate (S04)2" ions. Therefore,
nickel sulfate is not expected to adsorb to suspended solids or sediment in the water column, bioconcentrate in
aquatic organisms, or volatilize from water surfaces. In natural waters, nickel exists in both the ionic form and as
stable organic complexes; at pH values greater than 6.7 it exists as insoluble nickel hydroxides. In moist soils, nickel
sulfate is expected to dissociate into its component ions. Ionic nickel may be sorbed by iron and manganese oxides,
clay minerals, and organic matter; acid rain and complexing ligands may reduce the sorption of nickel. Volatilization
of nickel sulfate from soil surfaces is not expected to occur. If released to the atmosphere, nickel sulfate is expected
to exist as a particulate. Nickel sulfate is expected to be physically removed from the atmosphere by wet and dry
deposition. The rate of dry deposition will depend on particle size and prevailing wind patterns.
C-42
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CHEMICAL SUMMARY FOR PALLADIUM CHLORIDE
This summary is based on information retrieved from a systematic search limited to secondary sources. The only
exception is summaries of studies from unpublished TSCA submissions that may have been included. These sources
include online databases, unpublished EPA information, government publications, review documents, and standard
reference materials. No attempt has been made to verify information in these databases and secondary sources.
I. CHEMICAL IDENTITY AND PHYSICAL/CHEMICAL PROPERTIES
The chemical identity and physical/chemical properties of palladium chloride are summarized in Table 1.
TABLE 1. CHEMICAL IDENTITY AND CHEMICAL/PHYSICAL PROPERTIES OF PALLADIUM CHLORIDE
Characteristic/Property
Data
Reference
CAS No.
Common Synonyms
Common Synonyms
Molecular Formula
Chemical Structure
Physical State
Molecular Weight
Melting Point
Boiling Point
Water Solubility
Density
Vapor Density (air =1)
Koc
Log Kow
Vapor Pressure
Reactivity
Flammability
Flash Point
Dissociation Constant
Molecular Dif&sivity Constant
Air Dif&sivity Constant
Flenry's Law Constant
Fish Bioconcentration Constant
Odor Threshold
7647-10-1
Palladous chloride
Palladium (II) chloride
Cl2Pd
PdCl2
red rhombohedral crystals; hygroscopic
177.33
500°C (decomposes)
decomposed at high temperatures
soluble1
4.0 g/cm3
no data
no data; expected to be <10
no data; expected to be <1
no data; expected to be <10"6 mm Hg
no data
no data
no data
expected to dissociate into Pd2+ and CI"
no data
no data
no data; expected to be <1X10"8
no data
no data
CAS (1998)
Budavari et al. (1996)
Lide(1995)
Budavari et al. (1996)
Budavari et al. (1996)
Lide(1995)
Lide(1995)
Lide(1995)
Budavari et al. (1996)
Dean (1985)
Lide(1995)
SRC (1998)
SRC (1998)
SRC (1998)
SRC (1998)
SRC (1998)
1 This form of expressing solubility cannot be converted into g/L units
IL ENVIRONMENTAL FATE
A.
Aquatic Fate
If palladium chloride is released into the water column, it is expected to dissociate into palladium (Pd2+) and chloride
(CI ) ions. The dissociation of palladium chloride into its component ions indicates that palladium chloride is not
expected to bioconcentrate in aquatic organisms or volatilize from water surfaces. Palladium ions may adsorb to
charged surfaces of suspended sediments and humic materials in the water column (Evans, 1989). The chloride ion
may complex with heavy metals in natural waters, thereby increasing their solubility (Bodek et al., 1988). Adsorption
C-43
-------
of the chloride ion to suspended solids and sediment in the water column is not expected to be an important fate
process.
B. Atmospheric Fate
If palladium chloride is released to the atmosphere, the low vapor pressure expected for an ionic salt indicates that it
will exist as a particulate. Dry deposition of palladium chloride is expected to be the dominant fate process in the
atmosphere (Arimoto, 1989). The rate of dry deposition will depend on the prevailing winds and particle size (Bodek
et al., 1988). Palladium chloride is expected to undergo wet deposition (Arimoto, 1989) in rain, snow, or fog, based
upon its water solubility (Dean, 1985).
C. Terrestrial Fate
If palladium chloride is released to soil, it is expected to dissociate into its component ions in moist soils. The
dissociation of palladium chloride in moist soils indicates that palladium chloride is not expected to volatilize from
moist soil surfaces. While no specific information concerning the sorption of ionic palladium in soils was available,
some metals adsorb to charged surfaces of soil particles or form inner sphere complexes with variable-charge soil
surfaces (Evans, 1989). If this occurs with palladium then its rate of migration through soil may be slow. Chloride is
extremely mobile in soils (Bodek et al., 1988). The chloride ion may complex with heavy metals, thereby increasing
their solubility (Bodek et al., 1988) and potential for leaching into groundwater. The low vapor pressure expected for
an ionic salt indicates that palladium chloride will not volatilize from dry soil surfaces.
D. Summary
If released into water, palladium chloride will dissociate into palladium and chloride ions. Therefore, palladium
chloride is not expected to adsorb to suspended solids or sediment in the water column, bioconcentrate in aquatic
organisms, nor volatilize from water surfaces. Palladium ions may adsorb to charged surfaces of suspended
sediments and humic matter in the water column. Adsorption of the chloride ion to suspended solids and sediment in
the water column is not expected to be an important fate process. If released to soil, palladium chloride is expected to
dissociate into its component ions in moist soils. The dissociation of palladium chloride into its component ions
indicates that palladium chloride is not expected to volatilize from moist soil surfaces. Ionic palladium may adsorb
to charged surfaces of soil particles or form inner sphere complexes with variable-charge soil surfaces. Chloride is
extremely mobile in soils. The low vapor pressure expected for an ionic salt indicates that volatilization of palladium
chloride from soil surfaces is not expected to be an important fate process. If released to the atmosphere, palladium
chloride is expected to exist as a particulate. Palladium chloride is expected to be physically removed from the
atmosphere by wet and dry deposition. The rate of dry deposition will depend on particle size and prevailing wind
patterns.
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CHEMICAL SUMMARY FOR PHOSPHORIC ACID
This summary is based on information retrieved from a systematic search limited to secondary sources. The only
exception is summaries of studies from unpublished TSCA submissions that may have been included. These sources
include online databases, unpublished EPA information, government publications, review documents, and standard
reference materials. No attempt has been made to verify information in these databases and secondary sources.
I. CHEMICAL IDENTITY AND PHYSICAL/CHEMICAL PROPERTIES
The chemical identity and physical/chemical properties of phosphoric acid are summarized in Table 1.
TABLE 1. CHEMICAL IDENTITY AND CHEMICAL/PHYSICAL PROPERTIES OF PHOSPHORIC ACID
Characteristic/Property Data Reference
CAS No.
Common Synonyms
Molecular Formula
Chemical Structure
Physical State
Molecular Weight
Melting Point
Boiling Point
Water Solubility
Density
Vapor Density (air =1)
Koc
Log Kow
Vapor Pressure
Reactivity
Flammability
Flash Point
Dissociation Constant
Molecular Dif&sivity Constant
Air Dif&sivity Constant
Flenry's Law Constant
Fish Bioconcentration Constant
Odor Threshold
7664-38-2
orthophosphoric acid
h3o4p
h3po4
unstable, orthorhombic crystals; clear, syrupy liquid
98.00
42.35 °C (crystals); -11.8 °C (30% soln)
261 °C (crystals); 101.8 °C (30% soln)
5,480 g/1 at 20 °C (crystals);
354.1 g/1 at 20 °C (30% soln)
1.86 g/cm3 at 25 °C (crystals);
1.18 g/cm3 at 25 °C (30% soln)
no data
expected to be < 10
expected to be < 1
0.03 mm Fig at 20 °C (crystals);
16.3 mm Hg at 20 °C (30% soln)
relatively unreactive at room temperature
no data
no data
pKj: 2.15; pK2: 7.09; pK3: 12.32
no data
no data
expected to be < lxl 0"8 atm m3/mole
no data
no data
Lide(1995)
Budavari et al. (1996)
Budavari et al. (1996)
Budavari et al. (1996)
Budavari et al. (1996)
Budavari et al. (1996)
Gard (1996)
Gard (1996)
Weast et al. (1985)
Gard (1996)
SRC (1998)
SRC (1998)
Gard (1996)
Gard (1996)
Budavari et al. (1996)
SRC (1998)
IL ENVIRONMENTAL FATE
A. Aquatic Fate
Phosphoric acid is a weak tribasic acid with a pK, of 2.15 (Budavari et al., 1996) and, if released into the water
column at low concentrations, it will dissociate into dihydrogen phosphate (H2P04) and hydrogen (H+) ions.
Dihydrogen phosphate then dissociates into hydrogen phosphate ion (HP04~2; pK2 of 7.09) and orthophosphate ion
(P04~3; pK3 of 12.32). As a result, phosphoric acid is not expected to volatilize or bioconcentrate in aquatic
organisms. The phosphates become available in the water column and form salts, thus affecting biological
C-45
-------
productivity (Bodek et al., 1988). Phosphorous, in the form of phosphate, is an essential nutrient to plants in aquatic
environments (Bodek et al., 1988). In addition, the phosphates can complex with metal ions in sediment and water to
form insoluble species such as FeP04 and CaHP04 (Bodek et al., 1988).
B. Atmospheric Fate
If phosphoric acid is released to the atmosphere, its vapor pressure indicates it will exist predominantly as a vapor in
the ambient atmosphere. Wet deposition of phosphoric acid in rain, snow, or fog is expected to be the dominant fate
process in the atmosphere based upon its solubility in water (Arimoto, 1989).
C. Terrestrial Fate
If phosphoric acid is released to soil, it will dissociate into dihydrogen phosphate and hydrogen ions, ultimately
dissociating to the orthophosphate ion at high pH's. Phosphate added to soil as fertilizer is quickly sorbed and later
"fixed" (probably precipitated) into less soluble forms (Bodek et al., 1988). A similar fate is anticipated for
phosphate species from phosphoric acid. While the exact mechanism of sorption is uncertain, phosphate fixation is
appreciable in all but very coarse-textured soils; only about one-fourth of the fertilizer phosphate is usable by plants,
the rest being lost to the occluded soil fraction (Bodek et al., 1988). Phosphorous, in the form of phosphate, is an
essential nutrient to plants (Bodek et al., 1988).
D. Summary
Phosphoric acid is a tribasic acid in which the first hydrogen is strongly ionizing, the second moderately weak, and the
third very weak. Both acidic and basic salts can be formed from phosphoric acid. If released into water, phosphoric
acid will dissociate into dihydrogen phosphate (H2P04) and hydrogen (H+) ions, eventually dissociating into the
orthophosphate ion (P04~3) under the proper conditions. Therefore, phosphoric acid is not expected to adsorb to
suspended solids or sediment in the water column, bioconcentrate in aquatic organisms, nor volatilize from water
surfaces. The phosphates become available in the water column and form salts, affecting biological productivity, and
complexing with metal ions form insoluble species such as FeP04 and CaHP04. If released to soil, phosphoric acid is
expected to dissociate into its component ions in moist soils. Phosphate added to soil as fertilizer is quickly sorbed
and later "fixed" into less soluble forms; phosphate fixation is appreciable in all but very coarse-textured soils; only
about one-fourth of the fertilizer phosphate is usable by plants, the rest being lost to the occluded soil fraction.
Phosphorous, in the form of phosphate, is an essential nutrient for aquatic and terrestrial plants. Volatilization of
phosphoric acid from soil surfaces is not expected to occur. If released to the atmosphere, phosphoric acid is
expected to exist as a gas. Phosphoric acid is expected to be physically removed from the atmosphere by wet
deposition based upon its water solubility.
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CHEMICAL SUMMARY FOR POTASSIUM AUROCYANIDE
This summary is based on information retrieved from a systematic search limited to secondary sources. The only
exception is summaries of studies from unpublished TSCA submissions that may have been included. These sources
include online databases, unpublished EPA information, government publications, review documents, and standard
reference materials. No attempt has been made to verify information in these databases and secondary sources.
I. CHEMICAL IDENTITY AND PHYSICAL/CHEMICAL PROPERTIES
The chemical identity and physical/chemical properties of potassium aurocyanide are summarized in Table 1.
TABLE 1. CHEMICAL IDENTITY AND CHEMICAL/PHYSICAL PROPERTIES OF POTASSIUM
AUROCYANIDE1
Characteristic/Property Data Reference
CAS No. (deleted)
CAS No.
Common Synonyms
Common Synonyms
Molecular Formula
Chemical Structure
Physical State
Molecular Weight
Melting Point
Boiling Point
Water Solubility
Water Solubility
Density
Vapor Density (air =1)
Koc
Log Kow
Vapor Pressure
Reactivity
Flammability
Flash Point
Dissociation Constant
Molecular Dif&sivity Constant
Air Dif&sivity Constant
Flenry's Law Constant
Fish Bioconcentration Constant
Odor Threshold
554-07-4
13967-50-5
gold potassium cyanide
potassium dicyanoaurate(I)
C2AuKN2
KAu(CN)2
dihydrate, crystalline powder
288.13
no data; expected to be > 350 °C
no data; expected to be > 500 °C
Approximately 130 g/L2
1 g dissolves in 0.5 ml boiling F120
3.45 g/cm3
no data
no data; expected to be < 10
no data; expected to be < 1
no data; expected to be <10-6 mm Fig at 25 C
stable in aqueous solution2
not flammable
no data; expected to be > 350 °C
readily dissociates to K+ and [Au(CN)J~
no data
no data
no data; expected to be < lxlO"8
no data
no data
CAS (1998)
CAS (1998)
Budavari et al. (1996)
Budavari et al. (1996)
Budavari et al. (1996)
Budavari et al. (1996)
Budavari et al. (1996)
Budavari et al. (1996)
SRC (1998)
SRC (1998)
Budavari et al. (1996)
Budavari et al. (1996)
Weast (1986)
SRC (1998)
SRC (1998)
SRC (1998)
Cotton and Wilkinson (1966)
ECDIN (1998)
SRC (1998)
Cohn and Stern (1994)
SRC (1998)
1 Both electrochemical and electroless gold plating processes that use potassium aurocyanide under basic conditions may contain potassium
cyanide as a complexing agent (Gmelin, 1998; Cohn and Stern, 1994; McDermott, 1974). The concentration of KCN is typically
approximately 6 g/L (0.1 M), although values as high as 200 g/L (3 M) have been reported (Gmelin, 1988).
2 Estimated from a reported solubility of 1 g dissolves in 7 ml F120 (Budavari et al., 1996).
3 Potassium aurocyanide is stable in aqueous solution under both basic and neutral conditions (Cotton and Wilkinson, 1966; Cohn and Stern,
1994). It is also stable in aqueous solutions under acidic conditions (Cohn and Stern, 1994), although common acids such as HC1, F[2SC>4,
F[NC>3, and F12S are known to degrade potassium aurocyanide (Gmelin, 1998) and release F1CN and gold monocyanide (Budavari et al., 1996;
Gmelin, 1998). Concentrated acids and elevated temperatures, or both, are required (Gmelin, 1998). Potassium aurocyanide is commonly
used in warm (35-55°C) acidic plating solutions at a pFl of approximately 4 (Gmelin, 1998) and stabilized acidic plating baths containing
C-47
-------
potassium aurocyanide have been reported down to a pH of 1.5 (McDermott, 1974), yet it is generally considered stable in water above pH 3
(Renner and Johns, 1989). These data indicate that potassium aurocyanide is expected to be chemically stable in the pH range 5-9 typically
found in the environment (Lyman et al, 1990), but not under highly acidic conditions such as those found in the stomach (pH 1-2).
IL ENVIRONMENTAL FATE
A. Aquatic Fate
If released to water, potassium aurocyanide will rapidly and completely dissociate into potassium (K+) and
aurocyanide ([Au(CN)2]~) ions (Cohn and Stern, 1994). The aurocyanide ion is expected to be stable to hydrolysis in
the pH range of 5-9 typically encountered in the environment (Lyman et al, 1990; SRC, 1998). The dissociation of
potassium aurocyanide into its component ions also indicates that it is not expected to volatilize from water surfaces
to the atmosphere, adsorb to sediment and suspended organic matter, orbioconcentrate in fish and aquatic organisms
(Bodeketal., 1988).
B. Atmospheric Fate
If released to the atmosphere, potassium aurocyanide will exist as a particulate. Its atmospheric fate will be
dominated by deposition to the Earth's surface via wet and dry processes, as potassium aurocyanide is not expected to
undergo degradation by the most common atmospheric oxidant, hydroxyl radicals (Lyman et al, 1990; SRC, 1998).
The rate of dry deposition will be dependent on the prevailing winds and particle size; fine particles of potassium
aurocyanide have the potential to be transported significant distances from their original point of release (Bodek et al,
1988). Potassium aurocyanide is expected to undergo efficient wet deposition in either rain or fog due to its water
solubility. Dissolution in clouds followed by wet deposition may also occur. Potassium aurocyanide is stable to
light (Cohn and Stern, 1994), and is not expected to undergo degradation by direct photolyis.
C. Terrestrial Fate
If potassium aurocyanide is released to soil, it is expected to display very high mobility based on its water solubility
of 143 g/L (Budavari, 1996). Therefore, it has the potential to leach into groundwater. Its rate of leaching through
soil may be attenuated by the formation of insoluble soil/aurocyanide complexes that can arise from reactions with
metals naturally present in soil (Bodek et al, 1988). The importance of complex formation for potassium aurocyanide
in soil is not known. The very high melting point and low vapor pressure expected for an ionic salt indicates that
potassium aurocyanide will not volatilize from either moist or dry soils to the atmosphere (Bodek et al, 1988).
D. Summary
If released to water, potassium aurocyanide will dissociate into K+ and [Au(CN)2]" ions. Therefore, it is not expected
to adsorb to sediment and suspended organic matter, bioconcentrate in fish and aquatic organisms, or volatilize from
water surfaces to the atmosphere. The aurocyanide ion is expected to be chemically stable and it is not expected to
hydrolyze in the pH range 5-9 typically found in the environment. In soil, potassium aurocyanide is likely to display
very high mobility as a result of its relatively high water solubility and it has the potential to leach to groundwater. Its
rate of leaching through soil may be attenuated by the formation of insoluble soil/aurocyanide complexes although
the importance of this process is not known. Volatilization from soil surfaces to the atmosphere is not expected to
occur. If released to the atmosphere, potassium aurocyanide is expected to exist as a particulate. Its atmospheric fate
is expected to be dominated by wet and dry deposition to the Earth's surface. Efficient removal from the atmosphere
during rain events is expected although the rate of dry deposition will be dependent on its particle size and the
prevailing wind patterns. Therefore, fine particles of potassium aurocyanide have the potential to travel significant
distances from their original point of release.
C-48
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CHEMICAL SUMMARY FOR POTASSIUM PEROXYMONOSULFATE
This summary is based on information retrieved from a systematic search limited to secondary sources. The only
exception is summaries of studies from unpublished TSCA submissions that may have been included. These sources
include online databases, unpublished EPA information, government publications, review documents, and standard
reference materials. No attempt has been made to verify information in these databases and secondary sources.
I. CHEMICAL IDENTITY AND PHYSICAL/CHEMICAL PROPERTIES
The chemical identity and physical/chemical properties of potassium peroxy mono sulfate are summarized in Table 1.
TABLE 1. CHEMICAL IDENTITY AND CHEMICAL/PHYSICAL PROPERTIES OF POTASSIUM
PEROXYMONOSULFATE
Characteristic/Property
Data
Reference
CAS No.
10058-23-8
CAS (1998)
Common Synonyms
Monopotassium peroxymonosulfurate
Flo ward and Neal (1992)
Common Synonyms
Peroxymonosulfiiric acid, monopotassium salt
Flo ward and Neal (1992)
Molecular Formula
ho5s.k
Flo ward and Neal (1992)
Chemical Structure
H00S(0)(0)0K
CAS (1998)
Physical State
no data
Molecular Weight
153.18
Flo ward and Neal (1992)
Melting Point
no data
Boiling Point
no data
Water Solubility
no data
Density
no data
Vapor Density (air =1)
no data
Koc
no data; expected to be <10
Estimated
Log Kow
no data; expected to be <1
Estimated
Vapor Pressure
no data; expected to be <1X10"6 mm Fig
Estimated
Reactivity
no data
Flammability
no data
Flash Point
no data
Dissociation Constant
expected to dissociate
Bodek etal. (1988)
Molecular Dif&sivity Constant
no data
Air Dif&sivity Constant
no data
Flenry's Law Constant
no data; expected to be <1X10"8
Estimated
Fish Bioconcentration Constant
no data
Odor Threshold
no data
IL ENVIRONMENTAL FATE
A. Aquatic Fate
Most potassium salts are highly dissociated in natural waters (Bodek et al., 1988). Therefore, if potassium
peroxymonosulfate is released into water, it is expected to dissociate into potassium (K+) and peroxymonosulfate
(S05~) ions. The potassium ion is expected to exist predominately as the free ion in most natural waters (Bodek et al.,
1988). Ion exchange processes with suspended solids and sediment in the water column are expected to remove ionic
potassium from solution; however, ionic potassium may be displaced by other cations present in natural waters with a
C-49
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higher affinity for ion exchange sites (Bodek et al., 1988). Aqueous solutions of the impure potassium
peroxymonosulfate, i.e., those containing dipotassium sulfate and monopotassium sulfate, decompose yielding
mainly 02 and sulfate (S042 ), hydrogen peroxide and peroxydisulfate (S2082 ) occur in small amounts (Cotton and
Wilkinson, 1980). Sulfate ions may participate in oxidation-reduction reactions or react with cations present in the
water column to form soluble complexes or insoluble precipitates (Bodek et al., 1988). Sulfate-reducing
microorganisms are important mediators in redox reactions involving this ion (Bodek et al., 1988). Peroxy
compounds are short-lived because of the inherent instability of the 0-0 bond and are expected to degrade rapidly
(U.S. EPA, 1993).
B. Atmospheric Fate
If potassium peroxymonosulfate is released to the atmosphere, the low vapor pressure expected for an ionic salt
indicates that potassium peroxymonosulfate will exist as a particulate. Wet and dry deposition of potassium
peroxymonosulate is expected to be an important fate process in the atmosphere (Arimoto, 1989). The rate of dry
deposition will depend on the prevailing winds and particle size (Bodek et al., 1988).
C. Terrestrial Fate
If potassium peroxymonosulfate is released to soil, it may decompose in moist soils; the importance of this process is
not known. The low vapor pressure expected for an ionic salt indicates that potassium peroxymonosulfate will not
volatilize from dry soil surfaces. The uncomplexed potassium ion is expected to be the predominant species in well-
drained soils from pH 4 to pH 10 (Bodek et al., 1988). Ion exchange reactions are expected to attenuate the mobility
of the potassium ion in the subsurface environment, however ionic potassium may be displaced by other cations with
a higher affinity for ion exchange sites (Bodek et al., 1988). Peroxy compounds are short-lived because of the
inherent instability of the 0-0 bond and are expected to degrade rapidly (U.S. EPA, 1993).
D. Summary
If released into water, potassium peroxymonosulfate is expected to dissociate into potassium and peroxymonosulfate
ions. The dissociation of potassium peroxymonosulfate into its component ions indicates that potassium
peroxymonosulfate is not expected to volatilize from water surfaces or bioconcentrate in aquatic organisms. In most
natural waters, the potassium ion is expected to exist predominately as the free ion. Ion exchange processes with
suspended solids and sediment in the water column are expected to remove ionic potassium from solution; however
ionic potassium may be displaced by other cations in natural waters with a higher affinity for ion exchange sites.
Sulfate ions may participate in oxidation-reduction reactions or react with cations present in the water column to
form soluble complexes or insoluble precipitates; sulfate-reducing microorganisms are important mediators in redox
reactions involving this ion. If released to soil, potassium peroxymonosulfate may decompose in moist soils or
dissociate into its component ions. As a result, potassium peroxymonosulfate is not expected to volatilize from
moist soil surfaces. The low vapor pressure expected for an ionic salt indicates that potassium peroxymonosulfate is
not expected to volatilize from dry soil surfaces. The mobility of potassium ions will be retarded by ion exchange
processes with charged surfaces of soil particles. However, since the potassium ion is held weakly by ion exchange
processes, it may leach into groundwater. Peroxy compounds are short-lived because of the inherent instability of the
0-0 bond and are expected to degrade rapidly. If released to the atmosphere, potassium peroxymonosulfate is
expected to exist as a particulate based upon the low vapor pressure expected for an ionic salt. Wet and dry
deposition is expected to be the dominant fate process in the atmosphere.
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CHEMICAL SUMMARY FOR PROPIONIC ACID
This summary is based on information retrieved from a systematic search limited to secondary sources. The only
exception is summaries of studies from unpublished TSCA submissions that may have been included. These sources
include online databases, unpublished EPA information, government publications, review documents, and standard
reference materials. No attempt has been made to verify information in these databases and secondary sources.
I. CHEMICAL IDENTITY AND PHYSICAL/CHEMICAL PROPERTIES
The chemical identity and physical/chemical properties of propionic acid are summarized in Table 1.
TABLE 1. CHEMICAL IDENTITY AND CHEMICAL/PHYSICAL PROPERTIES OF PROPIONIC ACID
Characteristic/Property
Data
Reference
CAS No.
79-09-4
Flo ward and Neal (1992)
Common Synonyms
methyl acetic acid; ethyl formic acid
Budavari et al. (1996)
Molecular Formula
c3h6o2
Budavari et al. (1996)
Chemical Structure
ch3ch2cooh
Budavari et al. (1996)
Physical State
oily liquid
Budavari et al. (1996)
Molecular Weight
74.08
Budavari et al. (1996)
Melting Point
-21.5 °C
Budavari et al. (1996)
Boiling Point
141.1 °C
Budavari et al. (1996)
Water Solubility
lxl0+3 g/1 @ 25 °C
U.S. EPA (1981)
Density
d25'4, 0.99336
Budavari et al. (1996)
Vapor Density (air =1)
no data
Koc
36 (calculated)
Lyman et al. (1990)
Log Kow
0.33
Flansch etal. (1995)
Vapor Pressure
3.53 mm Fig @ 25 °C
Daubert and Danner (1985)
Reactivity
corrodes steel, metal
Weiss (1986)
Flammability
combustible
Lewis (1993)
Flash Point
136 °F (58 °C), open cup
Budavari et al. (1996)
Dissociation Constant
pKa = 4.88
Serjeant and Dempsey (1979)
Molecular Dif&sivity Constant
no data
Air Dif&sivity Constant
no data
Flenry's Law Constant
4.45x10"7 atm m3/mole @ 25 °C
Butler and Ramchandani (1935)
Fish Bioconcentration Factor
0.02 (calculated)
Lyman etal. (1990)
Odor Threshold
no data
IL ENVIRONMENTAL FATE
A. Aquatic Fate
Aerobic biodegradation is likely to be the most important removal mechanism of propionic acid from aquatic systems
(Dias and Alexander, 1971, as cited in HSDB, 1998). With a pKa of 4.88 (Seijeant and Dempsey, 1979), propionic
acid and its conjugate base will exist in environmental waters in varying proportions that are pH dependent. Under
neutral and alkaline conditions, propionic acid is expected to exist predominantly as its conjugate base, the propionate
ion (Lyman et al., 1990). In addition, at a pH of 4.88 propionic acid is 50% dissociated; even under mildly acidic
conditions, it will exist predominantly as the conjugate base. In general, organic ions are not expected to volatilize
from water or adsorb to particulate matter in water to the degree that would be predicted for their neutral
C-51
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counterparts. An estimated Koc of 36, determined from a log Kow of 0.33 (Hansch et al., 1995), indicates propionic
acid should not partition from the water column to organic matter contained in sediments and suspended solids.
Similarly, the Kow indicates that bioconcentration in fish and aquatic organisms is not an important fate process.
Propionic acid's Henry's Law constant of 4.45xl0"7 atm nfVmolc (Butler and Ramchandani, 1935) indicates that
volatilization of propionic acid from environmental waters should be extremely slow (Lyman et al., 1990).
Volatilization will be attenuated depending upon pH and the amount of propionic acid that is dissociated. Since
carboxylic acids are generally resistant to aqueous hydrolysis (Lyman et al., 1990), it is not expected to be an
important fate process for propionic acid. The direct photolysis (Calvert and Pitts, 1966, as cited in HSDB, 1998)
and reaction of propionic acid with photochemically-generated hydroxyl radicals in water (Anbar and Neta, 1967, as
cited in HSDB, 1998) are also not expected to be important fate processes.
B. Atmospheric Fate
Based on a vapor pressure of 3.53 mm Hg at 25 ° C (Daubert and Danner, 1985, as cited in HSDB, 1998), propionic
acid is expected to exist almost entirely in the vapor phase in the ambient atmosphere (Bidleman, 1988). The rate
constant for the reaction of propionic acid with photochemically-produced hydroxyl radicals in air has been
experimentally determined to be 1.22 x 10"12 cm3/molecule-sec at 25 °C (Daugautetal., 1988, as cited in HSDB,
1998). This corresponds to an atmospheric half-life of approximately 13 days. Since low molecular weight organic
acids have absorption bands at wavelengths well below the environmentally important range of 290 nm, the direct
photolysis of propionic acid in air is not expected to be important (Calvert and Pitts, 1966, as cited in HSDB, 1998).
Extensive monitoring data (Chapman et al., 1986; Hoffman and Tanner, 1986; Winkeler et al., 1988; Mazurek and
Simoneitt, 1986, as cited in HSDB, 1998) has shown that physical removal of propionic acid from the air by wet
deposition (rainfall, dissolution in clouds, etc.) may be an important fate process under the appropriate atmospheric
conditions.
C. Terrestrial Fate
Biodegradation is likely to be the most important removal mechanism of propionic acid from aerobic soil (Dias and
Alexander, 1971, as cited in HSDB, 1998). With a pKa of 4.88 (Seijeant and Dempsey, 1979), propionic acid and its
conjugate base will exist in varying proportions that are dependent on the pH of the soil. A Henry's Law Constant of
4.45xl0"7 atm nfVmolc (Butler and Ramchandani, 1935) indicates that volatilization of propionic acid from moist
soil should be extremely slow (Lyman et al., 1990). Yet, propionic acid should volatilize rapidly from dry surfaces
based upon a vapor pressure of 3.53 mm Hg at 25 ° C (Daubert and Danner, 1985, as cited in HSDB, 1998).
Volatilization will be attenuated depending upon pH and the amount of propionic acid dissociated. An estimated Koc
of 36, determined from a log Kow of 0.33 (Hansch et al., 1995), indicates that propionic acid may be highly mobile
in soil (Swann et al., 1983). In addition, monitoring data has shown that propionic acid can leach to groundwater
(Stuermer et al., 1982; Burrows and Rowe, 1975; Lema et al., 1988, as cited in HSDB, 1998). Organic ions
generally do not volatilize from moist soil surfaces and do not undergo adsorption to the extent of their neutral
counterparts, which is consistent with propionic acid's potential for displaying high mobility through soils under
conditions where rapid biodegradation does not occur.
D. Summary
With a pKa of 4.88, propionic acid and its conjugate base will exist in environmental media in varying proportions
that are pH dependent; under typical environmental conditions, propionic acid will exist predominantly as its
conjugate base. A Henry's Law constant of 4.45xl0"7 atm nfVmolc at 25 ° C indicates that volatilization of propionic
acid from environmental waters and moist soil should be extremely slow. Yet, based on a vapor pressure of 3.53 mm
Hg, propionic acid should volatilize rapidly from dry surfaces. However, volatilization of propionic acid will be pH
dependent; if propionic acid is dissociated, very little (about 1%) will be available for volatilization. A relatively low
estimated Koc indicates that propionic acid should not partition from the water column to organic matter contained in
sediments and suspended solids; the Koc also indicates that it should be highly mobile in soil. However, monitoring
data has shown that propionic acid has the potential to leach to groundwater under the appropriate conditions.
Propionic acid is miscible with water and monitoring data has shown that physical removal from air by wet deposition
is an important removal mechanism. Biodegradation is likely to be the most important removal mechanism of
propionic acid from aerobic soil and water. In the atmosphere, propionic acid is expected to exist almost entirely in
the gas phase and oxidative removal by photochemically-produced hydroxyl radicals has a half-life of 13 days. The
C-52
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hydrolysis in water, photolysis in air, and bioconcentration in aquatic organisms are not expected to be important fate
processes for propionic acid.
C-53
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CHEMICAL SUMMARY FOR SILVER NITRATE
This summary is based on information retrieved from a systematic search limited to secondary sources. The only
exception is summaries of studies from unpublished TSCA submissions that may have been included. These sources
include online databases, unpublished EPA information, government publications, review documents, and standard
reference materials. No attempt has been made to verify information in these databases and secondary sources. The
search identified sources of information for silver nitrate, other nitrate salts and silver.
I. CHEMICAL IDENTITY AND PHYSICAL/CHEMICAL PROPERTIES
The chemical identity and physical/chemical properties of silver nitrate are summarized in Table 1.
TABLE 1. CHEMICAL IDENTITY AND CHEMICAL/PHYSICAL PROPERTIES OF SILVER NITRATE
Characteristic/Property
Data
Reference
CAS No.
7761-88-8
Lide(1995)
Common Synonyms
silver(I)nitrate
Lide(1995)
Molecular Formula
AgNO,
Budavari et al. (1996)
Chemical Structure
AgNO,
Lide(1995)
Physical State
colorless, rhombohedral crystals
Lide(1995)
Molecular Weight
169.873
Lide(1995)
Melting Point
212 °C
Lide(1995)
Boiling Point
440 °C decomposes
Lide(1995)
Water Solubility
2,500 g/L water
Budavari et al. (1996)
Density
4.35 g/cm3
Lide(1995)
Vapor Density (air =1)
no data
Koc
no data; expected to be < 10
SRC (1998)
Log Kow
no data; expected to be < 1
SRC (1998)
Vapor Pressure
no data; expected to be <10-6 mm Fig at 25 °C
Estimated
Reactivity
can explode on contact with soot, organics
Renner(1993)
Flammability
not flammable
Prager (1995)
Flash Point
no data; expected to be > 350 °C
SRC (1998)
Dissociation Constant
no data
Molecular Dif&sivity Constant
no data
Air Diffiisivity Constant
no data
Flenry's Law Constant
no data; expected to be < IX10"8
SRC (1998)
Fish Bioconcentration Constant
no data
Odor Threshold
no data
IL ENVIRONMENTAL FATE
A. Aquatic Fate
If silver nitrate is released into water, it is expected to dissociate into silver (Ag+) and nitrate (N03)" ions. The
dissociation of silver nitrate into its component ions indicates that silver nitrate is not expected to volatilize from
water surfaces or bioconcentrate in aquatic organisms (Bodek et al., 1988). Ionic silver may form complexes with
hydroxide, sulfide ligands, halide ligands, and chelating organics (Bodek et al., 1988). Silver-organic complexes may
be important (Bodek et al., 1988). In aquatic systems with high halide concentrations, precipitation of insoluble
silver halides may occur (Bodek et al., 1988). Silver ions may sorb to organic matter and sediment that has high
C-54
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manganese dioxide, iron oxide, and clay content (Bodek et al., 1988). Nitrate is a minor constituent in natural waters,
where its concentration is limited by biological reactions that consume it (Bodek et al., 1988). In aquatic systems
where nitrogen is a limiting nutrient, high loadings of nitrate into surface waters can cause algal blooms (Bodek et al.,
1988). In natural waters with a low nitrate concentration, complexation with transition metals is not expected to be
an important process (Bodek et al., 1988).
B. Atmospheric Fate
If released to the atmosphere, silver nitrate's low vapor pressure indicates that it will exist as a particulate (Bidleman,
1988). Wet and dry deposition of silver nitrate is expected to be the dominant fate process in the atmosphere
(Arimoto, 1989). Silver nitrate's high water solubility (Budavari et al., 1996) indicates that it is expected to undergo
wet deposition in rain, snow, or fog. The rate of dry deposition will depend on the prevailing winds and particle size
(Bodek et al., 1988). Pure silver nitrate is not photosensitive (Cappel, 1997); however, trace amounts of organic
material promote its photodegradation (Budavari et al., 1996).
C. Terrestrial Fate
If released to soil, silver nitrate is expected to dissociate into its component ions in the presence of moisture. Silver
may adsorb to manganese dioxide, iron oxides, clays, and organic matter (Bodek et al., 1988); therefore, its rate of
migration through soil may be slow. The high boiling point, low vapor pressure, and low Henry's Law constant
expected for an ionic salt (SRC, 1998) indicates that silver nitrate will not volatilize from either moist or dry soil
surfaces. Inoic silver may form complexes with hydroxide, sulfide ligands, halide ligands, and chelating organics
(Bodek et al., 1988). Nitrate ions may be converted to gaseous N2 or nitrous oxide (N20) by microorganisms under
anaerobic conditions or may be assimilated by plants (Bodek et al., 1988). Sorption of nitrate ions by soils is
generally insignificant and therefore nitrate ions are expected to leach into groundwater (Bodek et al., 1988).
D. Summary
If released into water, silver nitrate will dissociate into silver and nitrate ions. Therefore, silver nitrate is not expected
to adsorb to suspended solids or sediment in the water column, bioconcentrate in aquatic organisms, or volatilize
from water surfaces. In natural waters, the concentration of nitrate is limited by biological reactions that consume it.
High loadings of nitrate into surface waters can cause algal blooms if nitrogen is a limiting nutrient. Silver nitrate is
expected to dissociate into its component ions in moist soils, and ionic silver may adsorb to manganese dioxide, iron
oxides, and clays. Nitrate is highly mobile in soils and therefore may leach into groundwater. Under anaerobic
conditions nitrate may be converted to gaseous N2 or nitrous oxide by microorganisms. Volatilization of silver
nitrate from soil surfaces is not expected to occur. If released to the atmosphere, silver nitrate is expected to exist as a
particulate. Silver nitrate is expected to be physically removed from the atmosphere by wet and dry deposition. Dry
deposition will depend on particle size and prevailing wind patterns. Pure silver nitrate is not photosensitive and will
not degrade in sunlight; trace amounts of organic material promote silver nitrate's photodegradation.
C-55
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CHEMICAL SUMMARY FOR SODIUM HYDROXIDE
This summary is based on information retrieved from a systematic search limited to secondary sources. The only
exception is summaries of studies from unpublished TSCA submissions that may have been included. These sources
include online databases, unpublished EPA information, government publications, review documents, and standard
reference materials. No attempt has been made to verify information in these databases and secondary sources.
I. CHEMICAL IDENTITY AND PHYSICAL/CHEMICAL PROPERTIES
The chemical identity and physical/chemical properties of sodium hydroxide are summarized in Table 1.
TABLE 1. CHEMICAL IDENTITY AND CHEMICAL/PHYSICAL PROPERTIES OF SODIUM HYDROXIDE
Characteristic/Property Data Reference
CAS No.
Common Synonyms
Molecular Formula
Chemical Structure
Physical State
Molecular Weight
Melting Point
Boiling Point
Water Solubility
Density
Vapor Density (air =1)
Koc
Log Kow
Vapor Pressure
Reactivity
Flammability
Flash Point
Dissociation Constant
Molecular Dif&sivity Constant
Air Dif&sivity Constant
Flenry's Law Constant
Fish Bioconcentration Constant
Odor Threshold
1310-73-2
Caustic soda
HNaO
NaOH
white orthohombic crystals; hygroscopic
39.997
323°C
1388°C
571.9 g/L
2.13 g/cm3
not pertinent
no data; expected to be <10
no data; expected to be <1
no data; expected to be <10"6 mm Fig
when wet, attacks metals such as aluminum, tin, lead,
and zinc to produce flammable hydrogen gas
not flammable
not flammable
readily dissociates into Na+ and OF!"
no data
no data
no data; expected to be <1X10"8
no data
not pertinent
CAS (1998)
Bodek et al. (1988)
Budavari et al. (1996)
Budavari et al. (1996)
Lide(1995)
Lide(1995)
Lide(1995)
Lide(1995)
Weastet al. (1985)
Lide(1995)
Weiss (1986)
SRC (1998)
SRC (1998)
Weiss (1986)
Weiss (1986)
Weiss (1986)
Weiss (1986)
SRC (1998)
SRC (1998)
Weiss (1986)
IL ENVIRONMENTAL FATE
A. Aquatic Fate
If sodium hydroxide is released into water, it will dissociate into sodium (Na+) and hydroxide (OH ) ions (Bodek et
al., 1988). The dissociation of sodium hydroxide into its component ions indicates that sodium hydroxide is not
expected to volatilize from water surfaces or bioconcentrate in aquatic organisms. Because it is strongly basic,
sodium hydroxide will react with any protic acids to form salts. Hydroxide is the conjugate base of water;
protonation of hydroxide produces water. The presence of hydroxide in natural waters is entirely dependent on the pH
of the water, but massive amounts of sodium hydroxide may raise the pH of the receiving water. Metals present in
natural waters may form complexes with the hydroxide ion; complexes with transition metals will result in
C-56
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precipitation of the sparingly soluble metal hydroxides (Bodek et al., 1988). The sodium ion is expected to exist
predominately as the free ion in most natural waters (Bodek et al., 1988). Ion exchange processes with suspended
solids and sediment in the water column are expected to remove ionic sodium from solution; however, sodium binds
weakly to ion exchange sites and is expected to be displaced by other cations present in natural waters (Bodek et al.,
1988).
B. Atmospheric Fate
If sodium hydroxide is released to the atmosphere, it is expected to exist as a particulate based upon the low vapor
pressure expected for this compound. Wet deposition of sodium hydroxide (Arimoto, 1989) in rain, snow, or fog is
expected to be the dominant fate process in the atmosphere based upon its high water solubility (Budavari et al.,
1996); however, carbon dioxide dissolved in atmospheric water may react with sodium hydroxide to form sodium
carbonate.
C. Terrestrial Fate
If sodium hydroxide is released to soil, it is expected to dissociate into its component ions in moist soils and react
with any protic acids present in soil to form the sodium salt and water. The low vapor pressure and low Henry's Law
constant expected for an ionic salt indicates that sodium hydroxide will not volatilize from either moist or dry soil
surfaces. In soil, ion exchange processes are important in retarding the mobility of sodium ions, however they may be
replaced by other soil cations since the sodium ion is held weakly by soils (Evans, 1989).
D. Summary
If released into water, sodium hydroxide will dissociate into sodium and hydroxide ions. The dissociation of sodium
hydroxide into its component ions indicates that sodium hydroxide is not expected to volatilize from water surfaces
or bioconcentrate in aquatic organisms. The hydroxide ion will react with protic acids to form water. Massive
amounts of sodium hydroxide may raise the pH of the water. The sodium ion is expected to participate in ion
exchange reactions with charged surfaces of suspended sediments and sediment in the water column. If released to
soil, sodium hydroxide is expected to dissociate into its component ions in moist soils and react with protic acids to
form water. Sodium hydroxide is not expected to volatilize from moist or dry soil surfaces. The mobility of sodium
ions will be retarded by ion exchange processes with charged surfaces of soil particles. However, since the sodium
ion is held weakly by ion exchange processes, it may leach into groundwater. If released to the atmosphere, sodium
hydroxide is expected to exist as a particulate based upon the low vapor pressure expected for an ionic compound.
Sodium hydroxide reacts with carbon dioxide to form sodium carbonate. Wet deposition in rain, snow, or fog is
expected to be the dominant fate process in the atmosphere based upon sodium hydroxide's high water solubility.
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CHEMICAL SUMMARY FOR SODIUM HYPOPHOSPHITE AND
SODIUM HYPOPHOSPHITE MONOHYDRATE
This summary is based on information retrieved from a systematic search limited to secondary sources. The only
exception is summaries of studies from unpublished TSCA submissions that may have been included. These sources
include online databases, unpublished EPA information, government publications, review documents, and standard
reference materials. No attempt has been made to verify information in these databases and secondary sources.
I. CHEMICAL IDENTITY AND PHYSICAL/CHEMICAL PROPERTIES
The chemical identity and physical/chemical properties of sodium hypophosphite and its monohydrate are summarized
in Tables 1 and 2, respectively.
TABLE 1. CHEMICAL IDENTITY AND CHEMICAL/PHYSICAL PROPERTIES OF SODIUM
HYPOPHOSPHITE
Characteristic/Property Data Reference
CAS No.
Common Synonyms
Molecular Formula
Chemical Structure
Physical State
Molecular Weight
Melting Point
Boiling Point
Water Solubility
Density
Vapor Density (air =1)
Koc
Log Kow
Vapor Pressure
Reactivity
Flammability
Flash Point
Dissociation Constant
Molecular Dif&sivity Constant
Air Dif&sivity Constant
Flenry's Law Constant
Fish Bioconcentration Constant
Odor Threshold
7681-53-0
Phosphinic acid, sodium salt
H2Na02P
NaH2P02
colorless, pearly, crystalline plates or white granular
powder
87.98
no data
decomposes
approximately 500 g/L 1
no data
no data
no data; expected to be <10
no data; expected to be <1
no data; expected to be < 10"6 mm Fig
Explosion risk when mixed with strong oxidizing
agents.
no data
no data
2.1 (phosphinic acid)
no data
no data
no data; expected to be <1X10"8
no data
no data
CAS (1998)
Budavari et al. (1996)
Budavari et al. (1996)
Budavari et al. (1996)
Lewis (1993)
Budavari et al. (1996)
Dean (1985)
Estimated
Estimated
Estimated
Estimated
Lewis (1993)
Fee et al. (1996)
Estimated
Estimated from a reported solubility of 100 parts in 100 parts at 25 °C for the monohydrate (Dean 1985).
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TABLE 2. CHEMICAL IDENTITY AND CHEMICAL/PHYSICAL PROPERTIES OF SODIUM
H YPOPHO SPHITE MONOHYDRATE
Characteristic/Property
Data
Reference
CAS No.
Molecular Formula
Chemical Structure
Physical State
Molecular Weight
Melting Point
Boiling Point
Water Solubility
Density
Vapor Density (air =1)
Koc
Log Kow
Vapor Pressure
Reactivity
Flammability
Flash Point
Dissociation Constant
Molecular Dif&sivity Constant
Air Dif&sivity Constant
Flenry's Law Constant
Fish Bioconcentration Constant
Odor Threshold
10039-56-2
NaPH202-H20
NaPH202-H20
white, monoclinic
105.99
loses water at 200 °C
decomposes
approximately 500 g/L 1
no data
no data
no data; expected to be <10
no data; expected to be <1
no data; expected to be < 10"6 mm Fig
no data
no data
no data
2.1 (phosphinic acid)
no data
no data
no data; expected to be <1X10"8
no data
no data
CAS (1998)
Dean (1985)
Dean (1985)
Dean (1985)
Dean (1985)
Dean (1985)
Dean (1985)
Estimated
Estimated
Estimated
Estimated
Fee et al. (1996)
Estimated
1 Estimated from a reported solubility of 100 parts in 100 parts at 25 °C (Dean 1985).
IL ENVIRONMENTAL FATE
A.
Aquatic Fate
Almost all sodium salts are highly dissociated in natural waters (Bodek et al., 1988). Therefore, if sodium
hypophosphite is released into water, it is expected to initially hydrate to form the monohydrate then dissociate into
hypophosphite (H2P02~) and sodium (Na+) ions. The pKa of phosphinic acid indicates that hypophosphite will exist
mainly in the dissociated state in the environment. The dissociation of sodium hypophosphite into its component ions
indicates sodium hypophosphite will not volatilize from water surfaces or bioconcentrate in aquatic organisms. The
sodium ion is expected to exist predominately as the free ion in most natural waters (Bodek et al., 1988). Ion
exchange processes with suspended solids and sediment in the water column are expected to remove ionic sodium
from solution; however, sodium binds weakly to ion exchange sites and is expected to be displaced by other cations
present in natural waters (Bodek et al., 1988). No information specifically regarding the environmental fate of the
phosphinic acid or hypophosphite ion in water was located in the available literature. Phosphinic acid and its salts are
a strong reducing agents; they are oxidized to phosphonic acid or phosphonate (H3P03 or HP032") (Fee et al., 1996).
It is unclear how rapidly this process will occur in the environment.
B.
Atmospheric Fate
If sodium hypophosphite or its monohydrate are released to the atmosphere, it is expected to exist as a particulate
based upon the low vapor pressure expected for this compound. Particulates of the unhydrated salt may also hydrate
when exposed to moisture in the atmosphere to form the monohydrate. Wet deposition of sodium hypophosphite in
C-59
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rain, snow, or fog is expected to be the dominant fate process in the atmosphere (Arimoto, 1989) based upon its high
water solubility (Betterman et al., 1991).
C. Terrestrial Fate
If sodium hypophosphite is released to soil, it is expected to initially hydrate to form the monohydrate then dissociate
into its component ions in moist soils. The pKa of phosphinic acid indicates that it will exist mainly in the
dissociated state in the environment. The low vapor pressure and low Henry's Law constant expected for an ionic salt
indicates that neither sodium hypophosphite nor its hydrate will volatilize from either moist or dry soil surfaces. In
soil, ion exchange processes are important in retarding the mobility of sodium ions, however they may be replaced by
other soil cations since the sodium ion is held weakly by soils (Evans, 1989). No information specifically regarding
the environmental fate of the phosphinic acid or hypophosphite ion in soils was located in the available literature.
Phosphinic acid and its salts are a strong reducing agents; they are oxidized to phosphonic acid or phosphonate
(H3PO3 or HP032") (Fee et al., 1996). It is unclear how rapidly this process will occur in the environment.
D. Summary
If released into water, sodium hypophosphite and its hydrate are expected to dissociate into sodium and hypophosphite
ions. The dissociation of sodium hypophosphite into its component ions indicates that it will not volatilize from
water surfaces or bioconcentrate in aquatic organisms. The sodium ion is expected to participate in ion exchange
reactions with charged surfaces of suspended sediments and sediment in the water column. If released into soil,
sodium hypophosphite and its hydrate are expected to dissociate into its component ions in moist soils. As a result,
sodium hypophosphite is not expected to volatilize from moist soil surfaces. The mobility of sodium ions will be
retarded by ion exchange processes with charged surfaces of soil particles. However, since the sodium ion is held
weakly by ion exchange processes, it may leach into groundwater. Phosphinic acid and its salts are a strong reducing
agents; they are oxidized to phosphonic acid or phosphonate (H3P03 or HP032"). It is unclear how rapidly this process
will occur in either soil or water environments. The low vapor pressure expected for an ionic salt indicates that
neither sodium hypophosphite nor its monohydrate are expected to volatilize from dry soil surfaces. If released to the
atmosphere, the low vapor pressure expected for an ionic salt indicates that sodium hypophosphite will exist as a
particulate in the ambient atmosphere. Wet and dry deposition will be the dominant fate process in the atmosphere.
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CHEMICAL SUMMARY FOR STANNOUS METHANESULFONIC ACID
This summary is based on information retrieved from a systematic search limited to secondary sources. The only
exception is summaries of studies from unpublished TSCA submissions that may have been included. These sources
include online databases, unpublished EPA information, government publications, review documents, and standard
reference materials. No attempt has been made to verify information in these databases and secondary sources.
I. CHEMICAL IDENTITY AND PHYSICAL/CHEMICAL PROPERTIES
The chemical identity and physical/chemical properties of stannous methanesulfonic acid are summarized in Table 1.
TABLE 1. CHEMICAL IDENTITY AND CHEMICAL/PHYSICAL PROPERTIES OF STANNOUS
METHANESULFONIC ACID
Characteristic/Property
Data
Reference
CAS No.
53408-94-9
CAS (1998)
Molecular Formula
C2H806S2Sn
SRC (1998)
Chemical Structure
[H3CS(0)(0)0]Sn[0S(0)(0)CH3]
SRC (1998)
Physical State
no data
Molecular Weight
310.89
SRC (1998)
Melting Point
no data
Boiling Point
no data
Water Solubility
no data
Density
no data
Vapor Density (air =1)
no data
Koc
no data; expected to be <10
Estimated
Log Kow
no data; expected to be <1
Estimated
Vapor Pressure
no data; expected to be <10"6 mm Fig at 25 °C
Estimated
Reactivity
no data
Flammability
no data
Flash Point
no data
Dissociation Constant
no data
Molecular Dif&sivity Constant
no data
Air Dif&sivity Constant
no data
Flenry's Law Constant
no data; expected to be <10"8
Estimated
Fish Bioconcentration Constant
no data
Odor Threshold
no data
IL ENVIRONMENTAL FATE
A. Aquatic Fate
If stannous methanesulfonic acid is released into water, it is expected to dissociate into tin (Sn2+) and
methanesulfonate (CH3S03~) ions. The dissociation of stannous methanesulfonic acid into its component ions
indicates that stannous methanesulfonic acid is not expected to bioconcentrate in aquatic organisms or volatilize from
water surfaces. Ionic tin may adsorb to charged surfaces of suspended sediments and humic materials in the water
column (Evans, 1989). Methanesulfonic acid has a pKa of -1.86 (Seijeant and Dempsey, 1979 as cited in
PHYSPROP, 1998) indicating that it will exist in the ionized at pH values typically encountered in the environment.
Therefore, volatilization of methanesulfonate from water surfaces is not expected to be an important fate process.
Methanesulfonate ions may adsorb to charged surfaces of suspended solids and sediment in the water column,
C-61
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although the importance of this process in the environment is not known. Limited data indicate that biodegradation of
methanesulfonate may be an important fate process (HSDB, 1998). An estimated BCF of 3 for methane sulfonic acid
(Meylan et al., 1997) suggests the potential for bioconcentration in aquatic organisms is low (Franke et al., 1994).
B. Atmospheric Fate
If stannous methanesulfonic acid is released to the atmosphere, the low vapor pressure expected for an ionic salt
indicates that it will exist as a particulate. Dry deposition of stannous methanesulfonic acid is expected to be the
dominant fate process in the atmosphere (Arimoto, 1989). The rate of dry deposition will depend on the prevailing
winds and particle size (Bodek et al., 1988). Wet deposition of stannous methanesulfonic acid may occur (Arimoto,
1989) in rain, snow, or fog.
C. Terrestrial Fate
If stannous methanesulfonic acid is released to soil, it is expected to dissociate into its component ions in moist soils.
The dissociation of stannous methanesulfonic acid into its component ions in moist soils indicates that stannous
methanesulfonic acid is not expected to volatilize from moist soil surfaces. The low vapor pressure expected for an
ionic salt indicates that stannous methanesulfonic acid is not expected to volatilize from dry soil surfaces. Ionic tin
may adsorb to charged surfaces of soil particles or form inner sphere complexes with variable-charge soil surfaces
(Evans, 1989) and therefore its rate of migration through soil may be slow. Methanesulfonic acid has a pKa of -1.86
(Seijeant and Dempsey, 1979 as cited in PHYSPROP, 1998) indicating it will exist in the ionized form in moist soils
in the environment. Therefore, volatilization of methanesulfonate from moist soil surfaces will not occur.
Methanesulfonate ions may adsorb to charged surfaces of soil particles, however the importance of this process in the
environment is unknown. Limited data indicate that biodegradation of methanesulfonate may be an important fate
process (HSDB, 1998).
D. Summary
If released into water, stannous methanesulfonic acid is expected to dissociate into tin and methanesulfonate ions.
The dissociation of stannous methane sulfonic acid into it component ions indicates that stannous methanesulfonic
acid is not expected to bioconcentrate in aquatic organisms nor volatilize from water surfaces. Ionic tin may adsorb
to charged surfaces of suspended sediments and humic materials in the water column. Methanesulfonate ions may
adsorb to charged surfaces of suspended sediments and humic materials in the water column, however the importance
of this process in the environment is unknown. If released to soil, stannous methanesulfonic acid is expected to
dissociate into its component ions in moist soils. The dissociation of stannous methanesulfonic acid into its
component ions in moist soils indicates that volatilization from soil surfaces is not expected to be an important fate
process. Ionic tin may adsorb to charged surfaces of soil particles or form inner sphere complexes with variable-
charge soil surfaces and therefore its rate of migration through soil may be slow. Methanesulfonate ions may adsorb
to charged surfaces of soil particles, however the importance of this process in the environment is unknown. The low
vapor pressure expected for an ionic salt indicates that stannous methanesulfonic acid is not expected to volatilize
from dry soil surfaces. Limited data indicate that biodegradation of methanesulfonate may be an important fate
process. If released to the atmosphere, stannous methanesulfonic acid is expected to exist as a particulate in the
ambient atmosphere based upon the low vapor pressure expected for an ionic salt. Wet and dry deposition will be the
dominant fate process in the atmosphere. The rate of dry deposition will depend on the prevailing winds and particle
size.
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CHEMICAL SUMMARY FOR SULFURIC ACID
This summary is based on information retrieved from a systematic search limited to secondary sources. The only
exception is summaries of studies from unpublished TSCA submissions that may have been included. These sources
include online databases, unpublished EPA information, government publications, review documents, and standard
reference materials. No attempt has been made to verify information in these databases and secondary sources.
I. CHEMICAL IDENTITY AND PHYSICAL/CHEMICAL PROPERTIES
The chemical identity and physical/chemical properties of sulfuric acid are summarized in Table 1.
TABLE 1. CHEMICAL IDENTITY AND CHEMICAL/PHYSICAL PROPERTIES OF SULFURIC ACID
Characteristic/Property
Data
Reference
CAS No.
7664-93-9
CAS (1998)
Common Synonyms
Battery acid
Weiss (1986)
Molecular Formula
h2o4s
Budavari et al. (1996)
Chemical Structure
h2so4
Budavari et al. (1996)
Physical State
colorless oily liquid
Lide(1995)
Molecular Weight
98.080
Lide(1995)
Melting Point
10.31 °C
Lide(1995)
Boiling Point
337°C
Lide(1995)
Water Solubility
1000 g/L at 25° C
Gunther et al. (1968) as cited in
PHYSPROP (1998)
Density
1.8 g/cm3
Lide(1995)
Vapor Density (air =1)
not pertinent
Weiss (1986)
Koc
no data; expected to be <10
Estimated
Log Kow
no data; expected to be <1
Estimated
Vapor Pressure
5.98X10"5 mm Fig at25°C
Daubert and Danner (1987)
Reactivity
very reactive, dissolves most metals; concentrated
acid oxidizes, dehydrates, or sulfonates most organic
compounds, often causes charring.
Lewis (1993)
Flammability
not flammable
Weiss (1986)
Flash Point
not flammable
Weiss (1986)
Dissociation Constant
pK^ = -3.00, pKa2=1.99
Bodek etal. (1988)
Molecular Dif&sivity Constant
no data
Air Dif&sivity Constant
no data
Flenry's Law Constant
no data; expected to be <1X10"8
Estimated
Fish Bioconcentration Constant
no data
Odor Threshold
greater than 1 mg/m3
Weiss (1986)
IL ENVIRONMENTAL FATE
A. Aquatic Fate
If sulfuric acid is released into the water column at low concentrations, a pKal of -3.00 (Bodek et al., 1988) indicates
sulfuric acid will dissociate into bisulfate (HS04~) and hydrogen (H+) ions. In virtually all natural waters, the
bisulfate ion will also dissociate into sulfate (S042 ) and hydrogen ions based upon a pKa of 1.99 (Bodek et al., 1988).
Sulfuric acid will form salts with basic components in water. The dissociation of sulfuric acid into its component
ions indicates that sulfuric acid is not expected to volatilize from water surfaces orbioconcentrate in aquatic
C-63
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organisms. Sulfate ions may participate in oxidation-reduction reactions or react with cations present in the water
column to form soluble complexes or insoluble precipitates (Bodek et al., 1988). Sulfate-reducing microorganisms
are important mediators in redox reactions involving this ion (Bodek et al., 1988). Large releases of the concentrated
acid into water, such as may result from a spill, will result in a lowering of the pH (Bodek et al., 1988).
B. Atmospheric Fate
If sulfuric acid is released to the atmosphere, its vapor pressure (Daubert and Danner, 1987) indicates it will exist as a
particulate in the ambient atmosphere. Wet deposition of sulfuric acid in rain, snow, or fog is expected to be the
dominant fate process in the atmosphere (Arimoto, 1989) based upon its high water solubility (Gunther et al., 1968
as cited in PHYSPROP, 1998). In the atmosphere, S02 is oxidized to sulfuric acid (Graedel et al., 1986).
C. Terrestrial Fate
If sulfuric acid is released to soil, it will dissociate into sulfate and hydrogen ions in moist soils and will form salts
with basic soil components. The dissociation of sulfuric acid into its component ions indicates that volatilization
from moist soil surfaces is not expected to occur. Sulfate is generally weakly retained by soils (Bodek et al., 1988)
and therefore it may leach into groundwater. Adsorption of the sulfate ion may be important in humic soils
containing Al and Fe oxides (Bodek et al., 1988). Sulfuric acid's vapor pressure (Daubert and Danner, 1987)
indicates that volatilization from dry soil surfaces is not expected to be an important fate process.
D. Summary
If released into water, sulfuric acid will dissociate into sulfate (S042 ) and hydrogen (H+) ions. Therefore, sulfuric
acid is not expected to adsorb to suspended solids or sediment in the water column, bioconcentrate in aquatic
organisms, nor volatilize from water surfaces. Sulfate ions may participate in redox reactions or react with cations
present in the water column. Sulfate-reducing microorganisms have been identified as important mediators in redox
reactions involving the sulfate ion. Sulfuric acid will form salts with basic components in water. If released to soil,
sulfuric acid is expected to dissociate into its component ions in moist soils and will form salts with basic soil
components. The dissociation of sulfuric acid into its component ions indicates that volatilization from moist soil
surfaces is not expected to be an important fate process. In general, sulfate is weakly retained by soils and therefore it
may leach into groundwater. Adsorption of the sulfate ion may be important in soils with high organic matter content
or soils containing Al and Fe oxides. Sulfuric acid's vapor pressure indicates that volatilization from dry soil surfaces
is not expected to occur. If released to the atmosphere, sulfuric acid is expected to exist as a particulate. Sulfuric
acid is expected to be physically removed from the atmosphere by wet deposition based upon its high water solubility.
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CHEMICAL SUMMARY FOR THIOUREA
This summary is based on information retrieved from a systematic search limited to secondary sources. The only
exception is summaries of studies from unpublished TSCA submissions that may have been included. These sources
include online databases, unpublished EPA information, government publications, review documents, and standard
reference materials. No attempt has been made to verify information in these databases and secondary sources.
I. CHEMICAL IDENTITY AND PHYSICAL/CHEMICAL PROPERTIES
The chemical identity and physical/chemical properties of thiourea are summarized in Table 1.
TABLE 1. CHEMICAL IDENTITY AND CHEMICAL/PHYSICAL PROPERTIES OF THIOUREA
Characteristic/Property
Data
Reference
CAS No.
62-56-6
CAS (1998)
Common Synonyms
Thiocarbamide
Lide(1995)
Common Synonyms
Urea, 2-thio
Howard and Neal (1992)
Molecular Formula
CH4N2S
Lide(1995)
Chemical Structure
H2NC(=S)NH2
Budavari et al. (1996)
Physical State
crystals
Budavari et al. (1996)
Molecular Weight
76.12
Lide(1995)
Melting Point
182°C
Lide(1995)
Boiling Point
no data
Water Solubility
201 g/L at 20 ° C
Yalkowsky and Dannenfelser (1992)
Density
1.405 g/cm3 at 25°C
Lide(1995)
Vapor Density (air =1)
no data
Koc
no data; estimated to be 2.8
Meylan etal. (1992)
Log Kow
-1.02
Hansch etal. (1995)
Vapor Pressure
3.11X10"4 mm Hg at 25°C (extrapolated)
Daubert and Danner (1992)
Reactivity
no data
Flammability
no data
Flash Point
no data
Dissociation Constant
no data
Molecular Dif&sivity Constant
no data
Air Dif&sivity Constant
no data
Henry's Law Constant
no data; estimated to be 1.6X10"7
Meylan and Howard (1991)
Institute (1992)
Odor Threshold
no data
IL ENVIRONMENTAL FATE
A. Aquatic Fate
If thiourea is released into water, an estimated Koc value of 2.8 (Meylan et al., 1992) indicates that thiourea is not
expected to adsorb to suspended solids and sediment in the water column (Swann et al., 1983). According to a
classification scheme (Franke et al., 1994), BCFs of <0.2 and <2 in carp (Chemicals Inspection and Testing Institute,
1992) indicate that bioconcentration in aquatic organisms is low. An estimated Henry's Law constant of 1.6X10"7
atm nfVmolc at 25 ° C (Meylan and Howard, 1991) indicates that thiourea is expected to be essentially nonvolatile
C-65
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from water surfaces (Lyman et al., 1990). Thiourea has been demonstrated to be resistant to biodegradation in a
variety of standard biodegradation tests (HSDB, 1998). Thiourea reached 2.6% of its theoretical biological oxygen
demand over 2 weeks in the Japanese MITI test using an activated sludge seed and an initial chemical concentration of
30 mg/L (Chemicals Inspection and Testing Institute, 1992). In the OECD-screening test, 3% degradation was
observed (Schmidt-Bleek et al., 1982 as cited in HSDB, 1998) and 17% C02 evolution was measured in a 5-day
German GSF Biodegradation Test (Rott et al., 1982 as cited in HSDB, 1998). Thiourea is stable to hydrolysis at
environmental pHs (Schmidt-Bleek et al., 1982 as cited in HSDB, 1998).
B. Atmospheric Fate
If thiourea is released to the atmosphere, an extrapolated vapor pressure of 3.1IX 10~4 mm Hg at 25 ° C (Daubert and
Danner, 1992) indicates that thiourea will exist as a gas in the ambient atmosphere (Bidleman, 1988). The rate
constant for the gas-phase reaction of urea with photochemically-produced hydroxyl radicals has been estimated to be
4.2X10"11 cm3/molecule-sec at 25° C (Meylan and Howard, 1993); this corresponds to a half-life of 9.2 hours.
C. Terrestrial Fate
If thiourea is released to soil, an estimated Koc value of 2.8 (Meylan et al., 1992) indicates that thiourea is expected
to have very high mobility in soils (Swann et al., 1983). Thiourea is not expected to volatilize from moist soil
surfaces (Lyman et al., 1990) based upon its estimated Henry's Law constant (Meylan and Howard, 1991) or from dry
soils based on its vapor pressure. Biodegradation of thiourea by soil microorganisms may be an important fate
process, although microflora activity may be suppressed for extended periods of time by high concentrations of this
compound (HSDB, 1998). Degradation of thiourea was also observed in sterilized soils (Kolyada, 1969 as cited in
HSDB, 1998) indicating that abiotic degradation may be an important fate process.
D. Summary
If released into water, thiourea is not expected to be adsorb to suspended solids and sediment in the water column.
Bioconcentration in aquatic organisms and volatilization from water surfaces are not expected to be important fate
processes. Several biodegradation tests indicate that thiourea may be resistant to biodegradation. Thiourea is stable
to hydrolysis at environmental pHs. If released to the atmosphere, thiourea is expected to exist as a gas in the ambient
atmosphere based upon its extrapolated vapor pressure. Gas-phase thiourea is expected to be degraded in the
atmosphere by reaction with photochemically-produced hydroxyl radicals; the half-life for this reaction in air has been
estimated to be 9.2 hours. If released to soil, thiourea is expected to have very high mobility and therefore may leach
into groundwater. Volatilization from moist or dry soil surfaces is not expected to be an important fate process.
Biotic and abiotic degradation of thiourea may be important fate processes, however, no rates were available for these
processes. High concentrations of thiourea may suppress the activity of soil microorganisms for extended periods of
time.
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CHEMICAL SUMMARY FOR TIN
This summary is based on information retrieved from a systematic search limited to secondary sources. The only
exception is summaries of studies from unpublished TSCA submissions that may have been included. These sources
include online databases, unpublished EPA information, government publications, review documents, and standard
reference materials. No attempt has been made to verify information in these databases and secondary sources. The
search identified sources of information for Tin.
I. CHEMICAL IDENTITY AND PHYSICAL/CHEMICAL PROPERTIES
The chemical identity and physical/chemical properties of Tin are summarized in Table 1.
TABLE 1. CHEMICAL IDENTITY AND CHEMICAL/PHYSICAL PROPERTIES OF TIN
Characteristic/Property
Data
Reference
CAS No.
7440-31-5
Flo ward and Neal (1992)
Common Synonyms
Tin white
Weast (1983)
Molecular Formula
Sn
Flo ward and Neal (1992)
Chemical Structure
Physical State
Metal
Budavari et al. (1996)
Molecular Weight
118.69
Budavari et al. (1996)
Melting Point
231.9°C
Weast (1983)
Boiling Point
2260°C
Weast (1983)
Water Solubility
Insoluble
Weast (1983)
Density
7.31g/mL
Weast (1983)
Vapor Density (air =1)
no data
Koc
no data
Log Kow
no data
Vapor Pressure
no data
Reactivity
Flammable solid
Budavari et al. (1996)
Flammability
no data
Flash Point
no data
Dissociation Constant
no data
Molecular Dif&sivity Constant
no data
Air Dif&sivity Constant
no data
Flenry's Law Constant
no data
Fish Bioconcentration Constant
no data
Odor Threshold
no data
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CHEMICAL SUMMARY FOR TIN CHLORIDE
This summary is based on information retrieved from a systematic search limited to secondary sources. The only
exception is summaries of studies from unpublished TSCA submissions that may have been included. These sources
include online databases, unpublished EPA information, government publications, review documents, and standard
reference materials. No attempt has been made to verify information in these databases and secondary sources.
I. CHEMICAL IDENTITY AND PHYSICAL/CHEMICAL PROPERTIES
The chemical identity and physical/chemical properties of tin chloride are summarized in Table 1.
TABLE 1. CHEMICAL IDENTITY AND CHEMICAL/PHYSICAL PROPERTIES OF TIN CHLORIDE
Characteristic/Property
Data
Reference
CAS No.
Common Synonyms
Common Synonyms
Molecular Formula
Chemical Structure
Physical State
Molecular Weight
Melting Point
Boiling Point
Water Solubility
Density
Vapor Density (air =1)
Koc
Log Kow
Vapor Pressure
Reactivity
Flammability
Flash Point
Dissociation Constant
Molecular Dif&sivity Constant
Air Dif&sivity Constant
Flenry's Law Constant
Fish Bioconcentration Constant
Odor Threshold
7772-99-8
Tin (II) chloride
Stannous chloride
Cl2Sn
SnCl2
white orthorhombic crystals
189.615
247 °C
623°C
approximately 600 g/L 1
3.90 g/cm3
no data
no data; expected to be <10
no data; expected to be <1
no data; expected to be < 10"6 mm Hg
violent reactions with BrF3, CaC2, ethylene oxide,
hydrazine hydrate, nitrates, K, Na, H202
no data
no data
expected to dissociate into Sn2+ and CI"
no data
no data
no data; expected to be <1X10"8
no data
no data
CAS (1998)
Lide(1995)
Lewis (1993)
Sax(1984)
Lide(1995)
Lide(1995)
Lide(1995)
Lide(1995)
Lide(1995)
Estimated
Lide(1995)
SRC (1998)
SRC (1998)
SRC (1998)
Sax(1984)
SRC (1998)
SRC (1998)
1 Estimated from a reported solubility of 84 parts in 100 parts water (Dean, 1985).
IL ENVIRONMENTAL FATE
A.
Aquatic Fate
Water hydrolyzes tin halides (Cotton and Wilkinson, 1980). Therefore, if tin chloride is released into water, it is
expected to dissociate into tin (Sn2+) and chloride (CI ) ions. In waters containing excess chloride ion, tin chloride is
expected to dissolve, yielding SnCl3" (Cotton and Wilkinson, 1980). As a result, tin chloride is not expected to
volatilize from water surfaces or bioconcentrate in aquatic organisms. Ionic tin may adsorb to charged surfaces of
C-68
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suspended sediments and humic materials in the water column (Evans, 1989). The chloride ion may complex with
heavy metals, thereby increasing their solubility (Bodek et al., 1988). Adsorption of the chloride ion to suspended
solids and sediment in the water column is not expected to be an important fate process.
B. Atmospheric Fate
If tin chloride is released to the atmosphere, the low vapor pressure expected for an ionic salt indicates that it will
exist as a particulate. Dry deposition of tin chloride is expected to be the dominant fate process in the atmosphere
(Arimoto, 1989). The rate of dry deposition will depend on the prevailing winds and particle size (Bodek et al.,
1988). Tin chloride is expected to undergo wet deposition (Arimoto, 1989) in rain, snow, or fog due to its high
water solubility (Dean, 1985).
C. Terrestrial Fate
Water hydrolyzes tin halides (Cotton and Wilkinson, 1980). Therefore, if tin chloride is released to soil, it is expected
to dissociate into its component ions in moist soils. Ionic tin may adsorb to charged surfaces of soil particles or form
inner sphere complexes with variable-charge soil surfaces (Evans, 1989) and therefore its rate of migration through
soil may be slow. The dissociation of tin chloride into its component ions in moist soils indicates that tin chloride is
not expected to volatilize from moist soil surfaces. The low vapor pressure expected for an ionic salt indicates that tin
chloride is not expected to volatilize from dry soil surfaces. Chloride is extremely mobile in soils (Bodek et al.,
1988). The chloride ion may complex with heavy metals, thereby increasing their solubility (Bodek et al., 1988) and
potential for leaching into groundwater.
D. Summary
If released into water, tin chloride is expected to dissociate into tin and chloride ions. The dissociation of tin chloride
into its component ions indicates that tin chloride is not expected to volatilize from water surfaces or
bioconcentration in aquatic organisms. Ionic tin may adsorb to charged surfaces of suspended sediments and humic
materials in the water column. The chloride ion may complex with heavy metals, thereby increasing their solubility.
Adsorption of the chloride ion to suspended solids and sediment in the water column is not expected to be an
important fate process. If released to soil, tin chloride is expected to dissociate into its component ions in moist soils.
The dissociation of tin chloride into its component ions in moist soils indicates that tin chloride is not expected to
volatilize from moist soil surfaces. The low vapor pressure expected for an ionic salt indicates that tin chloride is not
expected to volatilize from dry soil surfaces. Ionic tin may adsorb to charged surfaces of soil particles or form inner
sphere complexes with variable-charge soil surfaces and therefore its rate of migration through soil may be slow. The
chloride ion is extremely mobile in soils; it may complex heavy metals, thereby increasing their solubility and the
potential to leach into groundwater. If released to the atmosphere, tin chloride is expected to exist as a particulate in
the ambient atmosphere based upon the low vapor pressure expected for an ionic salt. Wet and dry deposition will be
the dominant fate process in the atmosphere. The rate of dry deposition will depend on the prevailing winds and
particle size.
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CHEMICAL SUMMARY FOR UREA
This summary is based on information retrieved from a systematic search limited to secondary sources. The only
exception is summaries of studies from unpublished TSCA submissions that may have been included. These sources
include online databases, unpublished EPA information, government publications, review documents, and standard
reference materials. No attempt has been made to verify information in these databases and secondary sources.
I. CHEMICAL IDENTITY AND PHYSICAL/CHEMICAL PROPERTIES
The chemical identity and physical/chemical properties of urea are summarized in Table 1.
TABLE 1. CHEMICAL IDENTITY AND CHEMICAL/PHYSICAL PROPERTIES OF UREA
Characteristic/Property
Data
Reference
CAS No.
57-13-6
CAS (1998)
Common Synonyms
Carbamide
Lide(1995)
Common Synonyms
Carbonyldiamide
Budavari et al. (1996)
Molecular Formula
ch4n2o
Lide(1995)
Chemical Structure
H2NC(=0)NH2
Budavari et al. (1996)
Physical State
Tetragonal prisms
Budavari et al. (1996)
Molecular Weight
60.06
Lide(1995)
Melting Point
132.7°C
Lide(1995)
Boiling Point
decomposes
Lide(1995)
Water Solubility
545 g/L at25°C
Yalkowsky and Dannenfelser (1992)
Density
1.3230 g/cm3 at 20°C
Lide(1995)
Vapor Density (air =1)
not pertinent
Weiss (1986)
Koc
8
Hance (1965) as cited in HSDB (1998)
Log Kow
-2.11
Hansch etal. (1995)
Vapor Pressure
1,2X 10"5 mm Fig at 25 ° C (extrapolated)
Jones (1960) as cited in PHYSPROP
(1998)
Reactivity
no reaction with water or common materials
Weiss (1986)
Flammability
not flammable
Weiss (1986)
Flash Point
not flammable
Weiss (1986)
Dissociation Constant
no data
Molecular Dif&sivity Constant
no data
Air Dif&sivity Constant
no data
Flenry's Law Constant
no data; estimated to be less than IX10"8
PHYSPROP (1998)
Fish Bioconcentration Constant
<10
Freitag et al. (1985) as cited in HSDB
(1998)
Odor Threshold
not pertinent
Weiss (1986)
IL ENVIRONMENTAL FATE
A. Aquatic Fate
If urea is released into water, a Koc value of 8 (Hance, 1965 as cited in HSDB, 1998) indicates that urea is not
expected to adsorb to suspended solids and sediment in the water column (Swann et al., 1983). According to a
classification scheme (Franke et al., 1994), a BCF of <10 in golden ide (Freitag et al., 1985 as cited in HSDB, 1998)
indicates that bioconcentration in aquatic organisms is low. An estimated Henry's Law constant of <1X10"8 atm
nfVmolc at 25 °C (PHYSPROP, 1998) indicates that urea is expected to be essentially nonvolatile from water
C-70
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surfaces (Lyman et al., 1990). In natural waters, biodegradation of urea is expected to be an important fate process;
ammonia and carbon dioxide have been identified as degradation products (HSDB, 1998). The rate of biodegradation
is expected to decrease with decreasing temperatures; at 8 ° C, negligible degradation was observed after incubation in
river water for 14 days, while at 20 ° C complete degradation was observed after 4 to 6 days incubation (Evans and
Patterson, 1973 as cited in HSDB, 1998). The presence of naturally-occurring phytoplankton in water is expected to
increase the rate of biodegradation (HSDB, 1998). Urea is used as an agricultural fertilizer (Lewis, 1993) and will be
taken up by plants as a source of nitrogen. Abiotic hydrolysis of urea occurs slowly yielding ammonium carbamate
(HSDB, 1998). At 5 ° C, 0.35% of urea hydrolyzed during a 10-day test period in demineralized/distilled water
(Atkinson, 1971 as cited in HSDB, 1998).
B. Atmospheric Fate
If urea is released to the atmosphere, a vapor pressure of 1.2X105 mmHg at 25 °C (Jones, 1960 as cited in
PHYSPROP, 1998) indicates that urea will exist as both a particulate and a gas in the ambient atmosphere (Bidleman,
1988). The rate constant for the gas-phase reaction of urea with photochemically-produced hydroxyl radicals has
been estimated to be 2.0X10"12 cm3/molecule-sec at 25 ° C (Meylan and Howard, 1993); this corresponds to a half-life
of 8.0 days. Particulate-phase urea is expected to be physically removed from the atmosphere by wet and dry
deposition (Arimoto, 1989).
C. Terrestrial Fate
If urea is released to soil, it is expected to hydrolyze to ammonia through soil urease activity (HSDB, 1998). The rate
of hydrolysis can range from 24 hours to weeks depending upon soil type, moisture content, and urea formulation
(Malhi and Nyborg, 1979 as cited in HSDB, 1998). Urea is used as an agricultural fertilizer (Lewis, 1993) and will
be taken up by plants as a source of nitrogen. While no specific studies were identified in the literature, it is
anticipated that urea will biodegrade rapidly in soil as has been reported in water. A Koc value of 8 (Hance, 1965 as
cited in HSDB, 1998) indicates that urea is expected to have very high mobility in soils (Swann et al., 1983). Urea is
not expected to volatilize from soil surfaces based upon its vapor pressure and estimated Henry's Law constant.
D. Summary
If released into water, urea is expected to be biodegraded yielding ammonia and carbon dioxide. Biodegradation is
expected to be more rapid in waters containing phytoplankton and during summer months when warmer water
temperatures prevail. Urea will be taken up by plants and used as a source of nitrogen. Bioconcentration in aquatic
organisms, adsorption to suspended solids and sediment in the water column, and volatilization from water surfaces
are not expected to be important fate processes. If released to the atmosphere, urea is expected to exist as both a
particulate and as a gas based upon its vapor pressure. Gas-phase urea is expected to be degraded in the atmosphere
by reaction with photochemically-produced hydroxyl radicals; the half-life for this reaction in air has been estimated
to be 8.0 days. Particulate-phase urea is expected to be physically removed from the atmosphere by wet and dry
deposition. The rate of dry deposition will depend upon particle size and prevailing wind patterns. If released to soil,
urea is expected to hydrolyze to ammonia through the activity of soil urease as well as biodegrade as is the case in
water. The rate of hydrolysis can range from 24 hours to weeks depending upon soil type, moisture content, and urea
formulation. Urea is used an agricultural fertilizer as a source of nitrogen. Urea is expected to have very high
mobility in soils and therefore may leach into groundwater. Volatilization from moist and dry soil surfaces is not
expected to be an important fate process.
C-71
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TRI93. 1995. Toxics Release Inventory, Public Data Release. Office of Pollution Prevention and Toxics, U.S. EPA,
Washington, DC.
U.S. Air Force. 1990. Copper - Elemental Copper. In: The Installation Restoration Toxicology Guide, Vol. 5.
Wright-Patterson Air Force Base, OH. pp: 77-1 - 77-44.
U.S. EPA. 1981. Treatability Manual I. Treatability Data. EPA-600/2-82-001A. U.S. EPA, Washington, DC.
U.S. EPA. 1987. Drinking Water Criteria Document for Copper. Environmental Criteria and Assessment Office,
Office of Health and Environmental Assessment, Environmental Criteria and Assessment Office, Cincinnati, OH.
ECAO-CIN-477.
U.S. EPA. 1993. Reregistration Eligibility Document (RED): Peroxy Compounds. EPA 738-R-93-030. Office of
Pesticide Programs, Special Review and Reregistration Division.
Verschueren, K. 1996. Handbookof Environmental Data on Organic Chemicals, 3rd Edition. VanNostrand
Reinhold, New York, NY.
VonOepenB., W. Koerdel and W. Klien. 1991. Title not available. Chemosphere 22: 285-304. Cited in HSDB.
1998.
Weast, R.C. 1983. CRC Handbookof Chemistry and Physics. CRC Press, Boca Raton, FL.
Weast, R.C. (Ed). 1983-1984. CRC Handbook of Chemistry and Physics, 64th Edition. CRC Press, Inc., Boca
Raton, Florida, p. B-139.
Weast, R.C., M.J. Astle and W.H. Beyer. 1985. CRC Handbook of Chemistry and Physics, 66th Edition. CRC
C-78
-------
Press, Boca Raton, FL. p. D-245.
Weast, R.C. 1986. CRC Handbook on Organic Compounds. (Cited in HSDS 1959).
Weiss, G. 1986. Hazardous Chemicals Data Book, 2nd Edition. Noyes Data Corporation, Park Ridge, NJ.
Winkeler, H.D., U. Puttins andK. Levsen. 1988. Title not available. VomWasser 70: 107-17. Cited in HSDB,
1998.
Yalkowsky, S.H. andR.M. Dannenfelser. 1992. Aquasol Database of Aqueous Solubility, Version 5. College of
Pharmacy, Univ. of Ariz, Tucson, AZ. PC Version.
Yaws, C.L. 1994. Handbook of Vapor Pressure, Vol. 1 - CI to C4 Compounds. Gulf Publishing Co, Houston, TX.
Zahn, R. and H. Wellens. 1980. Title not available. Z Wasser Abwasser Forsch 13:1-7. CitedinHSDB, 1998.
C-79
-------
Appendix D
Supplemental Exposure
Assessment Information
-------
Technical Memorandum RE: Modeling Worker Inhalation Exposure
D-l
-------
D.l Technical Memorandum RE: Modeling Worker Inhalation Exposure
TECHNICAL MEMORANDUM
TO:
Debbie Boger
PWB Project File, EPA # X823941-01-0
cc:
Lori Kincaid, Jack Geibig, Dean Menke, Diane Perhac
FROM: Bruce Robinson, Chris Cox, Nick Jackson, Mary Swanson
DATE: December 22, 1995
(Revised 8/96)
RE:
MODELING WORKER INHALATION EXPOSURE
I. INTRODUCTION
This technical memorandum is submitted for review by the RM2 work group. Air transport
models to estimate worker inhalation exposure to chemicals from printed wiring board (PWB)
making holes conductive (MHC) lines are presented here for review and comment. The purpose
is to reach agreement on our technical approach before proceeding with further analysis.
Three air transport models will be required to estimate worker exposure:
! Volatilization of chemicals induced by air sparging.
! Aerosol generation induced by air sparging.
! Volatilization of chemicals from the open surface of MHC tanks.
The total transport of chemicals from the air-sparged baths will be determined by summing the
releases calculated using each of the three models described above. Air-sparged baths include the
electroless-copper baths and some cleaning tanks. Only the third model will be applied to
determine the atmospheric releases of chemicals from unsparged baths. This document includes
a review of the relevant literature, descriptions of the models, and examples demonstrating the
proposed use of the models. The results of the model calculations will be compared to available
occupational monitoring data.
D-2
-------
II. VOLATILIZATION OF CHEMICALS FROM AIR-SPARGED PWB
MANUFACTURING TANKS
Mixing in plating tanks, e.g., the electroless copper plating tank, is commonly accomplished by
sparging the tank with air. This is similar to aeration in wastewater treatment plants, and the
volatilization of chemicals from these plants has been the focus of recent research. The
volatilization models used in that research are based on well accepted gas transfer theory,
discussed below.
Background
Volatilization of chemicals from water to air has been investigated by many researchers (Liss and
Slater, 1974; Smith etal., 1980; Roberts, 1983; Peng et al., 1993). In PWB manufacturing,
volatilization due to air sparging of process tanks is expected to be one of the main pathways for
contaminant transfer to the air. In bubble aeration systems, the volatilization rate is dependent
upon the volumetric gas flow rate, partial pressure of the gas, and the mass transfer rate
coefficient (Matter-Miiller, 1981). The volatilization characteristics for different diffuser types
and turbulent conditions were evaluated by Matter-Miiller (1981), Peng (1995), and Hsieh (1994).
Volatilization from aerated systems has been mainly quantified using the two-film theory (Cohen
et al., 1978; Mackay and Leinonen, 1975). This work is discussed below and is used to model
chemical transfer rates from air-sparged PWB process tanks. The main assumption of the theory
is that the velocity at a fluid interface is zero. Molecular diffusion across the interfacial liquid film
is the limiting factor for mass transfer to the air, and it is used to develop a simple equation
relating the overall mass transfer coefficient to the diffusion coefficient of the chemical in water.
The two-film model of gas transfer was expanded to include mass transfer in diffused aeration
systems (Matter-Miiller et al., 1981). Matter-Miiller et al. assumed that the system was
isothermal, hydraulic conditions were steady, and that pressure and volume changes within the
bubbles were negligible. Further, an overall mass transfer coefficient was applied to represent
transfer of contaminants to the bubble as they rose through the homogeneous liquid volume.
Parker (1993) demonstrated that liquid-phase concentration can be assumed constant during the
rise time of the bubble. Under these assumptions, Matter-Miiller et al. derived the following
relationship predicting the mass transfer rate from an aerated system:
F =QrH c
y.s y j
y Uy
-exp
_ ^OL,ya^L
HQ,
y^G
(1)
where:
FyiS = mass transfer rate of chemical y out of the system by sparging (m/t)
Qg = gas flow rate (l3/t)
Hy = dimensionless Henry' s constant for chemical y
cLy = concentration of chemical y in bulk liquid (m/13)
K()lv = overall mass transfer coefficient for chemical y (1/t)
D-3
-------
a = interfacial area of bubble per unit volume of liquid (12/13)
VL = volume of liquid (l3)
The overall mass-transfer coefficient is defined as the inverse sum of the reciprocals of the liquid
and gas-phase mass transfer coefficients; but, because molecular diffusion of oxygen and
nonpolar organic substances is 103 times greater in air than in water (Matter-Muller el al., 1981), it
is set equal to the liquid phase coefficient only. The mass transfer coefficient of a chemical can
then be related to oxygen using the following equation:
K,
OL,y
( \
D
y
D.
02
K,
0L,02
(2)
where:
Dy
D02
K(3L,y
Kql,02
= molecular diffusion coefficient for chemical y in water (l2/t)
= molecular diffusion coefficient for oxygen in water (l2/t)
= 2.1xl0"5 cm2/cm @ 25° C (Cussler, 1984)
= overall mass transfer coefficient for chemical y (1/t)
= overall mass transfer coefficient for oxygen in water (1/t)
The value of KOL,o2 at 25°C in diffused aeration systems can be estimated using a correlation
developed by Bailey and Ollis (1977):
Kqlo =031*
(PH20 P air^S
where:
db
V-H2cPo2
= bubble diameter (1)
1/3
D
02
d,
(3)
PH20 = density of water (m/13)
pair = density of air (m/13)
g = gravitational constant (1/t2)
Hmo = viscosity of water (m/l-t)
If a measured value of Dy is not available, then it can be calculated from the Hayduk and Laudie
correlation (Lyman etal., 1982):
rw 2/ \ 13.26x70
D (cm Isec)=
y 1.14 xrO.589
%20 Vm
(4)
where:
Vm = molar volume of solute (cm3/mol)
I^h2o = viscosity of water (centipoise)
D-4
-------
The mass transfer coefficient can be corrected for the bath temperature (°C) as follows
(Tschabanoglous, 1991):
KOL,y,T =KOL,y,25°cl.024(T-25) (5)
Bailey and Ollis (1977) developed a relationship for the interfacial area per unit volume (a) as a
function of the bubble diameter, gas flow rate, and tank geometry:
a=_6 0G h
VL db (6)
where:
h = tank depth (1); and
^ 18 h \iH20
t Z. '
(P H20 P air^S (7)
Values of Hy are often reported at 25°C. The Henry's constant can be corrected to the bath
temperature using the van't Hoff equation:
Hyj Hy25"CexP
A H -A H
gas aq
l l
R ^ 298.15 273.15+rJ
(8)
where:
Ar|gas = enthalpy of the chemical in the gas phase (cal/mol)
AHaq = enthalpy of the chemical in the aqueous phase (cal/mol)
R = gas constant (1.987 cal/mol-K)
Matter-Miiller (1981) concluded that surfactants do not significantly alter the rate of volatilization
from the water. Some agents did lower the overall mass transfer coefficient, but most showed no
appreciable difference. This was attributed to an increase in the specific interfacial area, a, when
the interfacial energy, or mass transfer coefficient, was decreased. The transfer rate of volatile
organic compounds (VOCs) was found to depend heavily upon the type of aerators used, and the
degree of saturation of the bubbles rising through the liquid.
III. AEROSOL GENERATION FROM BATHS MIXED BY SPARGING WITH AIR
Aerosols or mists have been identified as a major source of contaminants released by
electroplating baths to the atmosphere (Burgess, 1981) and should be investigated as a potential
source of contaminants from electroless baths. At least two sources of aerosols exist in
electroplating baths: 1) aerosols generated due to liquid dripping from parts as they are removed
D-5
-------
from the bath (drag-out drips); and 2) aerosols generated due to bursting of the bubbles at the
surface. Drag-out drips are insignificant compared to other sources of aerosols (Berglund and
Lindh, 1987; Cooper et al., 1993).
Bubbles in electroplating baths can originate from the dissociation of water at the electrode, or
mixing of the bath via air sparging. Bubbles in other plating baths (e.g., electroless plating baths)
can originate from reactions in the bath or mixing of the bath via air sparging. The rate of aerosol
generation per unit bubble volume decreases with increasing bubble size. Bubbles generated by
water dissociation are typically smaller than those generated by air sparging; therefore, aerosol
generation in electroless plating processes may be less significant than in electroplating
operations. The focus of this memo is aerosols generated by air sparging. Except for the
conductive polymer and non-formaldehyde electroless alternatives, MHC processes in PWB
manufacturing do not use electroplating and therefore would not dissociate water to form gas
bubbles. Information collection is continuing to allow prediction of aerosol formation in MHC
processes that do have an electroplating step. Importantly, Berglund and Lindh (1987) report that
aerosol generation from electroplating tanks is greatly reduced by sparging; the relatively large air
bubbles formed during air sparging coalesce the smaller bubbles formed by hydrolysis and
electroless plating reactions.
To estimate the emission of contaminants resulting from aerosols, the rate of aerosol generation
and the concentration of contaminant in the aerosol are required. Limited information
concerning the rate of aerosol formation was found in the literature. The following sources were
consulted:
! U.S. EPA (1991). Chemical Engineering Branch Manual for the Preparation of
Engineering Assessments.
! Chemical Abstracts, 1986 to date.
! Current and past text books in air pollution, chemical engineering, and water and
wastewater treatment.
! Perry's Handbook (1984) related to entrainment in distillation trays.
! The last five years of Water Environment Research and ASCE Journal of the
Environmental Engineering Division.
! A title key-word search of holdings in the library of the University of Tennessee.
! The ASPEN model commonly used for modeling chemical manufacturing processes. (It
was found that any aerosol formation routines within ASPEN would be relevant to
entrainment in devices such as distillation trays and not relevant to sparging of tanks.)
! The manager of the US EPA Center for Environmental Assessment Modeling in Athens,
Georgia, as well as an expert in the Air and Energy Lab - Emission Modeling Branch in
North Carolina.
D-6
-------
In this work, the aerosol formation rates will be predicted based upon limited measurements of
aerosol generation in electroplating (Berglund and Lindh, 1987) and other air-sparged baths
(Wangwongwatana et al., 1988; Wangwongwatana et al., 1990) found in the literature.
Berglund and Lindh (1987) developed several graphs relating aerosol generation to air sparging
rate (Figure la), bath temperature (Figure lb), air flow rate above the bath (Figure lc), and
distance between bath surface and the tank rim (Figure Id). Using Figures la-Id, the following
relationship may be developed:
where:
Ra = aerosol generation rate (ml/min/m2)
Qg/A = air sparging rate per unit bath area (1/min/m2)
Fx = temperature correction factor
Fa = air velocity correction factor
Fd = distance between the bath surface and tank rim correction factor
Wangwongwatana et al. (1988) presented figures relating the number of aerosol droplets
generated as a function of air flow rate, bubble rise distance, bubble size, and colloid
concentration (Figure 2). Droplet size distribution measurements by these researchers indicate
volume mean diameters of 5 to 10 |im. The aerosol generation rate can be calculated using the
following equation:
where:
Cd = droplet concentration (l"3)
Vd = droplet volume (1)
A = bath area (l2)
Contaminants may be present in aerosols at elevated concentration relative to the bath
concentration. Colloidal contaminants may be collected on the bubble surface as it rises through
the bath. As the bubble bursts, the contaminants on the bubble surface are incorporated into
aerosols. Wangwongwatana et al. (1990) report that in their experiments about one in two
aerosols contain polystyrene latex spheres, compared to about one in 250 expected based upon
the concentration of latex sphere in the bath. Organic contaminants may also partition at the air-
water interface. A correlation for the water-interface partitioning coefficient for nonpolar
compounds, kIW, defined as the ratio of the mass of contaminant per unit area of interface to the
mass of contaminant per unit volume of water is given by Hoff et al. (1993):
Ra = 5.5x10 5(Qg / ^+0.01 Ft Fa Fd
(9)
(10)
log V="8-58 "°-769 lo§ Cw
(11)
D-7
-------
where:
Csw = saturated aqueous solubility of the contaminant.
For more polar compounds a more complicated relationship is required:
log kIW = -7.508+log y +a (o -o -1.35a )/2.303i?r
O IW J w wa sa sws
(12)
IW '"6 I w .A wa sa
where:
yw = activity coefficient of the contaminant in water (dimensionless)
as = molar area of the solute (cm2/mol)
R = gas constant (8.314x107 erg/mol K)
oWA = surface tension of the water-air interface (dyne/cm)
oSA = surface tension of the solute-air interface (dyne/cm)
asw = surface tension of the solute-water interface (dyne/cm)
Hoff et al. (1993) also present a relationship for the ratio of the mass of contaminant sorbed at the
air-water interface to the mass of contaminant in the gas volume of the bubble:
Mi kiw
^b Hy(db / 6)
where:
M, = mass of contaminant at the interface
Mb = mass of contaminant in gas bubble
Only a small fraction of the bubble interface will be ejected as aerosols. It may be calculated
from the following equation:
Ra A d,
x _ A b
J IE 1
° &G Lb (14)
where:
fIE = fraction of bubble interface ejected as aerosols (dimensionless)
lb = thickness of bubble film (1)
The rate of mass transfer from the tank to the atmosphere by aerosols, Fy a (m/t) is given by:
M1
F = L f F
y,a j.A J IE y,s
Mt- (15)
D-8
-------
IV. VOLATILIZATION OF CHEMICALS FROM THE OPEN SURFACE OF MHC
TANKS
Most plating tanks have a free liquid surface from which chemicals can volatilize into the
workplace air. Air currents across the tank will accelerate the rate of volatilization. The model
presented in the Chemical Engineering Branch Manual for the Preparation of Engineering
Assessments (CEBMPEA) (US EPA, 1991) has potential application in this case. Some
limitations of the model should be pointed out. The model was developed to predict the rate of
volatilization of pure chemicals, not aqueous solutions. The model was also validated using pure
chemicals. As a result, the model implicitly assumes that mass transfer resistance on the gas side
is limiting. The model may fail in describing volatilization of chemicals from solutions when
liquid-side mass transfer controls.
CEBMPEA models the evaporation of chemicals from open surfaces using the following model:
Fy,0 = 2 cL,y Hy A [Dyiairvz/(7iz)]°-5 (16)
where:
Fyi0 = volatilization rate of chemical y from open tanks (m/t)
Dy,air = molecular diffusion coefficient of chemical y in air (l2/t)
vz = air velocity (1/t)
z = distance along the pool surface (1)
The value of vz recommended by CEBMPEA is 100 ft-min"1. The value of Dvair can be estimated
by the following formula (US EPA, 1991):
Dy,air = 4.09x10"5 T1-9 (1/29 + 1/M)0 5 M"a33/Pt (17)
where:
Dy,air = molecular diffusion coefficient of chemical y in air (cm2/s)
T = air temperature (K)
M = molecular weight (g/mol)
P, = total pressure (atm)
This equation is based on kinetic theory and generally gives values of Dy air that agree closely with
experimental data.
V. CALCULATION OF CHEMICAL CONCENTRATION IN WORKPLACE AIR
FROM EMISSION RATES
The indoor air concentration will be estimated from the following equation (US EPA, 1991):
Cy = Fy t/(Vr Rv k) (18)
D-9
-------
where:
cy
= workplace contaminant concentration (m/13)
Fy,x
= total emission rate of chemical from all sources (m/t)
vR
= room volume (l3/t)
Rv
= room ventilation rate (t"1)
k
= dimensionless mixing factor
The mixing factor accounts for slow and incomplete mixing of ventilation air with room air.
CEBMPEA sets this factor to 0.5 for the typical case and 0.1 for the worst case. CEBMPEA
commonly uses values of the ventilation rate Q from 500 ft3/min to 3,500 ft3/min. Appropriate
ventilation rates for MHC lines will be chosen from facility data and typical industrial
recommendations.
VI. EXAMPLE MODELING OF FORMALDEHYDE RELEASE TO ATMOSPHERE
FROM AIR-SPARGED ELECTROLESS COPPER BATH
In the examples below, the values of some parameters are based upon a site visit to SM
Corporation in Asheville, NC. Except where stated otherwise, final values of the various
parameters used in the models will be chosen based on the results of the Workplace Practices
Questionnaire, chemical suppliers information, site visits, and performance demonstrations. All
parameter values are based on preliminary information and are subject to change.
Values of site-specific parameters assumed in the example
Tank volume = 242 L
Tank depth = 71 cm
Tank width = 48 cm
Tank length = 71 cm
Air sparging rate = 53.80 L/min
Tank temperature = 51,67°C
H2CO Concentration in tank = 7,000 mg/L
Bubble diameter at tank surface = 2.00 mm
Room length = 20 m
Room width = 20 m
Room height = 5 m
Air turnovers/hour = 4 hr"1
Air velocity across tank surface = 0.508 m/s
Dimensionless mixing factor = 0.5
Site visit to SM Co., Asheville, NC
Assumed
Assumed
Assumed
Midpoint of values given in Perry's Handbook,
1985, pg 19.13
Site visit to SM Co., Asheville, NC
Product data sheets
Assumed
Assumed
Assumed
Assumed
Assumed
Default recommended by US EPA, 1991
Default recommended by US EPA, 1991
Volatilization induced by air sparging
Calculating overall mass transfer coefficient for oxygen in water:
D-10
-------
K,
OLDo
= 0.31*
(PH20 P air^S
V-H2cP,
02
= 0.0113 cm/sec
= 0.678 cm/min
1/3
D
02
d,
where:
db
PH20
Pgas
g
HffiO
Dq2
= 0.2 cm
= 0.997 g/cm3 (Dean, 1985)
= 0.00118 g/cm3 (Dean, 1985)
= 980 cm/sec2
= 0.0089 (g/cm-sec) (Dean, 1985)
= 2.1xl0"5 cm2/sec (Cussler, 1984)
Calculating molecular diffusion coefficient of formaldehyde in water:
D =
13.26x70
y 1.14 xrO.589
VH20 Vm
= 1.81xl0"5 cm2/sec
where:
Vm = 36.8 cm3/mol
|in2o = 0.89 centipoise
Calculating mass transfer coefficient of formaldehyde in water:
K,
OL,y
D
D.
02
K,
1.81x70
0L,02
2.10x70
* 0.678
= 0.584 cm/min
Correcting mass transfer coefficient for temperature:
K,
= Kot vW'c 1.024(T"25) = 0.584* 1.024(5L67"25) =1.10 cm/min
OL,y, 51.67 *V)L,y,25 C
Calculating tb
tu = -
18 h \iH20
db (Ph20~ Pair^S
= 0.291 sec
= 4.85xl0"3 min
D-ll
-------
where:
= 71 cm
Calculating inter facial area per unit volume:
6 Qq tb
a==
VLdb
= 0.0323 cm2/cm3
where:
Qg
VL
= 53,800 cm3/min
= 242,000 cm3
Correcting Henry's constant for temperature:
51.67 ^v.25"' exP
A.H -A H
gas aq
R
1
{ 298.15 273.
y
= 1.99xl0"5 (dimensionless)
where:
Hy,25°C = 1.7xl0"7 atm-m3/mol (Risk Assistant, 1995)
= 6.38xl0"6 (dimensionless)
DHgas = -27,700 cal/mol
DHaq = -35,900 cal/mol
R
= 1.987 cal/mol-K
Calculating mass transfer rate of formaldehyde by air sparging:
F = Qr H cT
y,v fc-'Cj y L,y
l-exp
. ^OL,ya^L
y^G
J
= 7.49 mg/min
The argument of the exponential function is -8031. This indicates that the formaldehyde
concentration in the air bubbles is essentially in equilibrium with the bath concentration.
Transport in aerosols
The aerosol generation rate will be estimated using data presented by both Berglund and Lindh
(1987) and Wangwongwatana et al. (1988).
Calculating aerosol generation rate using Berglund and Lindh (1987) data:
D-12
-------
Ra =
5.5xJ0^QcJA)+0.
01
ft fa fd
= 0.0187 mL/min/m2
where:
Qg/A = (53.8*10,000)/(71*48) = 158 (L/min/m2)
Ft = 0.95 @ 51,67°C (Figure lb)
Fa = 1.2 @ 0.508 m/s (Figure lc)
Fd =1.0 assumed (Figure Id)
Calculating aerosol generation rate using Wangwongwatana et al. (1988) data:
The air sparging rate used in the example (53.8 L/min) must be converted to an equivalent rate in
the experimental apparatus using the ratio of the area of the example bath (0.341 m2) to the area
of the experimental apparatus (0.123 m2). The equivalent rate is 19.4 L/min. The bubble rise
distance would be approximately 0.6 m. From Figure 2, it can be inferred that the droplet
concentration is not much greater than 100 droplets/cm3. The aerosol generation rate can now be
calculated:
v _ QGCdVd
A ~A
= 8.27x10"3 ml/m2/min
where:
Qg = 53800 cm3/min
Cd =100 droplets/cm3
Vd = (p/6) dd3 = 5.24xlO"10 cm3
dd = 0.001 cm (upper end of range reported by Wangwongwatana et al., 1988)
A = 0.341m2
The aerosol generation rates calculated by the two methods agree quite well. The model of
Berglund and Lindh (1987) will be used because it gives a slightly greater generation rate and is
easier to use.
Emission rate from bath. If it is assumed that the formaldehyde concentration in the aerosols is
equal to the bath concentration (7 mg/mL) then the formaldehyde emission rate is:
Fya = (7 mg/mL) • (0.0187 mL/m2/min) • (0.341 m2) = 4.46xl0"2 mg/min
To determine if accumulation of the contaminant at the air-water interface is significant, kIW must
be estimated using Equation 11. Since formaldehyde is a gas at the temperatures of interest,
interfacial tension data are not available; however, average values of other aldehydes may be used
(Hoff et al., 1993). Calculation of kIW@25°C is summarized below; information was not available
for calculating kIW at other temperatures.
D-13
-------
log kIW = -7.508+log Y +a (o -o -1.35a ) / 2.303RT
o IW J w wa sa sws
= -6.848
where:
yw = 1.452 Method 1, page 11-10 in Lyman et al. (1982)
as = 9.35xl08 cm2/mol Calculated from: as = 8.45x107 Vm23
R = 8.314x107 erg/mol K
oWA = 72 dyne/cm Hoff et al. (1993)
oSA =21.9 dyne/cm Value for acetaldehyde, Weast, 1980
osw = 14.6 dyne/cm Average value for n-heptaldehyde and benzaldehyde, Girfalco
and Good, 1957
kIW = 1.418xl0"7 cm
Formaldehyde emissions due to aerosols can now be calculated:
Calculating the ratio of contaminant mass sorbed at the air-water interface to mass in gas
volume of bubble:
Mi kiw
Mb Hy(db/6)
= 0.2138
Calculating fraction of bubble interface ejected as aerosols:
Ra A d,
x _ A b
Jie~b
6 Qq 4
= 4.35xl0"3
where:
lb = 5xl0"7 cm (Rosen, 1978)
Calculating formaldehyde mass transfer rate via aerosols from tank to the atmosphere:
Mr
F = If F
y'a M y's
= 0.00697 mg/min
Volatilization from open tanks
Calculating molecular diffusion coefficient of formaldehyde in air:
Dy,air = 4.09x10"5 T1-9 (1/29 + 1/M)0 5 M"033 / Pt
D-14
-------
= 0.174 cm2/sec
where:
T =298.15 K
M = 30.03 g/mol
Pt =1 atm
Calculating volatilization rate of formaldehyde from open tanks:
Fyi0 = 2 cLj Hy A [Dv airvz/(pz)]° 5
13.8 mg/min
where:
z
molecular diffusion coefficient of chemical in air (l2/t)
0.508 m/sec
0.48 m (shortest tank dimension gives highest mass transfer rate)
The gas side mass transfer coefficient (kg) in the above model is:
kg = 2[Dyairvz/(pz)]05
= 0.484 cm/sec
Thibodeaux (1979) reports a value of the liquid side mass transfer coefficient (k;) in large water
bodies of about 6xl0"4 cm/sec for wind speeds of 0.5 m/sec. Although not directly applicable to
the current situation, it can be used as a first estimate to determine the potential for liquid film
resistance to control the mass transfer rate.
Liquid side resistance = Hy/ kj = 3.3xl0"2 sec/cm
Gas side resistance = l/kg = 2.1 sec/cm
It can be concluded that formaldehyde volatilization from open tanks is controlled by gas-side
mass transfer resistance; therefore, the CEBMPEA equation appears to be valid. It should be
noted that it may be necessary to consider liquid-side mass transfer resistance for chemicals with
larger Henry's constants. In this case the CEBMPEA model would not be valid.
Surprisingly, volatilization due to air sparging is less significant than that from open tanks.
Although the concentration of formaldehyde in the bubbles is high (virtually at equilibrium with
the formaldehyde concentration in the bath), the volume of air sparged is small compared to the
volume of room air flowing over the top of the tanks.
D-15
-------
Concentration of formaldehyde in workplace air
cy = FvT/(Vr Rv k)
= 0.326 mg/m3
= 0.265 ppmv
where: FyX = 7.49 mg/min + 0.421 mg/min + 13.8 mg/min = 21.71 mg/min
VR = 20 m • 20 m • 5 m = 2000 m3
Rv = 4 hr-1 = 0.0667 min"1
k =0.5
VII. COMPARISON OF PREDICTED FORMALDEHYDE CONCENTRATIONS IN
WORKPLACE AIR TO MONITORING DATA
In this section, the concentrations of formaldehyde in the workplace air predicted by the model
are compared to available monitoring data. The purpose of the comparison is not to validate the
model but to determine if the modeling approach gives reasonable values of formaldehyde
concentration. Model validation would require calculation of formaldehyde concentrations using
the conditions specific to the monitoring sites. Such data are not available.
The results of an OSHA database (OCIS) search of monitoring data for formaldehyde (provided
by OPPT) include 43 measured air concentrations for 10 facilities in Standard Industrial
Classification (SIC) 3672 (printed circuit boards). The concentrations range from not detected to
4.65 ppmv. Most of the concentrations (37/42) range from < 0.04 to 0.6 ppmv, with all but one
less than 1.55 ppmv. Cooper et al. reports formaldehyde concentrations from three electroless
plating operations measured over a two day period. The mean concentrations ranged from 0.088
to 0.199 ppmv. The predicted concentration of formaldehyde in the workplace air was 0.263
ppmv. Thus the predicted value is within the range of concentrations determined by monitoring,
and less than the OSHA time-weighted-average concentration of 0.75 ppmv. The authors
conclude that the results are reasonable.
D-16
-------
REFERENCES
Bailey and Ollis. Biochemical Engineering Fundamentals. New York: McGraw-Hill, Inc., 1977.
Berglund, R. and E. Lindh. "Prediction of the Mist Emission Rate from Plating Baths." Proc.
Am. Electroplaters and Surface Finishers Soc. Annu. Tech. Conf., 1987.
Burgess, W.H. Recognition of Health Flazards in Industry: A Review of Materials and
Processes. New York: John Wiley and Sons, 1981.
Cohen, Y. and W. Cocchio. Laboratory Study of Liquid-Phase Controlled Volatilization Rates in
Presence of Wind Waves. Environ. Sci. Technol., 12:553, 1978.
Cooper, C.D., R.L. Wayson, J.D. Dietz, D. Bauman, K. Cheze and P.J. Sutch. Atmospheric
Releases of Formaldehyde from Electroless Copper Plating Operations. Proceedings of the
80th AESF Annual Technical Conference, Anaheim, CA. 1993.
Cussler, E.L. Diffusion: Mass Transfer in Fluid Systems. Cambridge: Cambridge University
Press, 1984.
Dean, J. A. (Ed). Lange's Handbook of Chemistry, 13th ed. New York: McGrawHill, 1985.
Girifalco, L.A. and R.J. Good. "A Theory for the Estimation of Surface and Interfacial Energies:
I. Derivation and Application to Interfacial Tension." J. Phys. Chem., 61(7):904-909, 1957.
Hoff, J.T., D. Mackay, R. Gillham and W.Y. Shiu. "Partitioning of Organic Chemicals at the Air-
Water Interface in Environmental Systems ."Environ. Sci. Technol., 27(10):2174-2180, 1993.
Hsieh, C., R. Babcock and M. Strenstrom. Estimating Semivolatile Organic Compound Emission
Rates and Oxygen Transfer Coefficients in Diffused Aeration. Water Environ. Research, 66:206,
1994.
Liss, P.S. and P.G. Slater. Flux of Gases Across the Air-Sea Interface. Nature, 247:181, 1974.
Lyman, W. J., W.F. Reehl and D.H. Rosenblatt. Handbook of Chemical Property Estimation
Methods, Washington DC: American Chemical Society, 1982.
Mackay, D. and P.J. Leinonen. Rate of Evaporation of Low Solubility Contaminants from Water
Bodies to Atmosphere. Environ. Sci. Technol., 9:1178, 1975.
Matter-Miiller, C., W. Gujer and W. Giger. Transfer of Volatile Substances from the Water to
the Atmosphere. Institute for Water Resources and Water Pollution Control (EAWAG), Swiss
Federal Institute of Technol., CH-8600 Dubendorf, Switzerland, 15:1271, 1981.
Parker, W., D. Thompson and J. Bell. Fate of Volatile Organic Compounds in Municipal
Activated Sludge Plants. Water Environ. Research, 65:58, 1993.
D-17
-------
Peng, J., J.K. Bewtra and N. Biswas. Transport of High-Volatility Chemicals from Water into
Air. Proceeding of1993 Joint CSCE-ASCE National Conf. on Environmental Eng., 120:662,
1993.
Peng, J., J. Bewtra and N. Biswas. Effect of Turbulence on Volatilization of Selected Organic
Compounds from Water, Water Environ. Research, 67:000, 1995.
Perry, R.H., D.W. Green and J.O. Maloney (Eds). Perry's Chemical Engineers' Handbook, New
York: McGraw-Hill Book Company, 1984.
Risk Assistant Software. Alexandria, VA: Thistle Publishing, 1995.
Roberts, P.V., P. Dandliker and C. Matter-Muller. Volatilization of Organic Pollutants in
Wastewater Treatment-Model Studies, EPA-R-806631. U.S. EPA, Munic. Environ. Res. Lab.,
Cincinnati, Ohio, 1983.
Rosen, M.J. Surfactants andInterfacialPhenomena. New York: John Wiley & Sons, 1978.
Smith, J. H., D.C. Bomberger and D.L. Haynes. Prediction of the Volatilization Rates of
High-Volatility Chemicals from Natural Water Bodies, Environ. Sci. Technol., 14:1332, 1980.
Thibodeaux, L.J. Chemodynamics: Environmental Movement of Chemicals in Air, Water and
Soil. New York: John Wiley & Sons, 1979.
Tschabanoglous, G. andF.L. Burton. Wastewater Engineering: Treatment, Disposal, and
Reuse. New York: McGraw-Hill, Inc., 1991.
U.S. Environmental Protection Agency. Chemical Engineering Branch Manual for the
Preparation of Engineering Assessments. Washington, DC: U.S. EPA Office of Toxic
Substances. February 28, 1991.
Wangwongwatana, S., P.V. Scarpino and K. Willeke. "Liquid-to-Air Transmission of Aerosols
from a Bubbling Liquid Surface." J. Aerosol Sci., 19(7):947-951, 1988.
Wangwongwatana, S., P.V. Scarpino, K. Willeke and P.A . Baron. "System for Characterizing
Aerosols from Bubbling Liquids." Aerosol Sci. Technol., 13(3):297-307, 1990.
Weast, R.C. (Ed.) CRC Handbook of Chemistry and Physics, 61st ed. Boca Raton, FL: CRC
Press, 1980.
D-18
-------
D-19
-------
-f= IO2 r
Bubble rise distance (cm)
Figure 2. Effect of bubble rise distance on droplets number concentration. (From
Wangwongwatana et al., 1990)
D-20
-------
Appendix E
Drag-Out Model
-------
Contents
Summary of Non-conveyorized HASL Chemicals in Process Wastewater E-l
Summary of Conveyorized HASL Chemicals in Process Wastewater E-2
Summary of Non-Conveyorized Nickel/Gold Chemicals in Process Wastewater E-3
Summary of Non-conveyorized Nickel/Palladium/Gold Chemicals in Process Wastewater . . E-4
Summary of Non-conveyorized OSP Chemicals in Process Wastewater E-5
Summary of Conveyorized OSP Chemicals in Process Wastewater E-6
Summary of Conveyorized Immersion Silver Chemicals in Process Wastewater E-7
Summary of Non-conveyorized Immersion Tin Chemicals in Process Wastewater E-8
Summary of Conveyorized Immersion Tin Chemicals in Process Wastewater E-9
Prediction of Water Quality From Printed Wiring Board Processes E-10
-------
Estimates of Drag-out, Wastewater and Surface Water Concentrations
Process Name: Non-conveyorized HASL
Production Rate, sq.m./d: 553
Number of Process Tanks: 2
Plant WW Flowrate, L/d: 27911
Stream Flow rate, L/d: 13,300,000
Summary of all Chemicals in Process Wastewater
Chemical Name
Drag-out,
Bath
Total in
Concentration
Stream
Treatment
Stream
g/d
Replacement,
Wastewater,
in Wastewater,
Concentration
Efficiency,
Concentration
g/d
g/d
mg/L
w/o Treatment,
mg/L a
%
Following POTW
Treatment, mg/L
1,4-Butenediol
861
507
1368
49
0.10
90
0.010
Alkylakyne diol
8.4
4.7
13
0.47
0.00098
Alkylaryl sulfonate
42
23
65
2.3
0.0049
0
0.0049
Alkylphenol ethoxylate
106
59
165
5.9
0.012
Alkylphenolpolyethoxyethanol
999
558
1557
56
0.12
Aryl phenol
2.9
1.7
4.6
0.16
0.00034
Citric acid
1679
937
2616
94
0.20
93
0.014
Copper sulfate pentahydrate
3046
1792
4838
173
0.36
86
0.051
Ethoxylated alkylphenol
144
80
224
*
0.02
Ethylene glycol
3087
1731
4818
173
0.36
Ethylene glycol monobutyl ether
1271
709
1980
71
0.15
90
0.015
Fluoboric acid
684
382
1066
38
0.080
Gum
12
6.8
18
0.66
0.0014
Hydrochloric acid
1157
646
1802
65
0.14
Hydrogen peroxide
3434
2021
5454
195
0.41
90
0.041
Hydroxyaryl acid
16
10
26
0.92
0.0019
Hydroxyaryl sulfonate
28
17
45
1.6
0.0034
Phosphoric acid
3391
1893
5285
189
0.40
Potassium peroxymonosulfate
6883
4051
10934
392
0.82
90
0.082
Sodium benzene sulfonate
8.3
4.6
13
0.46
0.00097
Sodium hydroxide
12
6.8
18
0.65
0.0014
Sulfuric acid
13132
7543
20675
741
1.6
a Numbers in bold indicate the estimated stream concentration (without wastewater treatment) that exceeds the aquatic toxicity concern concentration.
-------
Estimates of Wastewater and Surface Water Concentrations
Process Name: Conveyorized HASL
Production Rate, sq.m./d: 1108
Number of Process Tanks: 2
Plant WW Flowrate, L/d 44829
Stream Flowrate, L/d: 13,300,000
Summary of all Chemicals in Process Wastewater
Chemical Name
Bath
Concentration in
Stream
T reatment
Stream Concentration
Replacement,
Wastewater,
Concentration w/o
Efficiency,
Following POTW
g/d
mg/L
Treatment, mg/La
%
Treatment, mg/L
1,4-Butenediol
1016
23
0.076
90
0.0076
Alkylakyne diol
9.4
0.21
0.00070
Alkylaryl sulfonate
47
1.0
0.0035
0
0.0035
Alkylphenol ethoxylate
119
2.6
0.0089
Alkylphenolpolyethoxyethanol
1118
25
0.084
Aryl phenol
3.4
0.076
0.00025
Citric acid
1879
42
0.14
93
0.0099
Copper sulfate pentahydrate
3593
80
0.27
86
0.038
Ethoxylated alkyphenol
161
3.6
0.0121
Ethylene glycol
3470
77
0.26
Ethylene glycol monobutyl ether
1422
32
0.11
90
0.011
Fluoboric acid
766
17
0.057
Gum
14
0.30
0.0010
Hydrochloric acid
1294
29
0.097
Hydrogen peroxide
4050
90
0.30
90
0.030
Hydroxyaryl acid
19
0.43
0.0014
Hydroxyaryl sulfonate
33
0.75
0.0025
Phosphoric acid
3795
85
0.28
Potassium peroxymonosulfate
8120
181
0.61
90
0.061
Sodium benzene sulfonate
9.3
0.21
0.00070
Sodium hydroxide
14
0.30
0.0010
Sulfuric acid
15120
337
1.1
a Numbers in bold indicate the estimated stream concentration (without wastewater treatment) that exceeds the aquatic toxicity concern concentration.
-------
Estimates of Drag-out, Wastewater and Surface Water Concentrations
Process Name: Non-conveyorized Nickel/Gold
Production Rate, sq.m./d: 113.9
Number of Process Tanks: 6
Plant WW Flowrate, L/d 9595
Stream Flow rate, L/d: 13,300,000
Summary of all Chemicals in Process Wastewater
Chemical Name
Drag-out, g/d
Bath
Total in
Concentration in
Stream Concentration
Treatment
Stream Concentration
Replacement,
Wastewater,
Wastewater, mg/L
w/o Treatment, mg/L a
Efficiency, %
Following POTW
g/d
g/d
Treatment, mg/L
Aliphatic acid A
136
82
219
23
0.016
Aliphatic acid B
20
12
32
3.4
0.0024
Aliphatic acid E
306
184
491
51
0.037
Aliphatic dicarboxylic acid A
96
58
154
16
0.012
Aliphatic dicarboxylic acid C
45
27
73
7.6
0.0055
Alkylamino acid B
337
45
383
40
0.029
Alkyl diol
581
93
673
70
0.051
Alkylphenolpolyethoxyethanol
206
33
239
25
0.018
Ammonia compound B
1.0
0.57
1.5
0.16
0.00011
Ammonium chloride
745
100
845
88
0.064
Ammonium hydroxide
480
65
545
57
0.041
Citric acid
134
16
150
16
0.011
Copper sulfate pentahydrate
627
123
750
78
0.056
86
0.0079
Ethoxylated alkylphenol
12
2.0
14
1.5
0.0011
Hydrochloric acid
7601
569
8170
851
0.61
Hydrogen peroxide
500
98
598
62
0.045
90
0.0045
Hydroxyaryl acid
3.3
0.66
4.0
0.42
0.00030
Inorganic metallic salt A
0.029
0.017
0.046
0.0048
0.0000035
Inorganic metallic salt B
1.9
1.1
3.1
0.32
0.00023
Inorganic metallic salt C
0.020
0.012
0.032
0.0033
0.0000024
Malic acid
205
123
328
34
0.025
Nickel sulfate
508
306
814
85
0.061
24
0.051
Palladium chloride
18
2.4
20
2.1
0.0015
Phosphoric acid
581
93
673
70
0.051
Potassium compound
959
577
1535
160
0.12
Potassium gold cyanide
41
5.5
46
4.8
0.0035
66
0.0045
Sodium hydroxide
2.4
0.47
2.8
0.30
0.00021
Sodium hypophosphite mono hydrate
585
352
936
98
0.070
Sodium salt
1229
164
1393
145
0.10
Substituted amine hydroxhloride
818
109
928
97
0.070
80
0.014
Sulfuric acid
2796
491
3287
343
0.25
Transition metal salt
8.2
1.1
9.3
1.0
0.00070
Urea compound B
0.7
0.4
1.1
0.1
0.00008
a Numbers in bold indicate the estimated stream concentration (without wastewater treatment) that exceeds the aquatic toxicity concern concentration.
-------
Estimates of Drag-out, Wastewater and Surface Water Concentrations
Process Name: Non-conveyorized Nickel/Palladium/Gold
Production Rate, sq.m./d: 86
Number of Process Tanks: 8
Plant WW Flowrate, L/d 12703
Stream Flow rate, L/d: 13,300,000
Summary of all Chemicals in Process Wastewater
Chemical Name
Drag-out, g/d
Bath
Total in
Concentration in
Stream
Treatment
Stream Concentration
Replacement, g/d
Wastewater, g/d
Wastewater,
mg/L
Concentration w/o
Treatment, mg/L a
Efficiency, %
Following POTW
Treatment, mg/L
Aliphatic acid B
15
9.2
24
1.9
0.0018
Aliphatic acid E
308
186
494
39
0.037
Aliphatic dicarboxylic acid A
72
44
116
9.1
0.0087
Aliphatic dicarboxylic acid C
34
21
55
4.3
0.0041
Alkylamino acid B
451
61
512
40
0.038
Alkyldiol
438
70
509
40
0.038
Alkylpolyol
389
892
1282
101
0.096
Amino acid salt
21
1.4
22
1.7
0.0017
Amino carboxylic acid
10
23
34
2.7
0.0025
Ammonia compound A
513
69
582
46
0.044
Ammonia compound B
0.72
0.44
1.2
0.091
0.000087
Ammonium hydroxide
615
83
698
55
0.052
Citric acid
124
15
139
11
0.010
Copper sulfate pentahydrate
474
93
567
45
0.043
86
0.0060
Ethoxylated alkylphenol
9.3
1.5
11
0.85
0.00081
Ethylenediamine
46
105
150
12
0.011
Hydrochloric acid
1268
159
1427
112
0.11
Hydrogen peroxide
378
74
452
36
0.034
90
0.0034
Hydroxyaryl acid
2.5
0.50
3.0
0.24
0.00023
Inorganic metallic salt B
6.6
13
19
1.5
0.0015
82
0.00026
Maleic acid
20
47
67
5.3
0.0051
Malic acid
155
93
248
20
0.019
Nickel sulfate
604
365
969
76
0.073
24
0.055
Palladium salt
33
74
107
8.4
0.0080
Phosphoric acid
438
70
509
40
0.038
Potassium compound
724
437
1160
91
0.087
Potassium gold cyanide
31
4.1
35
2.7
0.0026
Propionic acid
75
171
246
19
0.018
Sodium hydroxide
1.8
0.35
2.1
0.17
0.00016
Sodium hypophosphite mono hydrate
625
463
1088
86
0.082
Sodium salt
1548
166
1714
135
0.13
Substituted amine hydrochloride
618
83
701
55
0.053
80
0.011
Sulfuric acid
1646
324
1970
155
0.15
Surfactant
1.0
2.3
3.4
0.27
0.00025
Transition metal salt
6.2
0.83
7.0
0.55
0.00053
Urea compound B
1.0
0.62
1.7
0.13
0.00120
a Numbers in bold indicate the estimated stream concentration (without wastewater treatment) that exceeds the aquatic concern concentration.
-------
Process Name:
Production Rate, sq.m./d:
Number of Process Tanks:
Plant WW Flowrate, L/d
Stream Flow rate, L/d:
Non-Conveyorized OSP
686
3
21631
13,300,000
Summary of all Chemicals in Process Wastewater
Chemical Name
Drag-out, g/d
Bath
Total in
Concentration in
Stream
Treatment
Stream Concentration
Replacement,
Wastewater,
Wastewater,
Concentration w/o
Efficiency,
Following POTW
g/d
g/d
mg/L
Treatment, mg/La
%
Treatment, mg/L
Acetic acid
4951
339
5289
245
0.40
Alkylaryl imidazole
4054
277
4332
200
0.33
90
0.033
Aromatic imidizole productb
519
35
554
26
0.042
Aryl phenol
3.6
2.1
5.7
0.26
0.00430
Copper ion
4054
277
4332
200
0.33
86
0.046
Copper salt C
112
8
119
5.5
0.0089
86
0.00130
Copper sulfate pentahydrate
3778
2225
6003
278
0.45
86
0.063
Ethoxylated alkyphenol
74
42
116
5.4
0.0087
Ethylene glycol
3829
2149
5978
276
0.45
Gum
14
8
23
1.1
0.0017
Hydrochloric acid
1639
916
2555
118
0.19
Hydrogen peroxide
1525
898
2423
112
0.18
90
0.018
Hydroxyaryl acid
20
12
32
1.50
0.0024
Hydroxyaryl sulfonate
35
21
56
2.6
0.0042
Phosphoric acid
3497
1954
5451
252
0.41
Sodium hydroxide
14
8
23
1.10
0.0017
Sulfuric acid
21683
12751
34433
1592
2.6
a Numbers in bold indicate the estimated stream concentration (without wastewater treatment) that exceeds the aquatic toxicity concern concentration.
b This ingredient not evaluated further as there was not enough information provided to identify a specific chemical.
-------
Process Name: Conveyorized OSP
Production Rate, sq.m./d: 1500
Number of Process Tanks: 3
Plant WW Flowrate, L/d 32232
Stream Flow rate, L/d: 13,300,000
Summary of all Chemicals in Process Wastewater
Chemical Name
Bath
Concentration in
Stream
Treatment
Stream Concentration
Replacement,
Wastewater,
Concentration w/o
Efficiency,
Following POTW
g/d
mg/L
Treatment, mg/La
%
Treatment, mg/L
Acetic acid
2963
92
0.22
Alkylaryl imidazole
2427
75
0.18
90
0.018
Aromatic imidizole productb
310
10
0.023
Arylphenol
4.6
0.14
0.00034
Copper ion
2427
75
0.18
86
0.025
Copper salt C
67
2.1
0.0050
86
0.00070
Copper sulfate pentahydrate
4865
151
0.36
86
0.051
Ethoxylated alkyphenol
91
2.8
0.0068
Ethylene glycol
4699
146
0.35
Gum
18
0.6
0.0014
Hydrochloric acid
2002
62
0.15
Hydrogen peroxide
1964
61
0.15
90
0.015
Hydroxyaryl acid
26
0.81
0.0019
Hydroxyaryl sulfonate
45
1.4
0.0034
Phosphoric acid
4272
133
0.32
Sodium hydroxide
18
0.57
0.0014
Sulfuric acid
27877
865
2.1
a Numbers in bold indicate the estimated stream concentration (without wastewater treatment) that exceeds the aquatic toxicity concern concentration.
b This ingredient not evaluated further as there was not enough information provided to identify a specific chemical.
-------
Estimates of Wastewater and Surface Water Concentrations
Process Name: Conveyorized Immersion Silver
Production Rate, sq.m./d: 376
Number of Process Tanks 4
Plant WW Flowrate, L/d 8083
Stream Flow rate, L/d: 13,300,000
Summary of all Chemicals in Process Wastewater
Chemical Name
Bath
Concentration in
Stream
Treatment
Stream Concentration
Replacement,
Wastewater,
Concentration w/o
Efficiency,
Following POTW
g/d
mg/L
Treatment, mg/La
%
Treatment, mg/L
1,4-Butenediol
390
48
0.029
90
0.0029
Alkylamino acid A
1603
198
0.12
Fatty amine
62
7.7
0.0047
95
0.00023
Hydrogen Peroxide
3462
428
0.26
90
0.026
Nitrogen acid
281
35
0.021
Nonionic Surfactantb
345
43
0.026
Phosphoric acid
2891
358
0.22
Silver Nitrate
8.4
1.0
0.00063
96
0.000025
Sodium hydroxide
621
77
0.047
Sulfuric acid
141
17
0.011
a Numbers in bold indicate the estimated stream concentration (without wastewater treatment) that exceeds the aquatic toxicity concern concentration.
b This ingredient not evaluated further as there was not enough information provided to identify a specific chemical.
-------
Estimates of Drag-out, Wastewater and Surface Water Concentrations
Process Name: Non-conveyorized Immersion Tin
Production Rate, sq.m./d: 321
Number of Process Tanks: 4
Plant WW Flowrate, L/d 23624
Stream Flowrate, L/d: 13,300,000
Summary of all Chemicals in Process Wastewater
Chemical Name
Drag-out,
Bath
Total in
Concentration
Concentration
T reatment
Concentration in
g/d
Replacement,
Wastewater,
in Wastewater,
in Stream,
Efficiency,
Stream following
g/d
g/d
mg/L
mg/La
%
POTW
Treatment, mg/L
Aliphatic acid D
493
33
526
22
0.039
Alkylalkyne diol
4.9
0.78
5.7
0.24
0.00042
Alkylamino acid B
779
51
830
35
0.062
Alkylaryl sulfonate
24
3.9
28
1.2
0.0021
0
0.0021
Alkylimine dialkanol
26
1.7
28
1.2
0.0021
Alkylphenol ethoxylate
61
9.8
71
3.0
0.0054
Bismuth compound
1.0
0.066
1.1
0.045
0.000080
Citric acid
14599
1056
15655
663
1.2
93
0.082
Cyclic amide
1983
131
2115
90
0.16
Ethoxylated alkylphenol
49
7.8
57
2.4
0.0042
Ethylene glycol monobutyl ether
738
118
856
36
0.064
90
0.0064
Fluoboric acid
397
63
461
19
0.035
Hydrochloric acid
279
18
298
13
0.022
Hydroxy carboxylic acid
1633
108
1741
74
0.13
Methane sulfonic acid
15636
1046
16682
706
1.3
Phosphoric acid
974
156
1130
48
0.085
Potassium peroxymonosulfate
3996
785
4780
202
0.36
90
0.036
Quantenary alkylammonium chlorides
922
61
983
42
0.074
90
0.0074
Silver salt
0.15
0.010
0.16
0.0067
0.000012
Sodium benzene sulfonate
4.8
0.77
5.6
0.24
0.00042
Sodium phosphorus salt
3475
231
3706
157
0.28
Stannous methane sulfonic acid
4352
288
4640
196
0.35
40
0.21
Sulfuric acid
10239
1325
11564
490
0.87
Thiourea
3799
251
4050
171
0.30
90
0.030
Tin chloride
544
36
580
25
0.044
40
0.026
Unspecified tartrate
973
64
1037
44
0.078
Urea
3503
231
3735
158
0.28
Urea compound C
779
51
830
35
0.062
90
0.0062
Vinyl polymer
493
33
526
22
0.039
a Numbers in bold indicate the estimated stream concentration (without wastewater treatment) that exceeds the aquatic toxicity concern concentration.
-------
Estimates of Wastewater and Surface Water Concentrations
Process Name: Conveyorized Immersion Tin
Production Rate, sq.m./d: 226
Number of Process Tanks: 4
Plant WW Flowrate, L/d 8106
Stream Flow rate, L/d: 13,300,000
Summary of all Chemicals in Process Wastewater
Chemical Name
Bath
Concentration in
Stream
Treatment
Stream Concentration
Replacement,
Wastewater,
Concentration w/o
Efficiency,
Following POTW
g/d
mg/L
Treatment, mg/La
%
Treatment, mg/L
Aliphatic acid D
23
2.8
0.0017
Alkylalkyne diol
0.55
0.067
0.000041
Alkylamino acid B
36
4.5
0.0027
Alkylaryl sulfonate
2.7
0.34
0.00021
Alkylimine dialkanol
1.2
0.15
0.000092
Alkylphenol ethoxylate
6.9
0.85
0.00052
Bismuth compound
0.046
0.0057
0.0000035
Citric acid
742
92
0.056
Cyclic amide
92
11
0.0069
Ethoxylated alkylphenol
5.5
0.67
0.00041
Ethylene glycol monobutyl ether
83
10
0.0062
Fluoboric acid
45
5.5
0.0033
Hydrochloric acid
13
1.6
0.0010
Hydroxy carboxylic acid
76
9.4
0.0057
Methane sulfonic acid
735
91
0.055
Phosphoric acid
109
13
0.0082
Potassium peroxymonosulfate
551
68
0.041
90
0.0041
Quantenary alkylammonium chlorides
43
5.3
0.0032
Silver salt
0.0069
0.00086
0.00000052
Sodium benzene sulfonate
0.54
0.067
0.000041
Sodium phosphorus salt
163
20
0.012
Stannous methane sulfonic acid
202
25
0.015
Sulfuric acid
932
115
0.070
Thiourea
176
22
0.013
Tin chloride
25
3.1
0.0019
Unspecified tartrate
45
5.6
0.0034
Urea
163
20
0.012
Urea compound C
36
4.5
0.0027
Vinyl polymer
23
2.8
0.0017
Numbers in bold indicate the estimated stream concentration (without wastewater treatment) that exceeds the aquatic toxicity concern concentration.
-------
PREDICTION OF WATER QUALITY
FROM PRINTED WIRING BOARD PROCESSES
Final Report to the University of Tennessee Center for Clean Products and
Clean Technologies and to the U.S. Environmental Protection Agency
Part of the Verification of Finishing Technologies Project
EPA Grant X825373-01-2 (Amendment No. 2)
By
Dr. R. Bruce Robinson
Dept. of Civil and Environmental Engineering
73 Perkins Hall, University of Tennessee, Knoxville, TN 37996
Office: 865/974-7730, FAX: 865/974-2669, E-Mail: rbr@utk.edu
Dr. Chris Cox
Dept. of Civil and Environmental Engineering
73 Perkins Hall, University of Tennessee, Knoxville, TN 37996
Office: 865/974-7729, FAX: 865/974-2669, E-Mail: ccox9@utk.edu
Jennie Ducker
Dept. of Civil and Environmental Engineering
73 Perkins Hall, University of Tennessee, Knoxville, TN 37996
August 6,1999
E-10
-------
TABLE OF CONTENTS
INTRODUCTION
Objectives
LITERATURE REVIEW
Pollutant Generation Rate and Waste Generation Volume
Drag-out Tests at Micom, Inc.
Other Published Drag-out Estimates
Discussions with Experts in the Surface Finishing Industry
Summary of Drag-out Studies
Drag-out Prediction Equations
Rinsing Theory
Other Rinsing Theory Studies
Printed Wiring Board Pollution Prevention and Control Technology
Water Use Rates from Survey of MHC Facilities
RESEARCH APPROACH
LABORATORY DRAG-OUT EXPERIMENTS
Apparatus
Procedure
Quality Assurance and Quality Control (QA/QC)
Results and Discussion
DRAG-OUT MODEL DEVELOPMENT
PWB WASTEWATER MODEL
COLLECTION AND ANALYSIS OF FIELD SAMPLES
Process Characterization
Sample Collection
Temperature
pH
Conductivity
Viscosity
Specific Gravity
Surface Tension
Metals Analysis
Quality Assurance and Quality Control (QA/QC)
Results from Analysis of Field Samples
DYNAMIC MASS BALANCE MODEL FOR INTERPRETATION OF FIELD DATA
E-ll
-------
MODEL VALIDATION
CONCLUSIONS AND RECOMMENDATIONS FOR FUTURE WORK
Conclusions
Recommendations
REFERENCES
LIST OF SYMBOLS
E-12
-------
INTRODUCTION
The Design for the Environment (DFE) Project Printed Wiring Boards (PWB) Cleaner
Technologies Substitutes Assessment: Making Holes Conductive (MHC) was performed by the
Center for Clean Products and Clean Technologies (CCPCT) at the University of Tennessee. The
project and results were well received by industry and the U.S. Environmental Protection
Agency. However, all parties agreed that one weakness in the project was the evaluation of
impacts of chemicals in the wastewater discharges of bath solutions from the MHC plating lines.
Evaluation of these impacts was more difficult than anticipated partly because of insufficient
information from surveyed facilities on the water quality of their discharges. Attempts at a mass
balance to predict chemical discharges were also unsatisfactory due to insufficient data on
chemical use and ultimate fate.
An estimate of the pollutants in the raw wastewater from PWB plating processes is needed in
order to evaluate health risks, impacts on the environment, impacts on municipal wastewater
plants, and overall manufacturing costs which includes treatment/disposal costs. The main
source of pollutants in the raw wastewater is the drag-out from the baths. Hence, drag-out is the
key variable for determining pollutant mass.
PWB facilities analyze at most only a couple of chemicals in their wastewater, and the facilities
generally have insufficient data to calculate chemical mass balances. Therefore, a different
approach is required to estimate the pollutant loads and wastewater quality of the PWB
wastewater discharges. This report discusses the development, validation, and use of predictive
tools to satisfy this need.
Objectives:
The objectives of this research were:
• Develop tools and methodologies to predict, but more importantly to compare the mass
of pollutants in the raw wastewater discharges from PWB plating processes.
• Validate these tools and methodologies against data available in the literature and against
samples collected at PWB facilities.
E-13
-------
LITERATURE REVIEW
Literature was identified through a computerized search on several key words. Additional papers
were found from the references in papers and from a manual search of recent Chemical
Abstracts (1998).
Pollutant Generation Rate and Waste Generation Volume
The sources of the pollutants in the wastewater generated in the MHC and surface finishing
processes for PWB manufacturing are the chemicals that escape from the process baths and from
other processes such as stripping racks of plating deposits. Our assumption for estimating the
pollutant mass generation rate, e.g., kg Cu/day, is that the source of the pollutants is
predominantly the drag-out from the process baths. Whatever chemicals are drug out of the
process tanks by solution adhering to the surface of the boards and racks will be removed in the
rinse tanks and ultimately end up in the raw wastewater discharge before any treatment or metals
recovery. This is consistent with the literature (Mooney 1991) and is expressed in a simple mass
balance:
^mass of pollutants^ f mass of pollutants
in drag - out J vin rinse discharge.
f +„\
Eqn 1
As discussed later, the etchant process baths themselves are generally not dumped into the
wastewater at the end of their useful life, but are typically sent off-site for processing. Other
process baths are apparently not sent off-site and do need to be accounted for in the waste
generation. Although pollutants from the stripping of racks may be significant at times, the
average mass pollutants originating from this process should be less than that contributed by
drag-out. Therefore, an estimate of the expected drag-out from various process tanks under
differing conditions is critical for estimating the waste mass generation rate. The arrangement of
the rinse tanks and the rinse flow rates will not change the total mass of contaminants released,
only the concentration and the volume of wastes. The waste generation volume primarily
depends on the rinse flow rates since this is the main source of wastewater discharge. If certain
assumptions are made, then conventional rinsing theory may be used to estimate the volume of
waste based on the drag-out and needed final rinse water quality. Importantly, the primary goal
of this work is a methodology that can be used to compare the relative amounts of wastes
generated from alternative PWB surface finishing manufacturing processes.
There are many references giving advice on minimizing drag-out and rinse water. Factors that
will reduce the drag-out include slow withdrawal from the process tank, longer drainage times,
tilting the boards so that the liquid drains to a corner, using drip shields, using drag-out/drag-in
tanks, as well as others. Solution density, viscosity, which depends on the bath chemistry and
temperature, and surface tension also affect how well the liquid drains off the boards, and hence
affects drag-out. Because of the number of variables which have complex relationships with
drag-out, estimating drag-out for a series of baths is a difficult, unsolved problem. The following
sections review what is known about estimating drag-out, including several references that
include predictive equations and experimental measurements.
E-14
-------
Drag-Out Tests at Micom, Inc.
The MnTAP/EPA Write study (Pagel 1992) at Micom, Inc. evaluated the ability of two
modifications to reduce waste from PWB surface finishing processes. At the time of the study,
Micom produced 92 -111 m2/day of double-sided and multilayered PWBs with the average
board being 0.46 m by 0.53 m and having 8000 holes. Micom had already implemented several
waste reduction measures, including countercurrent rinses, flow restrictors, softened water in the
rinses (softened water improved the rinsing and increased the efficiency of the ion exchange
waste treatment system), and air and mechanical agitation. However, Micom evaluated whether
changes to the way PWBs were transferred from process baths to the rinse tanks could further
reduce the amount of waste by reducing the drag-out.
Two processes were tested at Micom, Inc. in their MHC line: 1) a micro-etch bath and the
countercurrent rinse tanks following it; and 2) an electroless copper bath and the countercurrent
rinse tanks following it. The PWBs were moved from tank to tank in racks. The racks were 0.86
m high by 0.50 m wide by 0.33 m deep and could hold 24 boards. Typically, the operator
controlled a hoist and allowed the rack to drain for 3-5 seconds before going into the next tank.
The residence time was about 75 seconds in the micro-etch tank, 30 minutes in the electroless
copper tank, which held two racks at a time, and 2-3 minutes in each rinse tank.
The modifications evaluated at Micom were: 1) slowing the withdrawal rate of the racks from the
process bath; and 2) using an intermediate rack withdrawal rate combined with a longer drain
time over the process bath before going into the rinse tanks. Slowing the withdrawal rate was
achieved by lowering the speed of the motor on the mechanical hoist used to move the racks.
Installation of new equipment prohibited matching the withdrawal rates used in the first
modification with tests on the second modification, hence the designation of "intermediate"
withdrawal rate. Withdrawal time was defined as the time it took to raise the boards from the
bath to a height needed to clear the tank walls, a total of 0.91 m. Increasing the drain time was
achieved by the operator simply waiting longer before placing the boards in the next bath. Drain
time was defined from the moment that the rack cleared the water surface until half of the rack
was over the adjacent rinse tank. Measurement of drag-out was accomplished by shutting off the
rinse water and then measuring the increase in copper concentration after a known quantity of
boards had been rinsed. Copper was measured by atomic absorption spectrophotometry. The
electroless copper samples were preserved with a hydrochloric/nitric acid mixture rather than just
nitric, because copper precipitated out of solution as the solution cooled when nitric acid alone
was used. There were some analytical difficulties of unknown origin in that the copper
measurements done by an outside laboratory showed about 1800-2200 mg/L of copper whereas
Micom's laboratory analyses showed about 2400 mg/L.
Baseline drag-out measurements were made over a twelve day period using 136 samples for 12
pairs of racks. The first modification experiments were also made using 136 samples for 12 pairs
of racks, and the second modification experiments used 109 samples for 9 pairs of racks.
The results of the experiments are summarized in Tables 1 and 2. It should be noted that the
values for drag-out, withdraw rate, and drain time are averages of a rather broad range of values
grouped by relative magnitude by Page 1.
E-15
-------
Table 1. Drag-Out Test Results on the Microetch
3ath at Micom, Inc.
Parameter
Baseline
Slow Withdrawal Rate
Intermediate Withdrawal Rate
& Longer Drain Time
Drag-out, mL/m2
129
72.1
76.4
Withdrawal time, sec
1.7
14.9
4.3
Withdrawal rate, m/sec
0.51
0.056
0.20
Drain time, sec
3.4
2.5
12.1
Total time, sec
5.1
17.4
16.4
Surface area/rack, m2
8.2
7.7
8.6
Water flow rate, 1pm
9.8
—
—
Table 2. Drag-Out Test Results on the Electroless Bath at Micom, Inc.
Parameter
Baseline
Slow Withdrawal
Rate
Intermediate Withdrawal Rate
& Longer Drain Time
Drag-out, mL/m2
64.6
32.3
31.4
Withdrawal time, sec
1.8
13.9
4.3
Withdrawal rate, m/min
0.48
0.061
0.175
Drain time, sec
5.2
3.2
11.9
Total time, sec
7.0
17.1
16.3
Surface area/rack, m2
15.7
15.0
16.3
Water flow rate, 1pm
12.5
—
—
For the micro-etch bath, the first modification reduced the drag-out by 45% while the second
modification reduced drag-out by 41%. For the electroless copper bath, the reductions were 50%
and 52%, respectively. Because it was easier for Micom to control the drain time than the
withdrawal rate, they implemented a longer drain time.
It should be noted that reducing the drag-out from the micro-etch affects the bath. This bath
removes copper until the etchants are exhausted. Make-up chemicals may be added to replace
etchant solution is lost in drag-out. Reducing drag-out may mean that the entire bath must be
replaced more frequently, because of increased copper build-up in the bath. However, Micom
preferred to retain the copper in the bath and replace the bath, because there is greater
opportunity to recover metals in the etchant bath than in the rinses. For the electroless bath,
drag-out reduction helps retain the chemicals in the bath and increase its life, providing that build-
up of impurities does not offset this advantage. Reduction of drag-out from upstream baths
would help in this regard.
E-16
-------
Other Published Drag-Out Estimates
SiiP (1990) evaluated several ways to minimize drag-out, including the effect of the inclination
angle during drainage, the withdrawal rate, and the drainage time. Several experiments focused
on the inclination angle in the design of electroplating product holders and its effect on drag-out.
The holders were not for PWBs but apparently for a variety of electroplated products. The
holders typically had horizontal cross-braces or struts. SiiP noted that the drag-out from the
holder could be as much as 50% of the total drag-out in these cases. SiiP experimented with
holder designs that had struts of different angles and showed that drag-out could be reduced
significantly. The effect of the inclination angle of the struts on drag-out is shown in Table 3.
Struts tilted at a 45° angle to horizontal had only 36% of the drag-out as a horizontal one.
Table 3. Effect of Inclination Angle of the Product Ho
der Strut on Drag-Out
Angle to Horizontal
Drag-Out
mL/m2
% of Maximum
0°
44
100
15°
35
80
30°
25
57
45°
16
36
90°
22
50
SiiP (1990) also experimented with chromium plated sheets suspended from the holders to
determine the effect of drainage time and inclination angle of the sheet. The experiments used
either 19-20 g/L or 240-250 g/L Cr03 electrolytes. The effect of drainage time and inclination
angle is shown in Table 4. (Note: the data reported in Table 4 were read from two graphs in SiiP
(1990) and include representative data, but not all the data.). As seen in the table, a 45° inclination
angle had about 33% less drag-out at short drainage times compared to a horizontal angle and
nearly 50% less drag-out at long drainage times. An increase in the drainage time greatly
reduced drag-out up to about 20-30 seconds, but had a relatively small effect for longer times.
Further experiments were conducted on the effect of withdrawal rate and inclination angle of the
sheet. The effect of withdrawal rate is shown in Table 5. Slower withdrawal rates reduced the
drag-out, but not as much as inclination angle. A plate withdrawn at 60 m/min had roughly 25-
30% more drag-out volume than a plate withdrawn at 6 m/min. The drag-out volumes reported
by SiiP are approximately a factor of two less than the drag-out volumes reported in the Micom
study (Pagel 1992) discussed above. One explanation for the difference may be that the boards
in the SiiP study did not contain holes but the boards used in the Micom study did. It should be
noted that SiiP was not clear how the drag-out was calculated. It appears to be American practice
to report the drag-out in terms of the area of one side of the board. It is possible that SiiP
calculated his drag-out based on the area of both sides of the board, leading to numbers which
are half as large. If this were the case, then to be comparable to American practice, his drag-out
volumes should be doubled. However, in a later paper, SiiP (1992) used an equation which was
developed for drag-out on the basis of one side of the board. It is likely that he was aware of the
assumptions built into the equation, and considering that his values are comparable to the Micom
study, we will assume that SiiP's drag-out volumes are directly comparable to other values. In
either case, the trends are the same.
E-17
-------
Table 4. Effect of Drainage Time and Inclination Angle on Drag-Out.
Drainage
Time, s
Drag-Oiil, in 1 ./in~
280-320 g/L ('!¦(),.
0" single. 40"C
280-320 g/L ( r()t.
45" angle. 40"(
20 g/L C1O3,
0"angle. 20"(
20 g/L ( ¦•(),.
45"angle. 20"C
0
57
--
64
~
10
28
21
33
24
20
22
13
28
19
30
20
11
25
15
45
19
~
21
13
60
19
10
19
11
Table 5. Effect of Withdrawal Rate on Drag-Out.
Drag
-Onl
Withdrawal kale,
ni/niin
240-250 g/|. C r(),
(40±|"C)
l«)-20 g/l. ( r(),
(20±|"C)
niL/nr
nil./nr
3.6
17
21
6
22
26
9
24.5
29
18
26.5
32
36
27
33
60
28
33
In a second paper, Slip (1992) evaluated two drag-out prediction equations by comparing
measured volumes of drag-out to predicted values. The first equation was from Kushner (1951):
, H'h
f = 0.02 1- Eqn 2
P-K
or:
E-18
-------
/ = 0.02 >
¦VA
where:
f
film thickness, cm
V-
dynamic viscosity of electrolyte, g/(cms)
h
height of metal sheet
P
density of electrolyte, gm/cm3
tw
withdrawal time, s
v =
kinematic viscosity, cm2/s
VA
withdrawal rate of metal sheet, cm/s
The second equation was:
Eqn 3
2V -h-vA
f= ^ Eqn 4
J ^9g(h+4vjdr)
where:
g = gravity, 981 cm/s2
tdr = drainage time, s
Experiments were conducted on 21.0 x 21.4 cm metal sheets which had no holes. The sheets
were withdrawn from the bath at 20 cm/s and allowed to drain for 10 seconds.
Neither of the two equations predicted the measured values very well. Sixteen different
electrolytes were tested with concentrations ranging from 17 to 300 gm/L of material, densities
ranging from 1.015 to 1.562 g/cm3, dynamic viscosities ranging from 0.713 to 8.6 cP, and
temperatures ranging from 18 to 59.5°C. The average measured drag-out was 47.4 mL/m2 with a
standard deviation of 16.3 mL/m2. The average predicted drag-out and standard deviation
predicted by equation 3 were 96.8 and 17.8 mL/m2, respectively, while equation 4 had average
predicted drag-out and standard deviation of 15.6 and 2.06 mL/m2, respectively. A linear
regression of measured versus predicted drag-out volumes gave an r2 of 0.021 and 0.012 for
equations 3 and 4, respectively. Taking an average of the two equations yielded no better results.
A scatter plot of the measured drag-out and the predicted drag-out is shown in Figure 1.
E-19
-------
Measured drag-out vs predicted
| 160
hJ WO
5 120
100
80
60
40
20
0
3
0
1
W)
-
Eqn 1
lEqn 3
Ave Eqn 1&3
20 40 60 80 100
Measured drag-out, mL/sq.m
Figure 1. Measured Versus Predicted Drag-Out for Results by Slip (1992).
SuP commented that the equations do not account for electrolyte that adheres to the surface and
bottom edge even after long drain times, i.e., there is a minimal film thickness left. This becomes
increasingly important for rougher surfaces. SiiP recommended that drag-out estimations for use
in recycling procedures and wastewater treatment should be based on measurements rather than
calculations. Part of the reason that poor correlation was found between SiiP's measured drag-
out and the predictive equations is that SiiP's drag-out showed little variation with viscosity as
shown in Figure 2.
Viscosity vs Drag-out by SuP's data
en
c«
100
80
60
40
20
0.5 1 1.5 2
Kinematic viscosity, cSt
2.5
Figure 2. Measured Drag-out as a Function of Kinematic Viscosity for
Results of SiiP (1992).
E-20
-------
McKesson and Wegener (1998) at RD Chemical Company experimentally measured the amount
of drainage from PWBs as a function of time. They pointed out that longer "hang" or drainage
times allows more liquid to drain from the PWB with consequently less drag-in into the rinse
tanks and thus more efficient rinsing. However, too long of a drainage time may result in lower
PWB quality due to drying and tarnishing. McKesson and Wegener tested two outer layer
boards with solder mask and solder plated and one inner layer board with no holes. A typical
result is shown in Figure 3. (This figure is reconstructed from a figure in McKesson and
Wegener.)
Hang time, seconds
Figure 3. Drainage vs Hang Time (McKesson and Wegener 1998).
The results for all three PWBs lay virtually on top of each other in Figure 3. The authors chose to
report just the percentage of liquid that remains on the board rather than mass or volume. This
allowed the authors to see the great similarities in drainage among varying conditions. The figure
shows two drainage phases. For short times, the liquid drains very quickly followed at longer
times by a much slower drainage rate. The authors concluded that 30 seconds appeared to be an
optimal drain time. The authors also studied the effect of surfactants and found very little
difference. They also tested canting the boards at about a 15-20° angle and saw only minor
differences.
It appears that the most influential reference for typical drag-out volumes is the Electroplating
Engineering Handbook (Pinkerton 1984). These values seem to go back to work by Soderberg
published in 1936. Typical drag-out volumes are given in Table 6 as reported by Pinkerton.
E-21
-------
Table 6. Drag-Out per Unit Area (Pinkerton 1984).
Condition
l)ni$>-Oiil 1111./nr
Vertical parts, well drained
16.21
Vertical parts, poorly drained
82
Vertical parts, very poorly drained
160
Horizontal parts, well drained
32
Horizontal parts, very poorly drained
410
Cup shaped parts, very poorly drained
320-980
1 Suggested by Pinkerton as being the absolute minimum for drag-out on a vertical sheet.
Hanson and Zabban (1959) discussed the design of a wastewater treatment plant at an IBM plant.
To design the plant, an estimate of the wastewater quality was needed. Because a primary source
of the contaminants was the plating lines, the drag-out was estimated based on information
published by Graham in the Electroplating Engineering Handbook. (Note: the data given are
the same as that in a more recent version of the Handbook given by Pinkerton [1984] and
experimental data from another IBM plant which showed drag-out volumes ranging from 100 to
160 mL/m2.) For design, a drag-out value of 200 mL/m2 was used.
Yost (1991) studied the effect of various rinsing arrangements on the costs of cadmium
electroplating wastewater costs. In doing the calculations, Yost arbitrarily assumed drag-out of
200 mL/m2 with no reference for the value.
Chang and McCoy (1990) used a drag-out value of 160 mL/ft2 to evaluate waste minimization for
PWB manufacture. No source was given for their drag-out value, but this value appears to be
commonly used by several researchers.
Discussions with Experts in the Surface Finishing Industry
Contacts were made with several experts in the surface finishing industry. One expert source
(Sharp 1998) had the following comments on drag-out:
• CH2M-Hill did a drag-out study for Merix Corporation sometime in the mid-80s (our
efforts to obtain the report from Merix were unsuccessful). CH2M-Hill used a bath tank
and one rinse tank and dipped the boards in the bath and rinsed them sequentially and
monitored the conductivity of the rinse tank. The boards were vertical and had no holes
(interlayer boards about 20 mils thick), but the hang time and other variables can only be
found in the original report. The amount of drag-out was IV2 gallons of process bath
liquid per 3,000 ft2 (102 mL/m2) of board area (one side only).
• Holes make a difference for drag-out since the holes are small enough that the liquid does
not drain out of them very well. "Hang time" also affects the drag-out.
E-22
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• Horizontal lines have drag-out of about 2-5 gallons per 3,000 ft2 (39-66 mL/m2) of board
area (one side only) for boards with no holes. The drag-out is lower for horizontal lines
compared to vertical lines because of the rollers used to squeegee the water off. Vertical
boards are the older process, and the trend is to go to horizontal boards. Currently, the
industry is about '/2 vertical and V2 horizontal.
• One vendor has suggested that the drag-out is about 15 gallons per 3,000 ft2 (200 mL/m2)
of board area (one side only). However, this appears too high because the experts's mass
balances on his own plating line didn't work out using this number.
• Based on the mass balances on the expert's surface finishing line, i.e., accounting for the
amount of chemicals added, consumed, and those in the waste, etc., the drag-out ought to
be about 7 gallons per 3,000 ft2 (95 mL/m2) of board area (one side only) for circuit
boards with holes, and about 3 gallons per 3,000 ft2 (41 mL/ft2) for interlayer boards.
• There are not any available computer models that could be used to predict wastewater
concentrations, flows, etc. for plating lines.
Most of the baths used at the expert's facility (Sharp 1998) have a specific gravity of about 1.08,
but the the viscosity and surface tension are unknown. The expert thought that chemical supply
companies know the viscosity or surface tension of the process baths, but it is nearly impossible
to get those data from the suppliers.
Summary of Drag-Out Studies
Table 7 summarizes the reported drag-out quantities from researchers and practitioners.
E-23
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Table 7. Summary of Reported Drag-Out Volumes in the Literature.
lioil I'll
Oricnliilion
liiilli
Coiulil ions/ Description
in 1 ./in ~
Role re ncc
Vertical
Microetch
Baseline
130
Pagel 1992
((
((
Slow withdrawal rate
72
((
((
((
Intermediate withdrawal rate & longer
drain time
76
((
((
Electroless
Baseline
65
((
((
((
Slow withdrawal rate
32
((
((
((
Intermediate withdrawal rate & longer
drain time
31
((
Vertical
Not
specified
CH2M-Hill study
103
Sharp 1998
Horizontal
((
Based on experience
27-67
((
Vertical
((
Boards with holes
95
((
((
((
Interlayer boards without holes
41
((
((
((
Vertical parts, well drained
161
Pinkerton 1984
((
((
Vertical parts, poorly drained
82
((
((
((
Vertical parts, very poorly drained
160
((
((
((
Rack plating (used to estimate metals in
wastewater for design of wastewater
treatment system)
203
Hansan &
Zabban 1959
Not specified
Not
specified
Drag-out value assumed in order to
compare costs of rinsing alternatives
162
Yost
((
((
Drag-out value assumed to evaluate waste
minimization
160
Chang &
McCoy 1990
Vertical
19-20 g/L &
240-250 g/L
Cr03
Studies at varying drainage angles,
drainage times, and withdrawal rates
12-65
SiiP 1990
Vertical
Various
electrolytes
Experimental determinations to test
theoretical equations
18-94
SiiP 1992
1 Suggested by Pinkerton as being the absolute minimum for drag-out on a vertical sheet.
Drag-Out Prediction Equations
Kushner (1951a) was one of the first researchers to study drag-out in detail. Kushner
distinguished two stages in the generation of drag-out. The first stage is the "withdrawal" stage in
which the work piece is moving out of the liquid but is still in contact with it. The second stage is
"drainage" in which the work piece is completely out of the liquid, but is still over the bath and
liquid is still running off the piece. Kushner considered the withdrawal stage the more important,
because the withdrawal determined the thickness of the adhering liquid film. The factors that
E-24
-------
control the film thickness are the velocity of withdrawal, viscosity of the liquid, density of the
liquid, and surface tension of the liquid although he believed surface tension was a minor factor.
Using dimensional analysis, Kushner derived the following equation:
Eqn 5
where:
f
K
V
n
p
g
film thickness
unknown constant determined by experiments
velocity of withdrawal
viscosity
density
acceleration of gravity
unknown exponent determined by experiments
m
Based on experimental work of others, Kushner concluded that the best fit equation was equation
3 presented earlier:
Note that although equation 3 was derived by dimensional analysis, it does not appear
dimensionally consistent, because the acceleration of gravity is dropped as a term. This is also
the equation referenced by Pinkerton and Graham in the Electroplating Engineering Handbook
(1984). Importantly, this equation is for work pieces with smooth surfaces, unlike PWBs which
have many small holes. This equation will tend to underestimate drag-out for PWBs. Notably,
this is one of two equations tested by Slip (1992) and discussed above. The equation performed
poorly in predicting drag-out for a variety of electrolytes.
Kushner (1951b) argued that equation 3 gives good drag-out predictions for short drainage times,
but increasingly overestimates the drag-out with longer drainage times, because it does not allow
for the liquid that drains off the work piece. Conceptually for a rectangular sheet, the volume of
liquid that drains off the sheet is:
Eqn 3
A^= A'fdr = A- Fdr(f ,p,g,n,o ,tdr)
Eqn 6
where:
AV
A
volume of liquid that drains from the rectangular sheet
area of the sheet
thickness of the film that drains off the sheet
function describing a relationship between the independent variables and
thickness of the film that drains from the sheet
surface tension of the liquid
drainage time
°dr
tdr
E-25
-------
Hence, the net film thickness or the drag-out volume per unit area after any drainage time, tdr, is:
The volume of liquid that drains from the board is a complex process and Kushner was not able
to develop a predictive equation. He did, however, make qualitative statements about the effect
of several variables. Kushner believed that viscosity was the most important property of the
plating solution. Higher viscosities tend to increase the liquid adhering to the sheet as it is
withdrawn from the bath and tend to decrease the liquid that drains. Some chemicals in
particular are surface active and have molecular structures that increase viscosity. These
chemicals may cause a "surface viscosity" that give higher drag-out. Higher densities tend to
decrease the liquid adhering to the sheet and increase the drainage. However, the increase in
density due to a higher concentration of chemicals in solution is usually outweighed by the
increase in viscosity. Kushner gave an example of increasing a sucrose solution from 20% to
60%. This increases the density by 18% while the viscosity increases by 2700%). Lower surface
tension will thin the film thickness as the sheet is withdrawn and also increase the drainage as
well as reducing the volume of the bead of liquid along the bottom edge of the sheet. Of course,
wetting agents are surface active and will concentrate in the drag-out, and hence will be removed
at a higher rate than other chemicals. Longer withdrawal times and drain times will reduce drag-
out, but Kushner believed that it is better to have a longer withdrawal time than a longer drain
time. His rationale was to start with the smallest volume on the work piece to begin with. He
also referenced work by Soderberg that drainage times beyond 60 seconds have little effect.
Finally, Kushner recommended that work pieces be oriented to minimize the drainage distance
and that the pieces be tilted.
Rinsing Theory
The primary source of the quantity of wastewater generated is rinse water. Most process baths
are followed by two rinses, but sometimes just one rinse and sometimes three rinses. The
development of rinsing theory can be traced at least as far back as Kushner (1949). Pinkerton and
Graham (1984) summarized some of the fundamental mathematical relationships for rinsing. For
a non-running rinse tank and assuming that ideal, instantaneous mixing occurs, the concentration
of a contaminant in the rinse tank is given by:
/ = 0.02Jv • - Fdr(f,p,g,ji,o,tdr)
Eqn 7
Eqn 8
where:
C,
concentration of contaminant in rinse tank after t min
concentration of contaminant solution being drug into rinse tank
volume of rinse tank
volume of drag-over or drag-out on rack and work rinsing operation
number of rinsing operations in t min
V,
D
n
E-26
-------
Most rinse operations at larger facilities use multiple countercurrent cascade rinses. In this case,
the concentration in the effluent from the rth rinse tank is:
(Q-t/D)-i
(Q-t/D)'*1- 1
Eqn 9
where:
Cr
Q
concentration of contaminant in the effluent of the rth rinse tank
rate of fresh water flow
time interval between rinsing operations
number of rinse tanks in series
t
r
Talmadge (1968) presents equations similar to the above but with an extra term to account for
imperfect mixing, i.e., imperfect removal of the contaminant from the work piece.
An approximate equation for multiple, countercurrent rinses has apparently been used by some
(Hanson andZabban 1959; Mohler 1984):
Mohler (1984) discussed how rinsing equations can be used in practice. In general the rinse must
not cause a loss in product quality. There is, then, a maximum allowable concentration in the
final rinse called the "contamination limit." The ratio of the concentration in the drag-in, C0, into
the first rinse tank (or drag-out from the process bath) to the concentration in the final rinse, Cr, is
the dilution factor or "rinsing ratio," C
-------
The approach above is consistent with Kushner (1949). Kushner observed that the purpose of
the rinse tanks are to "stand guard between baths to keep one solution from mixing with another
and contaminating it." The rinse water flow rate partially determines the concentration of
carryover into the next plating tank and thus the plating quality. Kushner believed that each rinse
system in a facility would have its own unique rinsing ratio, C
-------
Other Rinsing Theory Studies
Several other rinsing theory studies have been conducted by various researches. Some of these
have focused on how well the drag-out is dispersed into the rinsing tank. While interesting, these
studies are not applicable to this project, because sufficient rinsing is used in practice such that
most of the drag-out ends up in the rinse water and thence the wastewater. For example,
Talmadge and Sik (1969) developed equations to describe the dispersing of the bead of liquid at
the bottom of a plate into the rinse water. They extended previous work that used diffusion
theory to predict the residual contaminant on a plate in a rinse tank. Talmadge and Buffham
(1961) and Talmadge et al. (1962) made detailed investigations of rinsing effectiveness in the
absence of mixing or agitation other than the flow of rinse water in the tank, i.e., molecular
diffusion is the dominant mass transfer mechanism. They found in such cases that about 10% of
the contaminant is left in the film a flat sheet as compared to typically less than 0.1% when using
ideal mixing rinse equations. However, the situation is not typical of practice, and as mentioned
above, using the ideal complete mixing equations gives a conservative estimate of contaminant in
the wastewater, i.e., less contaminant is left on the board.
PWB Pollution Prevention and Control Technology: Analysis of Updated Survey Results
As part of an EPA funded project, a questionnaire survey form on pollution prevention was sent
to 400 PWB shops in 1995 and 40 shops responded. A shortened survey was sent in 1997 to 250
PWB shops in California and 45 responded for a total of 85 between the two surveys. A
summary of information relevant to this project follows (U.S. EPA 1998).
Wastewater generation. Most of the wastewater generated is from rinsing. The best estimate of
water usage is 10 gallons/(layer-ft2 of production) or 410 1/m2 which is the "wetted" surface area
and was "calculated based on the total surface area of all layers of boards manufactured." This
value is the mean of the 20 largest shops. Large shops had the most reliable data. Smaller shops
were encouraged to estimate their data if they did not know, and this made their data suspect.
Recycle, recovery, and bath maintenance. The survey revealed several practices for recycle,
recovery, and bath maintenance:
• Nearly all shops responding to the survey reported using off-site recycling for one or
more of their spent process baths although the percentage recycled for each bath type was
not reported. The most common bath sent for recycle was spent etching because the
baths have high copper concentrations of about 150 g/L. About 80-85% of the
responders used an ammoniacal etchant and most of the rest used cupric chloride. The
volume of spent ammoniacal etchant solutions generated was 1 gallon per 30 ft2 (1.41/m2)
of inner- and outer-layer panels. Other types of spent baths were far less likely to be sent
off-site for recycle. Tin and/or tin-lead stripping solutions were the next most common
spent bath sent off-site and was reported by 20% of the survey responders.
Approximately 50% of the responders used a tin outer-layer etch resist and 50% used a
tin-lead etch resist. Only 10% of responders indicated that spent rack stripping solutions
are sent off-site.
E-29
-------
This stripping solution results from removing plating deposits from racks used to hold the
PWBs. This solution can be a significant waste. Based on the survey report, we will
assume that only spent etchant baths are sent off-site for recycle.
• The use of various technologies to recycle and recover baths and waste streams on-site
varied. Ion exchange was used by 45% of the responders to treat and recover discharges,
but many times this was part of their waste treatment system.
• The volume of wastes generated from spent baths was estimated as shown in Table 9.
Wastewater treatment. Wastewater treatment systems removed the metals by conventional
precipitation systems, ion exchange, or a combination of the two. Wastewater treatment sludges
generated are typically (88% of responders) sent off-site for recycle rather than disposed of in a
landfill. Sludge generation data were few. The three largest facilities reporting data had sludge
generation rates of 0.02, 0.31, and 0.24 kg/m2. The smallest number, 0.02 kg/m2, came from a
facility making only single sided boards whereas the other two had a larger mix of products
which generated more waste.
Drag-out reduction practices. Table 10 shows the drag-out reduction or recovery practices used
by the responders.
Drag-out reduction can reduce pollution, but it can cause problems for the process baths due to
greater build-up of contaminants in the bath. One or more bath maintenance techniques may be
required.
Water Use Rates from Survey of MHC Facilities
As part of a U.S. EPA sponsored research project, the University of Tennessee CCPCT (1997)
surveyed MHC PWB plating facilities. Part of the survey addressed water use for various MHC
process alternatives. Table 11 shows the estimated water consumption for MHC alternatives
based on the survey data and normalizing assumptions.
These water consumption rates are of the same order of magnitude as those from the U.S. EPA
(1998) survey discussed earlier which estimated water usage to be 10 gallons/(layer-ft2 of
production) as the mean of the 20 largest shops.
E-30
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Table 9. Selected Waste Volume Estimates From Spent Baths.
Process
Waste
Volume1
(per 1,000 ft2 of
4 layer boards)
Volume1
(per m2 of
4 layer boards)
Etching, inner and outer layers
Spent etchant
140 gallons
5.7 liters
Dry film resist developer
Spent developer
200 gallons
8.1 liters
Dry film resist stripper
Spent stripping solution
6 gallons
0.24 liters
Tin-lead stripper
Spent stripping solution
17 gallons
0.69 liters
Soldermask developer
Spend developer
60 gallons
2.4 liters
Microetch; inner and outer layers
Spent micro-etchant
16 gallons
0.65 liters
Sulfuric acid dips
Spent sulfuric acid baths
12 gallons
0.48 liters
Electroless copper
Waste electroless Cu bath
26 gallons
1.1 liters
Board trim
Waste copper-clad material
187.5 ft2, 42.9 lbs Cu
0.1875 m2, 19.6 kg
1 Assumptions:
a) Ammoniacal etchant used for both inner- and outer-layers, 70% of copper foils etched, 1 oz. copper used on all
layers, and 20 oz/gal carrying capacity of etchant.
b) 50% of film developed (30% outer, 70% inner), developer carrying of 3 mil-ft2/gal, and 1 mil film is used
throughout.
c) 50% of film stripped (70% outer, 30% inner), stripper carrying capacity of 100 mil-ft2/gal, and 1 mil film is used
throughout.
d) 30% metal area, tin-lead resist is 0.3 mil thick and stripper capacity of 15 oz/gal of metal.
e) 30% of mask developed, 1 mil thickness, 10 mil-ft2/gal carrying capacity.
f) Oxide, electroless Cu, and pre-pattern plate microetches (50%, 100%, and 30% of surface area etched,
respectively) considered. Many facilities may employ additional baths.
g) Microetches average etch and 4 oz/gal carrying capacity.
h) Bath life of 1 gallon/500 ssf, 3 sulfuric dips (oxide, electroless copper, and pattern plate lines).
I) 18x24 panels with 0.75 inch thief area and 0.25 inch spacing of 6 step-and-repeats, outer layer 2 oz copper (80%
trim area), inner layer 1 oz copper (50% trim area).
E-31
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Table 10. Drag-out Reduction or Recovery Practices Used by the Responders.
Drag-Out Reduction or Recovery Practice
PWB Responders
Using, Vo1
Plating Shops
Using, %2
Allow for long drip times over process tanks
76.3
60.43
Have drip shields between process and rinse tanks
60.5
56.9
Practice slow rack withdrawal from process tanks
52.6
38.1s
Use drag-in/drag-out rinse tank arrangements
34.2
20.83
Use drag-out tanks and return contents to process baths
34.2
61.03
Use wetting agents to lower viscosity
31.6
32.4
Use air knives to remove drag-out
26.3
2.23
Use drip tanks and return contents to process baths
10.5
27.03
Use fog or spray rinses over heated process baths
10.5
18.9s
Operate at lowest permissible chemical concentrations
7.9
34.6
Operate at highest permissible temperatures
5.2
17.9
Data from PWB survey.
2 Data from 1993-1994 survey of for the metal finishing industry.
3 Data are for manually operated methods, which are the predominant type for the plating operations surveyed during
the NCMS/NAMF project.
Table 11. Water Consumption Rates of PWI
MHC Alternatives.
Process Type
Water Consumption1
(gal/ft2)
(1/m2)
Electroless copper, non-conveyorized
11.7
476
Electroless copper, conveyorized
1.15
46.8
Carbon, conveyorized
1.29
52.5
Conductive polymer, conveyorized
0.73
30
Graphite, conveyorized
0.45
18
Non-formaldehyde electroless copper, non-conveyorized
3.74
152
Organic-palladium, non-conveyorized
1.35
54.9
Organic-palladium, conveyorized
1.13
46.0
Tin-palladium, non-conveyorized
1.80
73.2
Tin-palladium, conveyorized
0.57
23
1 Based on wetted board surface area.
E-32
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RESEARCH APPROACH
The objective of this study was to develop and validate methods to predict the quality of waste
water generated from PWB manufacturing processes. The methods can then be used to compare
alternative manufacturing processes in the PWB industry. In the DFE studies, industrial and
environmental exposure and risk are evaluated on a chemical-specific basis for individual
manufacturing operations. Wastewater data collected during routine regulatory sampling are
inadequate for these purposes because data are collected for only a few specific pollutants and
the samples contain wastewater from the entire plant rather than an individual process line. For
these reasons, a mass-balance calculation is the most suitable approach to estimating the load of
each pollutant emanating from a given process line.
The literature review revealed that drag-out was the source of most of the contaminants in the
wastewater from a given process. Process-specific waste loads originating from drag-out can be
estimated by the product of the drag-out volume and the chemical concentration in the process
baths. The latter are determined as an existing component of the DFE process. However,
according to the literature review, drag-out volume from PWBs and other flat, vertical pieces can
vary between about 10 and 120 mL/m2. Drag-out was affected by variables such as bath
chemistry, board withdraw rate, drain time, and orientation of the boards during withdraw.
Board surface characteristics and the number and geometry of holes drilled in the board may also
be significant, but these variables have not been systematically investigated to date. Equations
presently available in the literature fail to accurately predict the volume of drag-out from vertical
plates (Slip 1992).
The MHC process was selected as the basis of the research because a significant data base
already existed for this process as a result of the previously concluded DFE project. Also, the
research team was most experienced and familiar with this process line. The results of this work
apply to other PWB processes that employ process baths in which the boards are vertically
oriented.
The specific steps in the research plan were:
• To conduct limited laboratory drag-out experiments for the purpose of supplementing
existing data in the literature.
• To identify or develop an accurate and comprehensive drag-out model for PWB using a
data-base that includes data developed in this study and by others.
• To develop a computer model to predict wastewater quality and quantity from a PWB
processes that incorporates the new drag-out model.
• To validate the model using data from process bath and rinse water samples collected
from three MHC process lines.
E-33
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LABORATORY DRAG-OUT EXPERIMENTS
Laboratory drag-out experiments were conducted to supplement existing drag-out data in the
literature. Existing drag-out equations do not accurately predict the effect of fluid properties on
drag-out from vertical flat pieces such as PWBs (Slip 1992). While some studies have
investigated the effect of viscosity, another parameter that may exert significant influence, surface
tension, has received virtually no attention. The scope of this study did not allow a
comprehensive evaluation of the effect of these parameters. Instead, an alkaline cleaner bath was
selected as a bath that was more difficult to drain and a microetch bath was selected as one that
would be relatively easy to drain. During the study, viscosity and surface tension would be
measured to gain an indication of the relative influence of these parameters on drag-out.
The procedures for the laboratory drag-out experiments were devised to simulate conditions
occurring in the PWB manufacturing process. The drag-out volume was measured
gravimetrically as the boards were withdrawn from the process tanks. Experiments were
conducted using two heated process baths to determine the range of expected drag-out volumes
under various conditions. Because the alkaline cleaner/condition and microeth baths have
significantly different chemical compositions and properties, these baths were chosen for the
experiments to provide a realistic range of drag-out volumes. The board size was 0.457 m by
0.610 m. Experimental conditions that were studied were the orientation of the board during the
drain time, the length of the drain time, the board withdraw rate from the bath, and shaking the
board at the beginning of the drain period. Withdraw rates of 0.076 m/sec and 0.305 m/sec were
tested, and the boards were drained with the long edge horizontally, vertically, or at a 45° angle.
Drain periods of 10 seconds, 20 seconds, and 30 seconds were studied. The basic operating
conditions (BOC) for the majority of the tests were: 0.076 m/sec withdraw rate, 10 second drain
time, no shaking after board withdraw, 45° drain angle, and the board oriented with the long edge
horizontal. Nine sets of experiments were conducted on each bath for a total of eighteen drag-
out experiments. Several additional experiments were conducted with the microetch bath for a
drilled board with a different hole density and design. The matrix of experimental conditions that
were tested for each of the two baths is presented in Table 12.
For the alkaline cleaner/conditioner experiments, generally five repetitions were made for each
condition, with the circuit board remaining submersed in the bath for one minute on each test.
Since the etching process changed both the properties of the circuit board and the chemical
composition of the bath, only three repetitions for each condition were performed and the boards
were only allowed to remain submersed for 30 seconds. These conditions were taken into
account by assuming that the copper etch rate would remain constant over the duration of the
experiments. This assumption was verified by weighing the boards before and after the tests to
determine the mass of copper etched from the board.
E-34
-------
Table 12. Experimental Matrix for Laboratory Study of Drag-out Volumes for
Each Bath Type.
Kxpcrimcntiil
Con dilions
Drilled Hoard
1 nil rilled lion ril
Drilled. Klclied Hoard
0.076 m/sec withdraw
45° drain angle
10 sec drip time
no shaking
!
!
!
0.076 m/sec withdraw
long edge horizontal
10 sec drip time
no shaking
!
0.076 m/sec withdraw
long edge vertical
10 sec drip time
no shaking
!
0.076 m/sec withdraw
45° drain angle
20 sec drip time
no shaking
!
0.305 m/sec withdraw
45° drain angle
30 sec drip time
no shaking
!
1.0 fps withdraw
45° drain angle
10 sec drip time
no shaking
!
0.076 m/sec withdraw
45° drain angle
10 sec drip time
shake board
!
Apparatus
10 cm by 61 cm by 76 cm high density polyethylene (HDPE) tank, supported and
stabilized to prevent tipping.
Magna-Whirl Constant Temperature Water Bath, Model MW-1140A-1.
Pump, ITT Jabsco Self-Priming, Model 12290-0001, 115 volt, 3.3 amp, with thermal
overload protection.
6 m of 1.3 cm diameter stainless steel tubing, coiled to fit inside bottom of HDPE tank.
1.3 cm I.D. Nalgene tubing, lab/food grade, with connection clamps.
48 liters bath solution (Alkaline Cleaner/Conditioner or Microetch).
Mettler Toledo Electronic Analytical Balance, Model PR5002, Maximum 5100 grams,
with cardboard air current shield.
E-35
-------
• 0.457 m by 0.610 m circuit boards (copper clad with holes; copper clad without holes;
etched, with holes).
• Plastic bags, 0.50 mil, 110 1 capacity.
• Whittner Taktell Super-Mini Metronom, Model 886051, set at 120 beats per minute.
• Laboratory clamps and clips.
Procedure
1. For the first set of experiments, the Alkaline Cleaner/Conditioner bath was prepared
according to the manufacturer's specifications by filling the HDPE tank with 24 L of
deionized water. Next, 2.88 L of Electro-Brite ML-371 were added, and the tank was
brought to a volume of 48 L with deionized water to produce a 6% (by volume)
concentration. The solution was gently mixed. For the second set of experiments, the
Microetch bath was prepared according to the manufacturer's specifications by filling the
HDPE process tank with 24 L of tap water and adding 720 g of copper sulfate
pentahydrate (CuS045H20) and 8.64 L of 66° Baume sulfuric acid (H2S04). The acid was
added very slowly, taking care that the temperature of the mixture remained below 54° C.
A laboratory thermometer was inserted into the mixture to monitor temperature. Next,
3.34 L of Co-Bra Etch Inhibitor Makeup were added, and the mixture was brought to a
volume of 48 L with tap water.
2. The stainless steel heating coil was placed into the HDPE tank containing the simulated
bath. The coil inlet was connected to tubing from the water bath (with the in-line pump),
and the coil outlet connected to tubing discharging back to the water bath. The
experimental set up is presented as Figure 4.
3. The Magna-Whirl water bath was filled with approximately 95 liters of hot tap water. The
water bath heater and pump were turned on, allowing the bath to equilibrate to 57° C for
the alkaline cleaner/conditioner, and 52° C for the microetch bath. The water bath
thermostat was set, and a thermometer was placed in the bath to monitor the bath
temperature.
4. The bath temperature, pH, and density were measured in-situ in the tank. Conductivity,
viscosity, and surface tension were measured on a sample collected from the tank.
Analyses were performed as described later in the section entitled: COLLECTION AND
ANALYSIS OF FIELD SAMPLES.
5. The circuit board was cleaned with tap water and detergent, and thoroughly rinsed with
deionized water. The board was dried using compressed air to ensure no moisture
remained entrapped in the holes.
6. The board was centered on the analytical balance, and the weight was recorded to the
nearest 0.01 g.
7. A clean new plastic bag was weighed on the analytical balance, and the results recorded to
the nearest 0.01 g.
8. The plastic bag was opened, and carefully attached to the outside of the HDPE tank using
small laboratory clips.
E-36
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9. The metronome was turned on, and two laboratory clamps were attached to the circuit
board to serve as handles. The circuit board was slowly lowered into the tank so the
entire surface was completely submerged in the bath. The board was agitated slightly to
remove entrapped air bubbles, and then allowed to remain submerged for approximately
one minute in the alkaline cleaner/conditioner bath or 30 seconds in the microetch bath.
The process was timed by counting ticks on the metronome.
10. The board was removed vertically at the appropriate withdraw rate, stopping several
inches above the bath surface. Depending on the experiment, the board was then either
held steady or given one quick shake, and the board held so that its edge was either level
or at a 45° angle during the allotted drain time. The appropriate withdraw rates, drain
positions, and drain times were specified in the Table 12. Both the withdraw rate and drip
time were timed by ticks of the metronome.
11. The board was immediately placed into the plastic bag attached to the tank. Extra care
was taken to ensure that any drips after the specified drain period fell into the bag, and
that the sharp corners of the board did not puncture the bag.
12. The clamps were removed from the board, along with the clips holding the bag to the
tank. The bag was carefully sealed, removing as much air as possible.
13. The sealed bag containing the circuit board and drag-out was centered on the analytical
balance and weighed, the results were recorded to the nearest 0.01 g.
14. The circuit board was carefully removed from the bag, and the process was repeated,
beginning with weighing a clean new plastic bag.
15. After the specified number of runs were completed for each set of conditions, the bath
temperature, pH, and density were again measured in-situ in the tank. Conductivity,
viscosity, and surface tension were measured on a sample collected from the tank.
Analyses were performed immediately after collecting the sample, and the results were
recorded.
16. The drag-out volumes were calculated.
Before the actual drag-out experiments were conducted using PWB bath chemicals, a series of
four preliminary tests were conducted to validate the proposed methodology and to verify that
the drag-out could be measured accurately and precisely. The preliminary tests also served as
practice runs, and allowed for any necessary adjustments to the procedure and apparatus. The
coefficients of variation for the first two tests were 0.039 and 0.056, for eleven and nine trials,
respectively. The coefficients of variation in the third and fourth tests improved to 0.007 and
0.008, respectively, for series of seven trials each. Since preliminary tests were not designed to
cover the full range of operating variables, the following representative variables were selected: 1)
ambient temperature tap water was used to simulate bath chemicals; 2) a 0.265 m x 0.457 m
drilled etched board was used in the first two preliminary tests, and a 0.457 m by 0.610 m drilled
copper clad board was used for the third and fourth tests; and (3) the circuit board was
withdrawn at 0.15 m/sec, given one quick shake after removal, and allowed to drip for 10
seconds.
E-37
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Quality Assurance and Quality Control (QA/QC)
Prior to the experiments, all laboratory equipment was thoroughly cleaned with detergent
followed by a thorough deionized water rinse. The analytical balance used for weighing the
boards was allowed to warm up for at least 30 minutes before any measurements were made.
The balance was calibrated using calibration weights at the beginning and end of each laboratory
session, to ensure the instrument had not drifted. A large shield was placed around the balance to
decrease the effects of drafts while weighing the board.
Prior to mixing the actual baths, 500 ml batches of the solution were prepared per the
manufacturers' product information sheets. Measurements of viscosity, specific gravity, surface
tension, conductivity and pH were compared between the 500 ml batches and the full bath
volume. Temperature was monitored continuously during the drag-out experiments in the baths
by suspending a laboratory thermometer in the tank. Before the tests, the timing of the
metronome was checked with a clock to ensure proper timing. The tank was positioned in front
of a fume hood for adequate ventilation, and a large strip of tape was affixed to the fume hood
shield at a 45° angle from the horizontal to use as a guide during drain periods. Personal
protection equipment such as safety goggles, gloves, and aprons were used whenever feasible.
All waste material including plastic bags contaminated with the drag-out chemicals and the used
bath solutions were stored for proper disposal. All laboratory experimental information and data
were recorded in a laboratory notebook, with carbon copies given to the principal investigators
upon test completion.
Results and Discussion
Results of the laboratory drag-out volume experiments are presented in Tables 13 and 14 for the
alkaline cleaner/conditioner and microeth baths, respectively.
Table 13. Drag-*
Dut Results for Alkaline Cleaner/Conditioner Bath.
Test
Board Type
Drag-Out (ml/sq.m)
Coeff. of Variation
BOC
drilled, design 2
77.8
0.032
BOC, board edge horizontal
drilled, design 2
75.6
0.015
BOC, board edge vertical
drilled, design 2
81.3
0.021
BOC, 20 sec. drip time
drilled, design 2
68.2
0.040
BOC, 30 sec. drip time
drilled, design 2
64.5
0.047
BOC, 1 fps withdraw
drilled, design 2
98.7
0.013
BOC, with shake
drilled, design 2
77.8
0.032
BOC
undrilled
38.6
0.016
BOC
drilled, etched
89.2
0.038
Note: Design 1, 5619 holes; Design 2, 7824 holes.
E-38
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Table
4. Drag-Out Results for Microetch Bath.
Test
Board Type
Drag-Out, ml/sq m
Coeff. of Variation
BOC (2/2/99)
drilled, design 2
108.9
0.043
BOC (2/13/99)
drilled, design 2
107.8
0.023
BOC (2/13/99)
drilled, design 2
93.4
0.038
BOC, board edge horizontal
drilled, design 2
120.9
0.006
BOC, board edge vertical
drilled, design 2
113.0
0.006
BOC, 20 sec. drip time
drilled, design 2
98.1
0.015
BOC, 30 sec. drip time
drilled, design 2
94.4
0.007
BOC, 1 fps withdraw
drilled, design 2
133.1
0.016
BOC, with shake
drilled, design 2
111.9
0.021
BOC
drilled, design 2
69.8
0.038
BOC, etched board
drilled, design 2
112.3
0.022
BOC, etched board
drilled, design 2
118.3
0.021
Note: Design 1, 5619 holes; Design 2, 7824 holes.
The drag-out volume for each experimental condition was calculated using the mean drag-out
weight from the group of tests for the specific condition. This was generally five runs for the
alkaline cleaner/conditioner, and three runs for the microetch. In addition to calculating the mean
drag-out weight (in grams), the standard deviation and the coefficient of variation of the
measurements were checked for each condition. The coefficient of variation was less than 0.05
for all experiments.
The mean drag-out volume for all experimental conditions for the alkaline cleaner/conditioner
was 74.7 ml/m2, which is approximately 30% less than the mean drag-out volume of 108 ml/m2
for the microetch bath. The mean drag-out for all experimental conditions for both baths
combined was 91.1 ml/m2, and was calculated using only data from the same board hole design
so as not to skew the results. It appears that drain time has an affect on drag-out volume, as
reflected in the decreasing drag-out volumes as drain time increased. It also appears that the
drag-out volume increases as the board withdraw rate decreases. Board tilt and orientation did
not appear to affect the drag-out volume; however, drilled boards had more drag-out than
undrilled boards, as expected.
Results from the microetch experiments compare favorably to those performed at Micom, Inc.
(Pagel 1992), although a direct comparison was difficult since operating conditions were different.
Board hole density for both tests were similar, with Micom boards having 33,000 holes/m2
compared to 28,000 holes/m2 for the boards used in the microetch experiments in this study.
Pagel's drag-out volumes appear to be less than those measured in this study. At a withdraw rate
of 0.20 m/sec and drain time of 12.1 sec, Pagel reported a drag-out volume of 76.4 mL/m2. Under
similar conditions, specifically a withdraw rate of 0.305 m/sec and a drain time of 10 seconds, this
study resulted in a drag-out of 130 mL/m2. Other differences in experimental
E-39
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procedures that could affect drag-out volumes include: 1) a 45° drain angle used in this study,
compared to a 0° angle used by Pagel; 2) Pagel's experiments included drag-out associated with
the racks; and 3) drag-out was measured by completely different approaches; specifically, Pagel
used a concentration approach whereas this study used a weight approach.
Analyses of parameters for the alkaline cleaner/conditioner and microetch simulated baths were
performed before the drag-out tests were run, and again after the tests were completed. Results
of the tests are presented in Tables 15 and 16.
Table 15. Alkaline Cleaner/Conditioner Bal
h Properties.
Parameter
Before Experiments
After Experiments
pH
8.65 @ 58°C
8.47 @ 57°C
Conductivity mS/cm
0.21 @ 35°C
0.23 @ 35°C
Specific Gravity
8.65 @ 57°C
0.995 @ 57°C
Surface Tension, dynes/cm
34.7
34.7
Viscosity, cP
0.85
0.87
Ta
)le 16. Microetch Bath Analyses.
Parameter
Before Experiments
After Experiments
pH
-0.42 @ 53°C
-0.62 @ 55°C
Conductivity mS/cm
1374 @ 22°C
1562 @ 22°C
Specific Gravity
1.175 @53°C
1.205 @57°C
Surface Tension, dynes/cm
71
60
Viscosity, cP
1.44 @49°C
0.87 @ 50°C
As expected, there was no significant variation in the bath parameters for the alkaline
cleaner/condition bath comparing values before and after the drag-out tests. There were,
however, significant variations in the microetch bath characteristics, as expected. Conductivity,
specific gravity, hydrogen ion concentration and viscosity all increased, possibly due to the
increase in copper in the bath as a result of etching from the PWBs during the drag-out tests.
E-40
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DRAG-OUT MODEL DEVELOPMENT
As stated previously the goal of this project was to develop and validate methods for predicting
the quality of wastewater generated during PWB manufacturing. Drag-out and bath dumps are
the two major sources of process wastewater. The literature reports drag-out rates for flat panels
and PWBs ranging from 10 to 160 ml/m2. Currently-available models utilize solution viscosity
and withdraw rate as the primary independent variables. SiiP (1992) has demonstrated that drag-
out rates predicted using these models are poorly correlated with results from experiments.
Clearly there is a need for a more a more accurate means of predicting drag-out for PWB
manufacturing.
In addition to the drag-out data collected as part of this study, three data sets containing extensive
drag-out data for PWBs or flat panels were available in the literature (SiiP 1990; SiiP 1992; Pagel
1992; Ducker). An attempt was made to develop regression models to predict drag-out volumes
as a function of PWB manufacturing practices. Possible model variables that were either
recorded or varied in each study are summarized in Table 17.
Table 17. Potential Variables for
'WB Drag-Out Prediction Model.
SuP 1990
SuP 1992
Pagel
1992
This Study
Board Size
Withdraw Rate
Drain Time
Board Orientation
Board Angle
Board Surface
Holes
Shaking or Vibration
Bath Type
Kinematic Viscosity
Surface Tension
Of the variables listed in the table above, not all were evaluated for inclusion in the model. Board
surface (etched or unetched) and shaking were not included in the parameters to be evaluated
because the little data that were available for these parameters indicated they have a minor effect
on drag-out volumes. Board orientation during draining was also not considered because
relatively few data were available and it is not one of the waste minimization practices commonly
practiced. We hypothesized that kinematic viscosity and surface tension were two fluid properties
that may be most significant in determining drag-out volumes. However, SiiP (1992) showed
that drag-out volume was poorly correlated with kinematic viscosity. Furthermore, Pagel's data
set did not include data for either kinematic viscosity or surface tension of the baths and SiiP's
data did not include any surface tension data. It was judged that the quantity of data and range of
values for these two variables were insufficient to justify their inclusion in the model.
E-41
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In the data base used to develop the model, board size (m2), withdraw rate (m/sec), and drain
time (sec) were treated quantitatively by using the numerical value of the variable. Three other
variables were treated qualitatively using indicator variables having values of 1 or 0. The indicator
variable for board angle was assigned a value of 1 if the board was angled and a value of 0 if the
board edge was kept horizontal. Similarly, the indicator variable for holes was assigned a value of
1 if it contained holes and a value of 0 if the board did not contain holes. The hole density for the
drilled boards in the data base ranged from 20,000 to 33,000 holes/m2; however, data needed to
further quantify the effect of drilled holes, such as hole diameter and aspect ratio, were not
available. Three different indicator variables were included to specify bath type: alkaline cleaner,
micro-etch and electroless copper. The obvious disadvantage of this approach is that the model
can make bath-specific predictions only for these three bath types, but insufficient viscosity and
surface tension data are available to make the model more general.
The data set was not ideal for development of the model. The work of Slip (1990, 1992) was not
specific to the PWB industry; therefore, he did not use standard PWB process baths, his boards
were smaller than those often used in the PWB industry, and his boards did not contain drilled
holes. As a result, variables describing board size and holes were strongly correlated (0.904),
making it difficult to distinguish between the effects of these two parameters. Also, Slip did not
use actual PWB process baths, thus bath type and board size were also correlated. During model
development, it was necessary to be aware of the effects that these peculiarities may have on the
developed model.
Both a linear regression model and a multiplicative regression model were tested. The linear
model was:
WR
DO = a0 + axSIZE + a2WR + a^DT + a4 + a5WR ¦ DT +
a6HOLES + a-j ANGLE + agALK + a9MICRO + awELCTRS
where:
DO = drag-out volume, mL/m2
SIZE = board area, m2
WR = withdraw rate, m/sec
DT = drain time, sec
HOLES = 1 if the board is drilled and = 0 for undrilled boards
ANGLE = 1 of the board is tilted during draining and = 0 if the board is kept
horizontal
ALK = 1 if the bath is an alkaline cleaner bath and = 0 otherwise
MICRO = 1 if the bath is a micro-etch bath and = 0 otherwise
ELCTRLS = 1 if the bath is an electroless copper bath and = 0 otherwise
The multiplicative model was:
E-42
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DO =a0- SIZEai ¦ WRa2 ¦ DTa3 • a6HOLES ¦ a7 lX(;iJ':
„ ALK .t MICRO ELCTRLS „ 10
¦a 8 • <29 • <210 Eqn 12
which was rewritten in linear form for analysis by linear regression:
log DO = log a0 + ax log SIZE + a2 log WR+ a3 log I)T + HOLES\oga6 +
ANGLE log a-j + ALKXoga, + MICRO\oga9 + ELCTRLS\ogaw
Eqn 13
Both models were evaluated using stepwise regression (SSPS ver. 9). This procedure adds or
removes independent variables to the model based on criteria related to the reduction in the sum
of squares achieved by inclusion of the variable. The final model includes only the variables that
result in a statistically significant reduction in the sum of squares error. The stepwise regression
procedure yielded an r2 = 0.883 for the linear model and 0.814 for the multiplicative model. The
linear model was:
WR
DO = 3.63 + 694¦ SIZE - 180¦ ELCTRLS + 89.6•— Eqn 14
- 155-ALK + 38.6¦ HOLES + 29.9-WR - 0.443-DT-127 MICRO
The statistical package did not include the variables of ANGLE and WR-DT in the model because
they were not statistically significant. Inspection of this equation reveals that all three bath-type
coefficients are relatively large negative numbers, which would cause it to predict an erroneously
large drag-out for large boards (ca. 0.25 m2) with bath-types not explicitly accounted for in the
model. For small boards (ca. 0.05 m2) used with the bath-types accounted for in the model, it
could predict negative drag-out values. These anomalies were the result of correlation of the
independent variables, as described earlier. To correct this problem it was necessary to eliminate
one of the three bath types as a variable in the model. Each of the three bath types was evaluated
for elimination, the best fit was given by eliminating MICRO as a variable (R2 =0.852). The final
drag-out model was:
WR
DO = 18 + 201-SIZE - 60.1-ELCTRLS + 73¦
DT
-20.9-ALK + 26.0 ¦ HOLES + 26.1-WR - 0.355-DT Eqn 15
A comparison of predicted and measured drag-out volumes is shown in Figure 5. The groups of
vertically-aligned data points occur when the model predicts a near-constant drag-our for
conditions in which the measured drag-out is variable. While some of the variability is random
error, some is also the result of variation of the independent variables, indicating that the model is
not able to accurately account for all the variables that affect drag-out. A more comprehensive
data base in which the independent variables are systematically varied is needed if more accurate
predictions of drag-out from PWB manufacturing processes are desired.
E-43
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180
160 -
c
-------
PWB WASTEWATER MODEL
Given the volume of drag-out from and chemical composition of each bath, it is possible to
calculate the mass of each contaminant that would enter the waste stream for a given PWB
process line. A computer model was developed to facilitate such calculations. The model was
based on the following assumptions:
1. Contaminants in wastewater are from drag-out from process baths and from dumping of
some baths at the end of their useful life. Contaminants from the stripping of racks from
deposits are ignored.
2. Essentially 100% of the drag-out ends up in the wastewater, i.e., very efficient rinsing.
3. Predictions are for vertical boards only.
4. Various predictive equations reported in literature are of limited value for estimating
absolute values of drag-out as evidenced by the results of SiiP's work comparing
predicted versus measured drag-out. Equation 15 was used to estimate drag-out in the
model here.
5. Insufficient information exists to include surface tension as a variable although the
authors recognize that it may be an important variable.
6. The estimate of drag-out of contaminants in g/d is based on the PWB production rate,
chemical composition of each bath, and the estimated drag-out from each bath, according
to the following equation:
f kg / d of ^ i" pyvb production) ( Concentration of ^ ( drag - out from ^
contaminant i = , . , •, , •, . ,
I,rate, m /d J li inbathj, mg/Lj ^bathj, mL/m J Eqn 16
V from bath j J
The model is coded in an Excel Spreadsheet and utilizes a Visual Basic Macro. The user is
required to enter information in a separate spreadsheet defining the operating conditions of the
process line and the chemical composition of the baths. The effect of bath dumps on the overall
pollutant load can be included by specifying their frequency. The model calculates the mass of
contaminants coming from each process tank, together with the contaminant mass and
concentration for the entire process line. A user's manual is included in the Appendix.
E-45
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COLLECTION AND ANALYSIS OF FIELD SAMPLES
Samples of plating baths and rinse waters were collected from the MHC process line from three
different PWB facilities for the purpose of verifying the drag-out model. Three process baths at
each plant were selected for sampling: microetch, electroless copper, and Anti-Tarnish. Sodium
or potassium were selected as tracers for each bath because they are common ions in PWB baths,
and they tend to be relatively stable in solution. The relative amount of sodium and potassium in
the bath and downstream rinses can be used to estimate the drag-out from each tank and to verify
the overall mass balance approach to modeling wastewater quality from PWB facilities. In
addition to sodium and potassium, fluid properties (viscosity, surface tension and specific
gravity) that might effect the quantity of drag-out were measured. Routine measurements of
conductivity and pH were taken too. The project QA/QC plan (Robinson and Cox 1998),
submitted to and approved by EPA, was followed except where field conditions necessitated
minor changes.
Process Characterization
Operating practices affect the amount of drag-out and the concentration of contaminants in the
rinse-tank effluent. Extensive data characterizing the operating practices used at each site were
collected during the site visits. Operating practices potentially affecting the amount of drag-out or
the rinsing process are summarized in Tables 18-20. These data were later used to predict the
drag-out from each process bath using equation 15 and to independently calculate the drag-out
via a dynamic mass balance approach described later.
Table 18. Summary of MHC Operating Practices for the Field Sites.
Cycle Time, min
Withdraw Rate, m/sec
Board Tilt,
degrees
Hole Density, #/m2
Plant 1
30
0.173
5
100,000 to 570,000
Plant 2
37
0.163
0
NA
Plant 3
27
0.234
0
50,000
Table 19. Summary of Drip Times for Process Baths a
Bath
Drip Time,
sec
Plant 1 ME
5
Plant 1 EC
25
Plant 1 AT
5
Plant 2 ME
10
Plant 2 EC
15
Plant 2 AT
10
Plant 3 ME
5
Plant 3 EC
10
Plant 3 AT
5
Field Sites.
E-46
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Table 20. Summary of Rinsing Practices Used at Field Sites.
Rinse Time
(min:sec)
Rinse Tank
Vol (1)
Rinse Flow
Rate (1/min)
Rinse Water
Source
Mixing1
Plant 1 ME Rinse 1
1:20
832
7.6
ME Rinse 2
1,2
Plant 1 ME Rinse 2
1:00
832
7.6
city
1,2
Plant 1 EC Rinse 1
2:10
832
7.6
EC Rinse 2
1,2
Plant 1 EC Rinse 2
1:00
832
7.6
city
1,2
Plant 1 AT Rinse 1
3:20
832
7.6
AT Rinse 2
1,2
Plant 1 AT Rinse 2
2:00
832
7.6
city
1,2
Plant 2 ME Rinse 1
2:05
415
3.8
city
1,2
Plant 2 EC Rinse 1
8:00
415
3.8
AT Rinse 1
1,2
Plant 2 AT Rinse 1
3:55
415
3.8
city
1,2
Plant 3 ME Rinse 1
1:15
892
9.8
H2S04 rinse
1,2
Plant 3 EC Rinse 1
2:00
892
7.6
EC Rinse 2
1,2
Plant 3 EC Rinse 2
4:20
892
7.6
AT Rinse 1
1,2
Plant 3 AT Rinse 1
6:04
892
7.6
city
1
1 Mixing: 1 = Board Agitation; 2 = Aeration.
Sample Collection
Samples were collected for analyses from the laboratory drag-out study tanks in the UT
laboratory and from actual process baths and rinse tanks during the PWB industry site visits. For
the laboratory drag-out study in the UT laboratory, grab samples were collected for surface
tension and viscosity. The samples were collected directly from the experiment tank in a clean
beaker, and the analyses were immediately performed.
Samples were collected during the PWB site visits from the microetch (ME), electroless copper
(EC), and anti-tarnish (AT) process baths and their succeeding rinse tanks in the MHC process
line. Grab samples were collected using either a plastic measuring cup or a sampling beaker,
which consisted of a plastic beaker with a long handle attached. The sampling container was
thoroughly rinsed with the sampling fluid prior to sample collection. The grab sample was then
immediately transferred from the sampling cup or beaker into a clean 500 ml HPDE sample bottle
and capped. Before the sampling event, pre-printed labels were prepared in duplicate, with
one label pre-attached to the sample bottle. After the sample was collected, the remaining label
was attached to the Sub-Unit Data Collection Log, and the sample description, person taking the
sample, time of sample, sample volume, and method of preservation was recorded in ink.
Duplicate samples taken in identical manner were collected at plants 1 and 2. At plant 3, the two
samples were taken at different times in the board cycle. The first sample was taken just prior to
the boards entering the rinse tank while the second was taken just after the boards were removed.
Replicates were taken for approximately 20% of the samples. The sample bottles were sealed
with color-coded tamper-proof tape (to identify the sampler and establish chain-of-custody), and
placed in plastic lined containers for transport to the UT laboratory.
E-47
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Temperature
Temperature was measured in-situ in the laboratory drag-out tanks. In the field, temperature was
measured on grab samples collected from the process and rinse tanks. Measurements were made
immediately after collection.
pH
pH was measured in-situ in the laboratory drag-out tanks. In the field, pH was measured on grab
samples collected from the process and rinse tanks. Measurements were made immediately after
collection.
Apparatus
• Orion Digital Portable pH Meter, Model 250A.
• Orion Triode™ pH Electrode, Model 91-57BN.
Procedure for pH Measurements
1. After the meter was calibrated, the electrode was placed into the laboratory drag-out tank
or sample and agitated slightly.
2. When the pH display was stable, the pH was recorded on the Sub-Unit Data Collection
Log.
3. The electrode was rinsed with deionized water, and the process repeated.
The pH meter was calibrated prior to taking measurements for each sub unit. A two buffer
calibration was performed using the 4.01 and 7.00 buffers for the acid sub units, and 7.00 and
10.01 buffers for the alkaline sub units. The first measurement in a sub unit was made in the
samples from the last rinse tank, and the measurements progressed up-line, with the last
measurement made on the process bath sample.
Conductivity
Conductivity measurements were performed both in the UT laboratory and at the PWB site visits.
The instrument automatically compensates for temperature effects to a certain degree, except for
acids. Since many of the PWB baths and rinses were acids, and temperature could have a
significant effect on the conductance of these solutions, it was determined that all conductivity
measurements should be made at the reference temperature of 25° C. The conductivity
measurements originally made in the field at the PWB sites were re-analyzed on samples in the
UT laboratory at a controlled temperature of approximately 25° C. At the beginning of each lab
session, the conductivity meter was checked against a solution of known conductance to verify
accuracy.
The conductivity measurements of the rinse tanks were within the meter range of 0.0 to 199.9
mS/cm; however, as anticipated, the values of some of the process baths were higher. Since
conductivity is a nearly linear function of total dissolved solids (Snoeyink and Jenkins 1980), a
1:10 or 1:100 dilution with deionized water was performed on the sample if the initial reading was
above the highest range on the meter. The measurement was then taken on the diluted sample,
and the meter reading multiplied by the dilution factor.
E-48
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Two temperature and conductivity readings were taken on each sample, with the mean values
reported.
Apparatus
• Orion Conductivity/Temperature Meter, Model 122.
Viscosity
Viscosity was measured on site from grab samples collected from the rinse tanks, process baths,
and laboratory drag-out tanks.
Apparatus
• Gilmont Falling Ball Viscometer, size 1, with stainless steel ball, range 1 to 10 centipoise.
Procedure
1. The temperature of the rinse tank or process bath was taken using the laboratory
thermometer.
2. A grab sample was collected from the tank using a 2000 ml beaker. The viscometer,
stainless steel ball, and thermometer were immediately submerged into the sample for
approximately one minute to allow the laboratory equipment to equilibrate to the liquid
temperature.
3. The inside of the viscometer was rinsed with the sample, then slowly filled with rinse or
process bath liquid, making sure no air bubbles adhered to the sides of the viscometer.
4. The temperature of the liquid in the beaker was checked and compared with the tank
temperature. In general, if the temperature difference was more than approximately 5°C,
the beaker was emptied and a new sample collected.
5. The viscometer was held vertical in the center of the 2000 ml beaker. (The beaker still
contained the rinse or process liquid, which acted as a temperature bath for the
viscometer.) The stainless steel ball was carefully placed by hand into the filled
viscometer, making sure no air bubbles stuck to the ball.
6. A stopwatch was used to time the descent of the ball between the fiducial lines on the
viscometer. The time was recorded on the Sub-Unit Data Collection Log.
7. The viscometer and beaker were emptied, and the process repeated.
Using the mean descent time, the viscosity was calculated as follows:
jl=K{pf-p)t Eqn 17
where:
m = viscosity, centipoise
K = viscometer constant (0.257 with stainless steel ball, based on laboratory calibration
tests using deionized water and sucrose solutions, described below)
rf = density of ball, mg/1 (8.02 for stainless steel ball)
r = density of liquid, mg/1
t = time of descent, minutes
E-49
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The viscosity was recorded on the Sub-Unit Data Collection Log.
The viscometer, stainless steel ball, and beaker were thoroughly rinsed with deionized water prior
to the next test.
Before viscosity measurements were made in the field and on the laboratory drag-out tanks, a
series of tests were performed to establish the viscometer constant, K, for the falling ball
viscometer. The constant was obtained by measuring the time of descent of the stainless steel
ball in standard solutions of known viscosity, and was calculated using the following relationship:
K = -? -—r Eqn 18
Three solutions were used in the investigation: 30 percent sucrose (by weight), 40 percent
sucrose (by weight), and deionized water. Before the sucrose solutions were prepared, the
sucrose was dried in a desiccator, and all glassware was cleaned and completely air dried. A 1000
ml volumetric flask was weighed on an electronic analytical balance, and the weight recorded to
the nearest 0.01 gram. The appropriate amount of sucrose was weighed on the analytical balance
(338.10 g and 470.60 g for the 30 percent and 40 percent solutions, respectively), and added to the
clean, dry volumetric flask. Approximately 500 ml of deionized water was added to the flask,
and the mixture agitated by swirling. Additional deionized water was added slowly, while being
swirled, until the sucrose was completely dissolved and the bottom of the meniscus reached the
1000 ml reference line on the volumetric flask. The solution was allowed to rest to allow any
entrapped air bubbles to rise. The volumetric flask containing the solution was weighed on the
analytical balance, and the temperature was measured with a laboratory thermometer; both
measurements were recorded in a laboratory research notebook.
The density of the sucrose solutions and the deionized water was calculated using the following
relationship:
Eqn 19
where:
D = density, g/ml
m = mass of solution = mass of flask and solution - mass of flask, g/L
v = volume of solution, ml
Prior to the experiments to determine the viscometer constant, the sucrose solutions were gently
stirred to ensure a homogeneous mixture. A laboratory thermometer was used to measure the
temperatures of the sucrose solutions and deionized water, and the results were recorded in a
laboratory research notebook. The same procedure as described above was used except the
constant temperature bath was not needed because the experiments were done at ambient
temperature. Instead, the filled viscometer was held vertical in a 50 ml glass cylinder. The
viscometer constant, K, was determined to be 0.257 by fitting equation 17 to the experimental
time and literature values of viscosity.
E-50
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Specific Gravity
Specific gravity was measured in-situ in the laboratory drag-out tanks. In the field, specific
gravity was measured on grab samples collected from the process and rinse tanks.
Measurements were made immediately after collection.
Apparatus
• Hydrometer, Fisherbrand, range 0.890 to 1.000.
• Hydrometer, Fisherbrand, range 1.000 to 1.600.
• 500 ml glass cylinder (optional).
Before the hydrometers were used for measurements for the rinse tanks, process baths and
laboratory drag-out tests, the accuracy of the instruments was verified. Hydrometer readings
were taken on deionized water and a 40 percent (by weight) sucrose solution. The temperature of
the water and sucrose solution was measured with a laboratory thermometer, and the specific
gravity measurements were compared with published values. Results of the verification for
deionized water resulted in a value 0.15% higher than the expected published value of 1.000 at
20° C, and 0.5% less than the published value of 1.176 for the 40 percent sucrose solution at
20° C.
Surface Tension
Surface tension was measured in the UT laboratory on grab samples collected from the rinse
tanks, process baths, and laboratory drag-out tanks.
Apparatus
• Fisher Surface Tensiomat, Model 21, with platinum-iridium ring.
• 5 cm inch diameter glass vessel, approximately 1.3 cm deep.
• Magna-Whirl water bath.
Procedure
1. A water bath was prepared to simulate the temperature of the rinse tank or process bath as
measured in the field and recorded on the Sub-Unit Data Collection Log.
2. The rinse tank or process bath sample bottles were placed in the water bath, and allowed
to equilibrate to the bath temperature. The water bath and sample temperatures were
intermittently monitored using the thermometer. The sample bottles remained in the
water bath until used for the surface tension measurement.
3. The clean platinum-iridium ring was placed on the hook on the lever arm of the tensiomat.
4. A clean 5 cm diameter glass vessel was filled with a portion of the sample (transferred
immediately from the water bath) and placed on the sample table inside the tensiomat.
5. The sample table was raised until the ring was immersed in the liquid to a depth of
approximately 3 mm.
6. The torsion arm on the tensiomat was released, and the instrument was adjusted to a zero
reading by turning the knob on the right side of the case until the index and its image were
in line with the mark on the mirror. Care was taken to ensure the ring remained in the
liquid by adjusting the height of the sample table. The knob on the front of the case
beneath the main dial was adjusted until the vernier read zero on the outer scale of the
dial.
E-51
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7. The sample table was lowered until the ring was at the surface of the liquid. At the same
time, the knob on the right side of the case was adjusted to keep the index in line with the
mark on the mirror. The two simultaneous adjustments were continued until the
distended film at the surface of the liquid broke.
8. The reading on the scale at the breaking point (surface tension in dynes per centimeter)
was recorded on the Sub-Unit Data Collection Log.
9. The liquid was emptied from the glass vessel, and the process was repeated.
10. Both the platinum-iridium ring and glass vessel were rinsed with deionized water prior to
the next test.
Prior to the surface tension tests, the calibration of the tensiomat was checked and the platinum-
iridium ring was thoroughly cleaned.
To verify the calibration according to the instrument's instruction manual, the ring was placed on
the lever arm and the instrument was adjusted to a zero reading. A 600 mg piece of aluminum
foil was placed on the ring, and the knob on the right side of the case was adjusted until the index
and its image were in line with the mark on the mirror. The dial reading was recorded, and
compared with the calculated surface tension:
2^ Eqn 20
where:
S = dial reading = apparent surface tension in dynes/cm
M = weight (0.6 grams)
g = acceleration of gravity (980 cm/sec2)
L = mean circumference of ring (6.00 cm)
The platinum-iridium ring was cleaned per the manufacturer's instructions: the ring was: 1)
soaked in concentrated nitric acid for approximately 2 minutes, then rinsed with deionized water;
2) rinsed with acetone, followed by deionized water; and 3) flamed with a Bunsen burner.
Before surface tension measurements were made, the surface tension of deionized water was
checked at 20°C to verify accuracy. Seven measurements were made, with a mean value of 74.96
dynes/cm, a standard deviation of 2.03 dynes/cm. This mean value is 4.2 percent higher than the
expected value of 72 dynes/cm for the deionized water.
Metals Analysis
Sodium and/or Potassium analyses were conducted in the UT laboratory on grab samples
collected from the process baths and rinse tanks.
Apparatus
Allied Analytical Systems Atomic Absorption Spectrophotometer, IL Video 12, Serial
Number 1857.
Sartorius Analytical Balance, Model AC 120S, UT ID Number 427286.
E-52
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Reagents
• Sodium calibration standard, Fisher Scientific, 1000 mg/L.
• Potassium calibration standard, Fisher Scientific, 1000 mg/L.
• Potassium chloride (KC1), Fisher Scientific, certified grade.
• Lanthanum chloride (LaCl 6H20), Fisher Scientific, certified grade.
Procedure
1. Stock potassium chloride solution was prepared by dissolving 23.84 g. of potassium
chloride in 250 ml of deionized water in a volumetric flask. This produced a solution of
50,000 mg/L as K, which was used as an ionization suppressant for the sodium samples.
A stock solution of lanthanum chloride was prepared by dissolving 12.72 g. of lanthanum
chloride in 100 ml of deionized water in a volumetric flask. This produced a solution of
50,000 mg/L as La, which was used as an ionization suppressant for the potassium
samples.
2. Sodium and potassium standards were prepared by diluting the Fisher Scientific
calibration standards with deionized water to achieve the desired standards
concentrations.
3. The samples were prepared by performing dilutions with deionized water to get the
anticipated analyte concentrations within the linear range of the instrument. Volumetric
pipettes and volumetric flasks were used, and the samples were transferred to new, clean
125 ml HDPE sample bottles. Samples were acidified with ultrapure nitric acid, and
ionization suppressants were added to achieve a concentration of 2000 mg/L as K for the
sodium samples, and 1000 mg/L as La for the potassium samples.
4. The appropriate lamp was inserted in the atomic absorption spectrophotometer, and a
safety check of all settings was performed. The instrument electronics were turned on
and allowed to warm up for approximately 30 minutes.
5. The instrument printer, compressed air, and acetylene were turned on. The pilot was lit,
the flame adjusted, and the sampling tube was placed in a fresh beaker of deionized water.
6. The instrument was calibrated with the appropriate sodium or potassium standards. A
standards curve was printed, and a linear regression performed to check linearity of the
curve. If the value of r2 value was below 0.9950, the instrument was re-calibrated with
fresh standards.
7. The prepared samples were analyzed, beginning with the rinse samples and progressing
up-line to the process tank. Approximately ten analyses were run per sample, each lasting
approximately eight seconds. Results were printed and transferred to an Excel
spreadsheet.
8. The method of standard additions was performed on process bath samples to reduce
matrix effects. The samples were diluted 1:1 with known standards and analyzed in the
absorption mode. Generally, 0, 50, 100 and 200 mg/L standards were used for potassium
analyses, and 0, 20, 50 and 100 mg/L standards were used for sodium analyses; however
there was some variation since it was necessary to keep concentrations within the
instrument's linear range. A plot of absorption verses concentration of added standards
was then prepared, from which the actual concentration in the sample was derived. If
necessary, standard additions were performed on the succeeding rinse tanks, as described
later in this section.
E-53
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Before and during the atomic absorption analyses, all laboratory glassware and sample bottles
were acid washed in accordance with Standard Methods.
The analyte (sodium or potassium) was determined based on process bath composition, as
provided by either industry representatives, manufacturers' material safety data sheets, or
previous research conducted by the University of Tennessee's CCPCT.
Because of the extremely high anticipated concentration of analyte in some of the process baths,
along with the wide range of anticipated concentrations between the process baths and rinse
tanks, atomic absorption analyses were conducted using the least sensitive wavelengths (330.2
nm for sodium, and 404.4 nm for potassium) whenever possible. Dilutions were still necessary
on many of the samples. For sodium samples with very low sodium concentrations, it was
necessary to use the most sensitive wavelength of 589.0 nm.
The instrument was calibrated at the beginning of each lab session by using generally five
calibration standards within the linear range of the instrument, including a zero standard. The
standards used for the least sensitive wavelength for sodium (330.2 nm) were usually 0, 20, 50,
100, and 150 mg/L; however these occasionally varied depending on the anticipated
concentration of the sample. In all cases, the standards were chosen to best bracket the sample
concentration. Standards used for the most sensitive sodium analyses (589.0 nm wavelength)
were usually 0, 0.25 0.50. 0.75, 1.0 and 1.25 mg/L. Calibration standards for the least sensitive
wavelength for potassium (404.4 nm) were usually 0, 50, 100, 200 and 600. As with the sodium
analyses, standards were chosen to best bracket the sample potassium concentration. Standards
checks were performed during the measurements to ensure the instrument had not drifted. The
checks usually were performed after every four or five measurements, but always after ten
measurements were taken.
The samples were prepared for analysis by dilution with deionized water to achieve an anticipated
analyte concentration within the linear range of the instrument. The anticipated concentrations
were based on previous research conducted by the University of Tennessee's CCPCT. Alkali
salts were added to the samples and standards as an ionization suppressant. Potassium chloride
was added to sodium samples at 2000 mg/L, and lanthanum chloride at 1000 mg/L was added to
the potassium samples. Process and rinse tank samples and standard solutions were acidified to
pH < 2 in accordance with Standard Methods, using ultrapure concentrated nitric acid.
Electroless copper samples were not acidified due to the possibility of the baths containing
cyanide.
As an interference check, a standard additions analysis was performed on one sample for each
process bath, and compared with analysis results performed without standard additions.
Whenever there was a difference greater than 10 percent between the two measurements, a
standard addition analysis was performed on the duplicate bath sample, and the standard addition
results were used. If standard additions were necessary for the process bath samples, the
succeeding rinse tank samples were also checked, to determine if standard additions should be
used.
E-54
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Quality Assurance and Quality Control (QA/QC)
Prior to the site visit to collect the samples, the 500 ml new HDPE sample bottles were
thoroughly cleaned with detergent, triple rinsed with deionized water, and allowed to air dry.
Field blanks were used to monitor any contamination from the bottles. The field blanks were pre-
labeled and filled with deionized water in the UT laboratory prior to the site visits. During the
visit, the bottles were opened for approximately two minutes, then re-sealed.
All laboratory equipment transported to the site was thoroughly cleaned according to Standard
Methods prior to leaving the UT laboratory, and was again thoroughly cleaned between sites. All
laboratory equipment, including reagents and deionized water was transported from the UT
laboratory, including cleaning supplied. The samples remained in the custody of the sampling
team until arrival back to the UT laboratory, where they were placed in a limited access, locked
cold room until analyses.
Results from Analysis of Field Samples
Mean values of temperature, specific gravity, viscosity, conductivity, surface tension for each of
the field samples are summarized in Table 21.
Measurements of conductivity, specific gravity, surface tension, viscosity were all completed in
duplicate. The coefficients for all measurements were all excellent (conductivity 0.04, surface
tension 0.005, specific gravity 0.001% and viscosity 0.073).
Sodium and potassium concentrations are summarized in Table 22. Replicate samples at plants 1
and 2 were taken in identical manner, and the results were averaged and reported as a single
value. At plant 3, two samples were taken at different times in the board cycle time. Samples
labeled "A" were taken just prior to the boards entering the rinse tank and should normally
correspond to the lowest concentration present in the rinse tank. Samples "B" and "R" were
taken just after the boards were removed from the rinse tank and should be near the maximum
concentration in the rinse cycle. The individual samples from plant 3 were not averaged, but
reported individually. Details of the analytical procedure used for each sample are summarized in
the Appendix.
E-55
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Table 21. Temperature, Specific Gravity, Viscosity, Conductivity, Surface Tension for Field
Samples.
Siimplc \:imc
Tom p..
°C
Specific
(inmlY
Viscosity.
cP
(ondiicln ilv,
inS/cin. 25 "('
Surfsicc Tension,
ilvnes/cm
Plant 1 ME Process
30
1.110
1.140
304,000
76.2
Plant 1 ME Rinse 1
20
1.005
1.112
1,935
75.9
Plant 1 ME Rinse 2
20
1.004
1.142
213
75.6
Plant 1 EC Process
45.5
1.170
1.218
224,000
73.2
Plant 1 EC Rinse 1
21
1.003
.977
1,043
76.0
Plant 1 EC Rinse 2
20
1.005
1.097
224
76.3
Plant 1 AT Process
19
1.004
1.172
341
72.2
Plant 1 AT Rinse 1
20
1.002
1.097
229
74.4
Plant AT Rinse 2
20
1.002
1.022
223
76.2
Plant 1 FB
NA
NA
NA
1.8
76.2
Plant 2 ME Process
37
1.175
1.246
477,000
78.0
Plant 2 ME Rinse 1
15
1.004
1.172
2,170
77.0
Plant 2 EC Process
38
1.110
1.421
119,600
51.2
Plant 2 EC Rinse 1
20
1.002
.932
676
73.2
Plant 2 AT Process
19
1.005
1.202
353
75.0
Plant 2 AT Rinse
16.5
1.005
1.037
256
76.3
Plant 2 FB
NA
NA
NA
1.9
76.1
Plant 3 ME Process
29
1.145
1.340
168,400
77.6
Plant EC Process
54
1.115
1.139
261,000
56.2
Plant 3 EC Rinse 1
27
1.002
0.992
736
74.0
Plant 3 EC Rinse 2
30
1.003
NA
155
75.4
Plant 3 AT Process
25
1.005
1.127
543
72.2
Plant 3 AT Rinse
30.5
0.994
0.798
156
73.6
Plant 3 FB
NA
NA
NA
1.8
75.0
Table 22. Metals Concentrations Measured in Field Samples.
Snniple Niime
Soil in in. m»/l.
I'oliissiiim, m»/l.
Method
Plant 1 ME Process
20,380
Standard Additions
Plant 1 ME Rinse 1
77.4
Standard Curve
Plant 1 ME Rinse 2
<7.5
Standard Curve
Plant 1 EC Process
67,750
Standard Additions
Plant 1 EC Rinse 1
242
Standard Curve
Plant 1 EC Rinse 2
24.5
Standard Curve
E-56
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Sitmplc Nsime
Soil in in, m«/l.
I'oliissiiim, m»/l.
Method
Plant 1 AT Process
2.8
94
Standard Additions
Plant 1 AT Rinse 1
<7.5
Standard Curve
Plant 1 AT Rinse 2
<7.5
Standard Curve
Plant 1 Makeup water
20.15
<7.5
Standard Curve
Plant 1 FB
<7.5
Standard Curve
Plant 2 ME Process
62,300
Standard Additions
Plant 2 ME Rinse 1
98.8
Standard Curve
Plant 2 EC Process
63,450
Standard Additions
Plant 2 EC Rinse 1
128.6
Standard Curve
Plant 2 AT Process
30.8
<7.5
Standard Additions
Plant 2 AT Rinse
34.5
<7.5
Standard Curve
Plant 2 Makeup water
31.36
<7.5
Standard Curve
Plant 2 FB
<0.01
Standard Curve
Plant 3 ME Process
41,550
Standard Additions
Plant 3 ME Rinse 1-A
173.6
Standard Additions
Plant 3 ME Rinse 1-B
242
Standard Additions
Plant 3 ME Rinse 1-R
289
Standard Additions
Plant 3 EC Process
72,950
Standard Additions
Plant 3 EC Rinse 1-A
109.3
Standard Curve
Plant 3 EC Rinse 1-B
173.5
Standard Additions
Plant 3 EC Rinse 1-R
191.7
Standard Curve
Sample Name
Sodium, mg/L
Potassium, mg/L
Method
Plant 3 EC Rinse 2-A
24.3
Standard Curve
Plant 3 EC Rinse 2-B
24.4
Standard Curve
Plant 3 AT Process
111
Standard Additions
Plant 3 AT Rinse 1-A
19.1
Standard Curve
Plant 3 AT Rinse 1-B
19.1
Standard Curve
Plant 3 AT Rinse 1-R
23.2
Standard Curve
Plant 2 Makeup water
23.1
<7.5
Standard Curve
Plant 3 FB
<0.1
Standard Curve
E-57
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The pooled instrumental relative standard deviation for potassium was determined to be 0.77%,
based on eighteen potassium samples with a mean sample concentration of 113.6 mg/L, and a
pooled instrumental standard deviation of 0.87 mg/L. The pooled instrumental relative standard
deviation for sodium was determined to be 1.6% based on seventy-three analyses with a mean
concentration of 60.6 mg/L. The pooled instrumental standard deviation was 0.97 mg/L. Data on
which these calculations are based are included in the Appendix.
The relative standard deviation for duplicate potassium samples ranged from 0.17 to 6.95% for
tests run with no standard additions, with a pooled standard deviation of 3.46 mg/L. There were
no duplicate or replicate analyses for potassium using the method of standard additions. The
relative standard deviation for duplicate sodium measurements without standard additions ranged
from 0.11 percent to 18.94 percent, with a pooled standard deviation of 8.05 mg/L. The relative
standard deviation for duplicate sodium analyses performed with standard additions ranged from
0.52 to 6.13%), with a pooled standard deviation of 2.76 mg/L. Data for duplicate samples from
which these results were determined are listed in the Appendix.
E-58
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DYNAMIC MASS BALANCE MODEL
FOR INTERPRETATION OF FIELD DATA
The field data collected at the PWB manufacturers was used to validate the drag-out component
of the wastewater generation model. The output from the model is the average mass rate of
contaminant in the rinse water from a particular process bath; the model can also calculate
average concentrations in the rinse tank effluent by dividing by the rinse flow rate.
However, the average concentration predicted by the model does not correspond directly to the
contaminant concentrations measured in the field samples. The MHC process is dynamic in that
the concentrations of contaminants in the rinse effluent change as a function of time. The
operation cycle of a given rinse tank consists of a short period of time in which a board is
immersed in the tank, followed by a longer period of time during which no boards are in the
tanks. Contaminants are continually flushed from the rinse tank during the entire operation time
of the bath. As a result of this operational practice, the rinse-tank concentration history will be a
periodic saw-tooth wave function. In the field, instantaneous grab samples were collected from
the rinse tanks, usually immediately after removal of the board. Clearly, the concentrations in the
instantaneous grab samples may not be directly comparable to the average concentration
calculated by the model; therefore, a means of verifying the model is needed. A dynamic
material balance model was used to compare the concentration of contaminant in the grab
samples with the average concentration of contaminant predicted by the models.
The following material balance equation describes the concentration of contaminant in a
completely-mixed rinse tank:
The concentration of contaminant in the tank as a function of time can be determined by
separating the variables in equation 21 and integrating using appropriate boundary conditions.
Assume that when the line is first started (before the first board is dipped in the tank) that the
contaminant concentration in the tank is equal to the feed water concentration. Also assume that
at t=0 a rack of boards, containing mass of contaminant M, instantly releases all of its
contaminant to solution. Under these conditions, the concentration in the tank at t=0 is:
Eqn 21
where:
Q
flow rate through the tank, L3/t
tank volume, L3
concentration of contaminant in the tank, M/L3
concentration of contaminant in the feed water to the tank, M/L3
time, t
V
c
t
M
Eqn 22
c = C0 +
V
E-59
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The solution to equation 21 describing the concentration history after removal of the first board is
then given by:
(Q-dt-f dC Eqn23
Jo\/ J M/V+C0Qo-C
„ „ M ( Qt\ ^24
C = ca+—exp
V \ V J
As time progresses additional boards will enter the rinse tank. Assume that additional boards
enter the tank at a constant period of 1. It is convenient to redefine t as:
t = n X + 0 Eqn 25
where
n = number of cycles completed since t = 0
q = time elapsed in the current cycle, t
The effluent history during the rinsing cycle for the second board processed after start-up would
be given by:
reQ rc dC Eqn 26
—dd = \ , ,
Jo \/ J(/M/ \/)[1+exp(-QA/ V)]+C0 CQ~C
_ _ M ( QQ\ M ( Q(X+0^ Eqn 27
C = CQ+—exR ,+—exd —^ ,
° v \ v v \ v j
This result can be extended to represent the effluent history for the rinsing period after the nth
board is rinsed:
_ _ M ( Q9^ f kCpi]
E-60
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Steady-state is defined to occur when n = °°. Substituting
Eqn 29
yields an expression concentration history for a single rinse tank, operating at steady-state:
A rinsing tank receives a rack containing 60 ft2 of boards every 30 minutes. The drag-out rate is
10 mL/ft2 and the contaminant concentration in the process tank is 3000 mg/L. The rinse rate is 2
gpm and the tank is 220 gallons in volume. The feed water contains 40 mg/L of the contaminant.
Calculate the effluent concentration history during the 30 minute cycle period under steady-state
conditions:
Eqn 30
Example:
( 10mL^ ( 3000^ ( L > ( 1 > ( gal >
J { L { 1000/7?/.J { 220gal] { 3.78/.y
21.6 mg/L Eqn 31
Eqn 32
Equation 32 is plotted over the course of one process cycle in Figure 6.
E-61
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40 -I 1 1 1 1 1 1
0 5 10 15 20 25 30
time (min)
Figure 6. Example Concentration History of Rinse Tank Effluent During One
Plating Cycle.
E-62
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MODEL VALIDATION
The purpose of the field samples was to validate the drag-out prediction model and the overall
mass balance approach to predicting wastewater quality from PWB facilities. The dynamic
material balance model for the rinsing process was developed in the previous section to facilitate
this comparison. First, equation 30 was solved for the mass of contaminant in the drag-out:
M = {C -C0)Vexp!
(Q^\
[v )
\ (-QIY
1 - exp,
A V )
Eqn 33
The volume of the drag-out could then be calculated by dividing the mass of contaminant in the
drag-out by the bath concentration:
M
Vdrag-out = J, ^ 34
bath
The drag-out volumes calculated from the field data and the dynamic mass balance (equations 33
and 34) are compared to those predicted using the drag-out regression model (equation 15) in
Table 23. Replicate samples at the plants 1 and 2 were taken in identical manner, and the results
were averaged and reported as a single value. At plant 3, the duplicate samples were taken at
different times in the board cycle time. Samples labeled "A" were taken just prior to the boards
entering the rinse tank and should normally correspond to the lowest concentration present in the
rinse tank. Samples "B" and "R" were taken just after the boards were removed from the rinse
tank and should be near the maximum concentration in the rinse cycle. Samples 3MER1-A and -
B were taken soon after the MHC line had been shut down for a short period of time and may
have been erroneously low. The individual samples from plant 3 were not averaged; separate
calculations were made for each one. Sodium and potassium concentrations in the anti-tarnish
rinse tanks were too low to accurately calculate either the mass of contaminant in the drag-our or
the drag-out volume.
The drag-out volumes calculated from the field data are consistently less than those predicted by
the drag-out model. They are also significantly less than those measured both in the laboratory
experiments performed as a part of this work and the data collected by Pagel (1992). For
example, the drag-out volumes from Microetch baths calculated from our field data ranged from
22.8 to 53.6 mL/m2, compared to a range of 76 to 122 mL/m2 in this study and a range of 57 to
145 mL/m2 in Pagel's work. Similarly, the drag-out volumes from the Electroless baths
calculated from our field data ranged from 9.73 to 32.9 mL/m2, compared to a range of 20.4 to
81.8 mL/m2 in Pagel's work. A possible explanation is that the drag-out volumes calculated from
the field data were based on the assumption in the dynamic mass balance model that all the
contaminant was released instantaneously from the PWB and that the rinse tank was perfectly
mixed. The rinsing tanks used in PWB plants may not approximate this ideal behavior. Rinse
water typically enters the bottom of the rinse tank and flows over a weir at the water surface. As
the board enters the tank, it is likely that a significant fraction of the pollutant flows over the weir
prior to being mixed
E-63
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throughout the tank. Fluid shear may contribute to the loss of contaminant near the water
surface of the tank as the board enters the tank. The grab samples were generally collected
immediately following removal of the board from the rinse tank. We hypothesize that the short-
circuiting process described above may have caused a large fraction of the contaminant to be
removed from the rinse tank prior to the time that we collected the sample. Our laboratory drag-
out study, and the work of Pagel (in which the rinse water flow rate was set to zero during the
sampling) were not subject to this influence.
Table 23. Comparison of Drag-Out Volumes Calculated from Field Samples to Those
Predicted by Regression Model.
Siimple Description
l)r:i«-()til Volume ('iilcuhiled
from Held D.ilii, ml./iir
l)m<>-Oiil Volume C itlcuhtlecl
from Regression Model,
nil./nr
Plant 1, Microetch
53.6
127
Plant 1, Electroless Copper
32.9
59.1
Plan 2, Microetch
22.8
102
Plant 2, Electroless Copper
23.2
39.9
Plant 3, Microetch A
28.2
98.2
Plant 3, Microetch B
41.0
98.2
Plant 3, Microetch R
37.9
98.2
Plant 3, Electroless A
9.73
34.7
Plant 3, Electroless B
6.83
34.7
Plant 3, Electroless R
10.9
34.7
A regression equation was fitted to the data in Table 23, resulting in the following relationship^2
= 0.71):
vm = 036FpM + 0.68 Eqn 35
where:
Vfield = drag-out volume calculated from the field data
Vpredicted= is the drag-out volume predicted by the regression model
The slope of the regression equation suggests that about 2/3 of the total mass of contaminant
flows over the weir prior to being mixed. The relatively good correlation coefficient indicates that
the field and predicted drag-out volumes were comparative on a relative basis. This suggests that
the drag-out regression model and overall mass balance approach may be valid for making
relative comparisons between process alternatives.
E-64
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CONCLUSIONS AND RECOMMENDATIONS FOR FUTURE WORK
Conclusions
• Contaminant mass in PWB process wastewaters can be expressed as a mass balance in
which the mass of contaminant in the wastewater is equal to the mass of contaminant
released via drag-out from the process baths (which ultimately ends up in the rinse tanks),
periodic dumping of process tanks into the wastewater, and stripping deposits from racks.
Drag-out is generally considered to be the major contaminant source. Data quantifying
composition of the process baths, the volume of wastewater produced, and the frequency
of bath dumps are usually collected during the course of the DFE process. For example,
this information was collected for the MHC process during a previous study by the
University of Tennessee CCPCT (Kincaid et al. 1997).
• Very little data exists quantifying the rate of drag-out from PWB processes, i.e., the mass
or volume of drag-out per unit surface area of PWB, e.g., mL/m2. A study reported by
Pagel at Micom, Inc. is the only readily available study on PWB facilities. Limited drag-
out research has been conducted on flat pieces, most notably by Slip. However, the
numerous small holes present in PWBs renders application of drag-out volumes
measured from non-PWB pieces problematic. Practitioners tend to use rules-of-thumb or
historically accepted values for drag-out. This one-size-fits-all approach ignores process
specific information such as bath type, viscosity, surface tension, board withdrawal rate,
or drain time. Drag-out rates reported in the literature for vertically-oriented flat pieces,
range from 10 to 160 mL/m2.
• Commonly-cited equation found in the literature offer predictions of the drag-out rate as a
function of kinematic viscosity and board withdrawal rate. Slip showed that this equation
does not predict drag-out very well for the rectangular flat pieces that he studied. There
was no relationship between kinematic viscosity and drag-out, and two previously
proposed predictive equations performed poorly.
• Several variables have been shown to affect the drag-out rate. Studies at Micom, Inc.
reported by Pagel (1992) showed the importance of longer drainage time and slower
withdrawal rate in reducing drag-out. SiiP (1990, 1992) also found that these variables are
important as well as the angle of the board during drainage. No research was found that
addressed the effect of surface tension. Based on the present study, surface tension may
be an important variable.
• Considerable literature exists on rinsing theory which appears highly developed and well
studied for ideal mixing situations. While rinsing theory is not as well developed for non-
ideal mixing, previous researchers have concluded the assumption of ideal mixing is valid
for estimating long-term-average wastewater concentrations because nearly all of the
drag-out ultimately reaches the wastewater effluent.
• Laboratory studies conducted as part of this research expanded the data base of drag-out
rates for two PWB process baths and several operating conditions. The experimental
procedures showed good reproducibility, and the data were consistent with previous
research.
E-65
-------
• A regression model for predicting drag-out volume was developed using the available data
bases of SiiP (1990, 1992), Pagel (1992), and the present study. The dependent variables
were a choice of two types of process baths (plus a default for any other type of bath),
board withdrawal rate, drain time, board size, and presence of drilled holes. The model
had an R2 of 0.852.
• The regression model for predicting drag-out rate was incorporated in a computer model
for predicting contaminant mass loading and mean pollutant concentrations from PWB
manufacturing process lines. The model was written as a Visual Basic macro within an
EXCEL spreadsheet. Input variables included facility production rate, board size, number
and types of process baths, bath composition, frequency of bath dumps, and wastewater
production rate.
• Samples were collected from three PWB facilities in order to validate the drag-out model.
Samples were collected from various process and rinse tanks and analyzed for
temperature, specific gravity, viscosity, surface tension, conductivity, and potassium or
sodium concentration. Since it was not convenient to collect composite samples from the
rinse tanks, grab samples were collected at various times after a board was inserted into a
rinse tank. An equation was developed to relate the time-dependent concentration of
potassium or sodium in the rinse tank to the drag-out volume. Unfortunately, it appears
that poor mixing in the rinse tanks led to unrepresentative sampling. Although the
apparent drag-out rates were about 1/3 of the predicted rates, a comparison of drag-out
rates between process tanks showed a correlation (r2 = 0.71) with the previously
developed regression model, and in that sense lend support to it.
Recommendations
• The authors believe that this work has resulted in a more universally applicable method
for estimating the mass and concentration of contaminants in a PWB process wastewater
than currently exists, especially for relative evaluations. However, much can still be done
to improve the model since the existing data are so limited. Previous work has not
studied the effect of surface tension, but the laboratory studies in this work showed that
surface tension may be an important variable. Indeed, one of the drag-out reduction best
practices is to use a wetting agent which would reduce surface tension. The effect of
viscosity was previously thought to be important, but neither SiiP nor this work found it
to be significant. There has also been only one previously reported study of an actual
PWB facility. The authors believe that a better quantitative understanding of the variables
affecting drag-out could lead to the development of a better prediction equation. The first
phase of such research should focus determining the effect of bath fluid properties and
operating variables under controlled laboratory conditions. Expansion and testing of the
model could be accomplished by samples collected at PWB facilities during a second
phase of the study.
• Beyond determining the wastewater quality emanating from PWB manufacturing
processes, there is a need to assess the fate of the chemicals in the PWB wastewater both
in the onsite treatment processes at PWB manufacturing facilities and at Publicly-Owned
Treatment Works (POTW). Information of the effect of chemical speciation on the fate of
E-66
-------
pollutants is especially needed. For example, metals are one of the primary pollutants of
concern in PWB wastewater, and it is likely that many of the metals are chemically
complexed in PWB wastewater. On-site treatment processes are likely to preferentially
remove the least stable metal complexes, while the most stable complexes are discharged
to the POTW. Standard removal efficiencies for metals in activated sludge processes are
probably not applicable to these highly complexed metals and the potential for release of
the metals to the aquatic environment may be underestimated.
A third issue needful of better understanding is the volatilization of chemicals from tanks
and baths such as in PWB plating processes and other manufacturing processes. The
volatilization models used in the previous assessment of emissions for the MHC process
and the present assessment of surface finishing assume gas-side control of the mass
transfer, i.e., volatilization, of chemicals from the process baths. In the MHC, and
presumably in the surface finishing process, there were several chemicals whose mass
transfer appeared to be liquid-side controlled. The mass transfer model used does not
apply for this situation and could lead to an overestimate of the emission and consequent
risk for these chemicals. It would be productive to research the literature to find more
appropriate liquid-side control mass transfer models and applicable constants for various
types of manufacturing process tanks. For example, there is a body of literature available
on surface renewal theory models which would be more appropriate for liquid-side mass
transfer control. This literature search could be completed within a year and a decision
made at that time as to whether any lab based research is warranted.
E-67
-------
REFERENCES
American Chemical Society, Chemical Abstracts, American Chemical Society, Washington,
DC., 1998.
Chang, L., and McCoy, B. J., "Waste Minimization for Printed Circuit Board Manufacture,"
Hazardous Waste & Hazardous Materials, 7, No. 3, 293-318 (1990).
Hanson, N. H., and Zabban, W., "Design and Operation Problems of a Continuous Automatic
Plating Waste Treatment Plant," Plating, 909-918 (August, 1959).
Hatschek, Emil, "The Viscosity of Liquids," D. Van Nostrand Company, New York, 1928.
Kincaid, L.E., Geibig, J.R., Swanson, M.B., and PWB Engineering Support Team, Printed
Wiring Board Cleaner Technologies Substitutes Assessment: Making Holes Conductive, Center
for Clean Products and Clean Technologies, University of Tennessee, Knoxville, Tennessee
(1997).
Kushner, J.B., "Rinsing: I. With Single-Compartment Tank," Plating, 36, August, p. 798-801,
866 (1949).
Kushner, J.B., "Where Do We Go from Here? Part III - Water Control," Metal Finishing, 47,
No. 12, 52-58,67(1951).
Kushner, J.B., "Dragout Control - Part I," Metal Finishing, 49, November, 59-64 (1951).
Kushner, J.B., "Dragout Control - Part II," Metal Finishing, 49, December, 58-61,67 (1951).
Kushner, J.B., "Rinsing Techniques," in Metal Finishing: 47th Guidebook-Directory Issue 1979,
Vol. 77, No. 13, (January, 1979).
McKesson, Doug, and Wgener, M.J., "Rinsewater Quality .... Hard Data," Proceedings of the
Technical Conference IPC Printed Circuits Expo '98, p. S09-1-1 to S09-1-5, The Institute for
Interconnecting and Packaging Electronic Circuits, Long Beach, California, 1998.
Mohler, J.B., "Water Rinsing," in Metal Finishing: 52nd Guidebook-Directory Issue 1984, Vol.
82, No. 1A, (January, 1984).
Mooney, T., "Water Rinsing," in Metal Finishing: 59th Guidebook-Directory Issue 1991, Vol.
89, No. 1A, (January, 1991).
Pagel, Paul, Modifications to Reduce Drag out at a Printed Wiring Board Manufacturer,
EPA/600/R-92/114, Risk Reduction Laboratory, Office of Research and Development, U.S.
Environmental Protection Agency, Cincinnati, Ohio (1992).
E-68
-------
Pinkerton, H.L., and Graham, A.K., "Rinsing," in Electroplating Engineering Handbook,
Lawrence J. Durney, Ed., van Nostrand Rheinhold, New York, 1984.
Robinson, R.B. and Cox, C.D., QA/QC Plan for Verification of Hot Solder Finishing:
Prediction of Water Quality from Printed Wiring Board Processes, University of Tennessee,
Knoxville, TN, 1998.
Sharp, J., Teradyne Corp., Nashua, NH., Personal communication (September, 1998).
SliP, Von M., "Technologische MaPnahmen zur Minimierung von Ausschleppverlusten
(Technological Measures for Minimizing Drag Out)," Galvanotechnik, 81, No. 11, 3873-3877,
(1990).
SliP, Von M., "Bestimmung Elektrolytspezifischer Ausschleppverluste (Detemination of
Electrolyte Specific Losses Due to Drag-out)," Galvanotechnik, 83, No. 2, 462-465, (1992).
Talmadge, John A., "Improved Rinse Design in Electoplating and Other Industries," Proceedings
of the Second Mid-Atlantic Industrial Waste Conference, p.217-234, (1968).
Talmadge, John A., Buffham, Bryan A., and Barbolini, Robert R., "A Diffusion Model for
Rinsing AIChE Journal, 8, No. 5, 649-653, (1962).
Talmadge, John A., and Buffham, Bryan A., "Rinsing Effectiveness in Metal Finishing," J. Water
Pollution Control Federation, 33, No. 8, 817-828, (1961).
Talmadge, J. A., and Sik, U.L., "A Drop Dispersal Model for Rinsing," AIChE Journal, 15, No. 4,
521-526, (1969).
U.S. Environmental Protection Agency, Printed Wiring Board Pollution Prevention and Control
Technology: Analysis of Updated Survey Results, EPA/744-R-98-003, Design for the
Environment Branch, Economics, Exposure, and Technology Division, Office of Pollution
Prevention and Toxics, Washington, D.C. (1998).
Yost, K.J., "The Computer Analysis of Waste Treatment for a Model of Cadmium Electroplating
Facility," Proceedings Third International Cadmium Conference, p. 56-59 (1991).
Zaytsev, Ivan Demitrievich, and Aseyev, Georgiy Georgievich, Editors, Properties of Solutions
of Electrolytes, M. A. Lazarev and V. R. Sorochenko, Translators, CRC Press, Boca Raton, 1992.
E-69
-------
LIST OF SYMBOLS
area of the sheet
mass content of the component is kg of component per kg of solution
concentration of contaminant solution being drug into rinse tank
concentration of contaminant in the effluent of the rth rinse tank
concentration of contaminant in rinse tank after t min
volume of drag-over or drag-out on rack and work rinsing operation
coefficient calculated as shown below for each component for use in the
method given by Zaytsev and Aseyev
empirical coefficients chosen for each electrolyte component from a table
for use in the method given by Zaytsev and Aseyev
film thickness, cm
thickness of the film that drains off the sheet
function describing a relationship between the independent variables and
thickness of the film that drains from the sheet
gravity (981 cm/s2)
height of metal sheet
unknown constant determined by experiments
unknown exponent determined by experiments
number of rinsing operations in t min
rate of fresh water flow
number of rinse tanks in series
time interval between rinsing operations
temperature of solution, °C
drainage time, s
withdrawal time, s
velocity of withdrawal
withdrawal rate of metal sheet, cm/s
volume of rinse tank
volume of liquid that drains from the rectangular sheet
kinematic viscosity, cm2/s
density of electrolyte, gm/cm3
dynamic viscosity of electrolyte, g/(cms)
viscosity of water, Pa s
surface tension of the liquid
E-70
-------
Appendix F
Supplemental Performance
Demonstration Information
-------
APPENDIX F
F.l Modeling the Test Results
General linear models (GLMs) were used to analyze the test data for each of the 23 electrical
circuits in Table 4.1 at each test time. The GLM analysis determines which experimental factors or,
when possible, combinations of factors (interactions) explain a statistically significant portion of the
observed variation in the test results.
A GLM used to analyze the test results with respect to sites, flux type, and their interactions
(where possible) is expressed as the following 22-term equation:
Y = Po + Pi Di + P2D2 + P3D3 + P4D4 + P5D5 + P6^6 + P7D7 + PsDs + P9D9 + P10D10 + P11D11 (F.1)
+ P12D12 + P13D13 + P14D14 + P15D15 + P16D16 (Main effects)
+ P17D3D16 + Pi8D4Di6 + Pi9D6Di6 + P20D10D16 (Two-factor interactions)
+ P21D12D16 + P22D15D16
The coefficients in the GLM ((3o, (3i, P2, ...) are estimated using ordinary least squares regression
techniques. The dummy variables, Di to Di6, are set equal to 1 to identify type of surface
finish/manufacturing site and type of flux that are associated with individual test results. Otherwise,
the dummy variables are set to 0. The following dummy variables can be used to represent the
experimental variables for each test environment for each electrical response variable.
Di = 0 if surface finish is not HASL - Site 2
= 1 if surface finish is HASL - Site 2
D2 = 0 if surface finish is not HASL - Site 3
= 1 if surface finish is HASL - Site 3
D3 = 0 if surface finish is not OSP - Site 4
= 1 if surface finish is OSP - Site 4
D4 = 0 if surface finish is not OSP - Site 5
= 1 if surface finish is OSP - Site 5
D5 = 0 if surface finish is not OSP - Site 6
= 1 if surface finish is OSP - Site 6
D6 = 0 if surface finish is not immersion Sn - Site 7
= 1 if surface finish is immersion Sn - Site 7
D7 = 0 if surface finish is not immersion Sn - Site 8
= 1 if surface finish is immersion Sn - Site 8
D8 = 0 if surface finish is not immersion Sn - Site 9
= 1 if surface finish is immersion Sn - Site 9
D9 = 0 if surface finish is not immersion Sn - Site 10
= 1 if surface finish is immersion Sn - Site 10
D10 = 0 if surface finish is not immersion Ag - Site 11
= 1 if surface finish is immersion Ag - Site 11
Dn = 0 if surface finish is not immersion Ag - Site 12
= 1 if surface finish is immersion Ag - Site 12
D12 = 0 if surface finish is not Ni / Au - Site 13
= 1 if surface finish is Ni / Au - Site 13
D13 = 0 if surface finish is not Ni / Au - Site 14
= 1 if surface finish is Ni / Au - Site 14
D14 = 0 if surface finish is not Ni / Au - Site 15
= 1 if surface finish is Ni / Au - Site 15
D15 = 0 if surface finish is not Ni / Pd / Au - Site 16
= 1 if surface finish is Ni / Pd / Au - Site 16
Djg = 0 if flux is not water soluble
= 1 if flux is water soluble
F-l
-------
APPENDIX F
The "base case" is obtained by setting all D, = 0. Note that the surface finish/manufacturing site is
HASL / Site 1 if D i = D2 = D3 = D4 = D5 = Df, = D7 = Dg = Dg = D10 = D11 = D12 = D13 = D14 = D15 =
0. Likewise, if Di6 = 0, the flux is low-residue. Thus, the base case is HASL / Site 1 with LR flux.
Note the GLM in Equation F. 1 contains six interactions terms that represent the last six sites in
Table 4.2 (5, 6, 7, 11, 13, and 16) for which both LR and WS fluxes were used.
The GLM approach provides a tool for identifying the statistically significant experimental
variables and their interactions. That is, all terms in the model that are significantly different from the
base case are identified through tests of statistical hypotheses of the form:
H0: Pi = 0 versus Hi: P1 ^ 0 for all i
If the null hypothesis is rejected, then the coefficient of the corresponding term in the GLM is
significantly different from 0, which means that the particular experimental conditions represented by
that term (surface finish or flux type) differ significantly from the base case. If the null hypothesis is
not rejected, then the coefficient of the corresponding term in the GLM is not significantly different
from 0 and, therefore, the experimental conditions represented by that term do not differ significantly
from the base case. Such terms are sequentially eliminated from the GLM (see Iman, 1994, for
complete details).
The GLM approach is quite flexible and easily adaptable to a variety of requirements. For
example, if the focus is on surface finishes and not sites; the GLM in Equation F. 1 would be replaced
by one of the following form:
Y = p0 + P1D1 + p2D2 + P3D3 + p4D4 + p5D5 + p6D6 F.2
This model contains only main effects where the dummy variables are defined as follows.
Di = 0 if surface finish is not OSP
= 1 if surface finish is OSP
D2 = 0 if surface finish is not immersion Sn
= 1 if surface finish is immersion Sn
D3 = 0 if surface finish is not immersion Ag
= 1 if surface finish is immersion Ag
D4 = 0 if surface finish is not Ni / Au
= 1 if surface finish is Ni / Au
D5 = 0 if surface finish is not Ni / Pd / Au
= 1 if surface finish is Ni / Pd / Au
D
-------
APPENDIX F
Example of GLM Analysis
The data base for the electrical responses incorporates the dummy variables used to define the
experimental parameters for each measurement. The data base contains 164 rows (one for each PWA).
Sample data base entries for the GLM in Equation F.2 for leakage measurement on the 10-mil pads
(response number 18 in Table 4.1) in logio ohms could appear as follows:
Row OSP Imm Sn Imm Ag Ni/Au Ni/Pd/Au Flux Leakage
1
0
0
0
0
0
0
12.8
2
1
0
0
0
0
1
11.9
3
0
1
0
0
0
0
12.1
4
0
0
0
0
1
1
11.8
•
•
•
•
•
•
•
•
•
•
•
•
•
•
•
•
•
•
•
•
•
•
•
•
The interpretation of these data base entries is as follows. The first row has zeros for OSP,
immersion Sn, immersion Ag, Ni/Au, and Ni/Pd/Au. This implies that the surface finish is HASL.
The surface finishes for rows 2, 3, and 4 are OSP, immersion Sn, and Ni/Pd/Au, respectively. Water
soluble flux is used on rows 2 and 4. The leakage measurements are given in the last column. The
above table would be expanded to include other experimental parameters or products (interactions) of
the experimental parameters depending on the requirements of the GLM such as given in Equation F. 1.
The above table would also include columns containing the other 22 electrical measurements.
Computer software is used with the entries in the data base to find the least squares estimates of
coefficients in the GLM. For example, such an analysis for the GLM in Equation F.2 could produce
an estimated equation such as the following for leakage for the 10-mil pads.
Y = 12.5 - 0.200 OSP + 0.192 Immersion Sn - 0.164 Immersion Ag + 0.006 Ni/Au - 0.292 Ni/Pd/Au - 1.04 Flux
Note that the least squares process has simply solved a set of equations to determine an estimated
coefficient for each term appearing in the GLM in Equation F.2. However, it does not necessarily
follow that each of the terms in this estimated model makes a statistically significant contribution
toward explaining the variation in the leakage measurements. Rather, this determination is
accomplished by subjecting the coefficients in the full model to the following hypothesis test in a
sequential (stepwise) manner to determine if they are significantly different from 0:
H0: Pi = 0 versus Hi: ^ 0
If the coefficient is not significantly different from 0, it is eliminated from the model. Thus, the
only terms remaining in the model at the conclusion of this sequence of tests are those that are declared
to be significantly different from 0. This stepwise process eliminates some of the terms from the
model and the least squares calculations are repeated without those terms, which produces a reduced
model such as:
Y = 12.35 - 0.34 OSP - 0.38 Immersion Ag - 0.24 Ni/Pd/Au - 1.06 Flux
The intercept in this model, 12.35, is the estimated resistance for the base case—HASL processed with
LR flux. Mean predictions for other combinations of the experimental parameters can be made by
substituting the appropriate dummy variables into the model. For example, the mean prediction for a
OSP (Di=l, D2=0, D3=0, D4=0, D5=0) PWA processed with WS flux (D6=l) is found as:
F-3
-------
APPENDIX F
Y = 12.35 - 0.34 (1) - 1.06 (1) = 10.95
F.2 Overview of Test Results
Table F.l Anomaly Summary by Surface Finish after Exposure to 85/85
IIASI
MSN
Site
Flux
Circuit Test Technician Comments
083-2
1
WS
7 HF PTH 50MHz Open PTH
8 HF PTH f(-3dB) Open PTH
9 HF PTH f(-40dB) Open PTH
OSP
056-4
5
LR
7 HF PTH 50MHz Open PTH
8 HF PTH f(-3dB) Open PTH
9 HF PTH f(-40dB) Open PTH
Immersion Sn
030-4
9
WS
4 HVLC SMT
032-4
8
LR
7 HF PTH 50MHz Open PTH
8 HF PTH f(-3dB) Open PTH
086-2
7
WS
12 HF SMT f(-40dB) Waveform did not go to-40dB
102-4
10
WS
17 HFTLCRNR
Immersion Ag
082-2
11
LR
21 Gull Wing Burnt etch in multiple places
094-4
12
WS
7 HF PTH 50MHz Open PTH
8 HF PTH f(-3dB) Open PTH
9 HF PTH f(-40dB) Open PTH
Ni/Au
013-1
13
LR
6 HSDSMT Device failed, U3
015-4
14
LR
9 HF PTH f(-40dB) Wrong value capacitor
Table F.2 Anomaly Summary After Exposure to Thermal Shock
IIASI
MSN Site
Flux
Circuit Test Technician Comments
079-4 1
WS
12
HF SMT f(-40dB)
083-2 1
WS
7
HF PTH 50MHz Open PTH
8
HF PTH f(-3dB) Open PTH
9
HF PTH f(-40dB) Open PTH
10
HF SMT 50MHz Open PTH
11
HF SMT f(-3dB) Open PTH
12
HF SMT f(-40dB) Open PTH
096-4 3
WS
10
HF SMT 50MHz Open PTH
11
HF SMT f(-3dB) Open PTH
12
HF SMT f(-40dB) Open PTH
098-3 3
WS
10
HF SMT 50MHz Open PTH
11
HF SMT f(-3dB) Open PTH
12
HF SMT f(-40dB) Open PTH
098-4 3
WS
11
HF SMT f(-3dB) Waveform shifted
099-1 3
WS
12
HF SMT f(-40dB) Distorted Waveform (does not quite go to -40dB, reads at-
3dB)
111-3 3 WS 23 Stranded Wire 2 Minor
OSP
006-4 5 LR 12 HF SMT f(-40dB) Distorted waveform (goes to 40db but flattens and crosses
beyond 900mhz
009-2 6 LR 10 HF SMT 50MHz Open PTH on coil
11 HF SMT f(-3dB) Open PTH on coil
12 HF SMT f(-40dB) Open PTH on coil
F-4
-------
APPENDIX F
014-3
5
LR
10
HF SML 50MHz
Open PLH
11
HF SML f(-3dB)
Open PLH
12
HF SML f(-40dB)
Open PLH
056-2
5
LR
7
HF PLH 50MHz
Open PLH
8
HF PLH f(-3dB)
Open PLH
056-4
5
LR
7
HF PLH 50MHz
2 open PLHs
8
HF PLH f(-3dB)
2 open PLHs
9
HF PLH f(-40dB)
2 open PLHs
10
HF SML 50MHz
2 open PLHs
11
HF SML f(-3dB)
2 open PLHs
12
HF SML f(-40dB)
2 open PLHs
058-1
5
WS
10
HF SML 50MHz
Open PLH
12
HF SML f(-40dB)
Open PLH
060-1
5
ws
12
HF SML f(-40dB)
060-2
5
WS
10
HF SML 50MHz
Open PLH
12
HF SML f(-40dB)
Open PLH
Immersion Sn
028-2
9
LR
10
HF SML 50MHz
Open PLH
12
HF SML f(-40dB)
Open PLH
030-4
9
LR
4
HVLCSML
Burnt etch (visual)
032-4
8
LR
7
HF PLH 50MHz
Open PLH
8
HF PLH f(-3dB)
Open PLH
033-2
8
LR
17
HF LLC RNR
037-2
9
LR
5
HSD PLH
Likely component failure
10
HF SML 50MHz
Open PLH
11
HF SML f(-3dB)
Open PLH
12
HF SML f(-40dB)
Open PLH
084-1
7
LR
10
HF SML 50MHz
Open PLH
11
HF SML f(-3dB)
Open PLH
12
HF SML f(-40dB)
Open PLH
086-2
7
WS
5
HSD PLH
Likely component failure
WS
12
HF SML f(-40dB)
Distorted Waveform
087-3
7
WS
7
HF PLH 50MHz
High resistance on coil (acts like open PLH)
8
HF PLH f(-3dB)
High resistance on coil (acts like open PLH)
9
HF PLH f(-40dB)
High resistance on coil (acts like open PLH)
12
HF SML f(-40dB)
High resistance on coil (acts like open PLH)
088-3
7
LR
10
HF SML 50MHz
Open PLH
11
HF SML f(-3dB)
Open PLH
12
HF SML f(-40dB)
Open PLH
089-1
7
WS
7
HF PLH 50MHz
Open PLH
8
HF PLH f(-3dB)
Open PLH
9
HF PLH f(-40dB)
Open PLH
12
HF SML f(-40dB)
Open PLH
089-2
7
WS
10
HF SML 50MHz
High resistance on coil (acts like open PLH)
11
HF SML f(-3dB)
High resistance on coil (acts like open PLH)
12
HF SML f(-40dB)
High resistance on coil (acts like open PLH)
089-4
7
WS
10
HF SML 50MHz
Open PLH
11
HF SML f(-3dB)
Open PLH
12
HF SML f(-40dB)
Open PLH
090-2
7
WS
7
HF PLH 50MHz
Open PLH on coil
8
HF PLH f(-3dB)
Open PLH on coil
9
HF PLH f(-40dB)
Open PLH on coil
102-4
10
WS
17
HF LLC RNR
Immersion Ag
071-1
11
LR
10
HF SML 50MHz
Open PLH on coil
11
HF SML f(-3dB)
Open PLH on coil
12
HF SML f(-40dB)
Open PLH on coil
072-1
11
LR
7
HF PLH 50MHz
Open PLH
F-5
-------
APPENDIX F
8
HF PLH f(-3dB)
Open PLH
9
HF PLH f(-40dB)
Open PLH
073-3
11
LR
7
HF PLH 50MHz
Open PLH
8
HF PLH f(-3dB)
Open PLH
9
HF PLH f(-40dB)
Open PLH
15
HR LLC 1GHz
082-2
11
WS
12
HF SML f(-40dB)
Burnt etch
085-1
12
ws
7
HF PLH 50MHz
Open PLH
8
HF PLH f(-3dB)
Open PLH
9
HF PLH f(-40dB)
Open PLH
10
HF SML 50MHz
Open PLH
11
HF SML f(-3dB)
Open PLH
12
HF SML f(-40dB)
Open PLH
085-2
12
WS
7
HF PLH 50MHz
Open PLH (2 places)
8
HF PLH f(-3dB)
Open PLH (2 places)
9
HF PLH f(-40dB)
Open PLH (2 places)
10
HF SML 50MHz
Open PLH (2 places)
11
HF SML f(-3dB)
Open PLH (2 places)
12
HF SML f(-40dB)
Open PLH (2 places)
091-4
12
ws
12
HF SML f(-40dB)
094-1
12
ws
7
HF PLH 50MHz
Burnt Etch, High Resistance PLH, and Open PLH
8
HF PLH f(-3dB)
Burnt Etch, High Resistance PLH, and Open PLH
9
HF PLH f(-40dB)
Burnt Etch, High Resistance PLH, and Open PLH
10
HF SML 50MHz
Burnt Etch, High Resistance PLH, and Open PLH
11
HF SML f(-3dB)
Burnt Etch, High Resistance PLH, and Open PLH
12
HF SML f(-40dB)
Burnt Etch, High Resistance PLH, and Open PLH
094-4
12
ws
7
HF PLH 50MHz
Open PLH
8
HF PLH f(-3dB)
Open PLH
9
HF PLH f(-40dB)
Open PLH
Ni/Au
013-1
13
LR
6
HSD SML
Device failed, U3
015-2
14
LR
7
HF PLH 50MHz
Open PLH on coil
8
HF PLH f(-3dB)
Open PLH on coil
9
HF PLH f(-40dB)
Open PLH on coil
055-1
13
WS
7
HF PLH 50MHz
Open PLH
8
HF PLH f(-3dB)
Open PLH
9
HF PLH f(-40dB)
Open PLH
Ni/Pd/Au
036-1
16
ws
6
HSD SML
Likely component failure
Table F.3 Anomaly Summary After Mechanical Shock
(shaded entries signify carry over TS anomalies)
HASL
MSN
Site
Flux
Circuit
Test Technician Comments
039-2
2
LR
12
HF SML f(-40dB)
Waveform distorted
046-1
2
LR
10
HF SML 50MHz
Open PLH
11
HF SML f(-3dB)
12
HF SML f(-40dB)
046-2
2
LR
10
HF SML 50MHz
Open PLH
11
HF SML f(-3dB)
12
HF SML f(-40dB)
046-4
2
LR
12
HF SML f(-40dB)
Distorted waveform
076-1
1
LR
10
HF SML 50MHz
High resistance
11
HF SML f(-3dB)
12
HF SML f(-40dB)
076-2
1
LR
1
HCLVPLH
079-4
1
WS
12
HF SML f(-40dB)
Waveform does not go to -40dB
F-6
-------
APPENDIX F
080-4
1
WS
12
HF SML f(-40dB)
083-2
1
WS
7
HF PLH 50MHz
Open PLH
8
HF PLH f(-3dB)
9
HF PLH f(-40dB)
11
HF SML f(-3dB)
12
HF SML f(-40dB)
096-4
3
WS
7
HF PLH f(-3dB)
Open PLH, distorted waveform
10
HF SML 50MHz
11
HF SML f(-3dB)
12
HF SML f(-40dB)
13
HF LLC 50MHz
098-2
3
WS
12
HF SML f(-40dB)
098-3
3
WS
10
HF SML 50MHz
Open PLH
11
HF SML f(-3dB)
12
HF SML f(-40dB)
098-4
3
WS
10
HF SML 50MHz
Open PLH
11
HF SML f(-3dB)
Waveform shifted
12
HF SML f(-40dB)
099-1
3
WS
12
HF SML f(-40dB)
Distorted waveform
099-4
3
WS
12
HF SML f(-40dB)
Distorted waveform
100-3
3
WS
12
HF SML f(-40dB)
Distorted waveform
OSP
006-4
6
LR
12
HF SML f(-40dB)
Distorted waveform
007-3
6
LR
12
HF SML f(-40dB)
009-2
6
LR
10
HF SML 50MHz
Open PLH
11
HF SML f(-3dB)
12
HF SML f(-40dB)
010-1
4
LR
1
HCLVPLH
Distorted waveform
12
HF SML f(-40dB)
010-2
4
LR
12
HF SML f(-40dB)
010-4
4
LR
14
HF LLC 500MHz
014-1
5
LR
10
HF SML 50MHz
Open etch
11
HF SML f(-3dB)
12
HF SML f(-40dB)
014-3
5
LR
1
HCLVPLH
Open PLH
056-1
5
LR
12
HF SML f(-40dB)
Waveform does not go to -40 at the correct frequency
056-2
5
LR
1
HCLVPLH
Open PLH
7
HF PLH 50MHz
8
HF PLH f(-3dB)
9
HF SML 50MHz
10
HF SML f(-3dB)
12
HF SML f(-40dB)
056-3
5
LR
12
HF SML f(-40dB)
Waveform shifted
056-4
5
LR
7
HF PLH 50MHz
Open PLH - 2 places
8
HF PLH f(-3dB)
9
HF PLH f(-40dB)
10
HF SML 50MHz
11
HF SML f(-3dB)
12
HF SML f(-40dB)
057-1
5
WS
12
HF SML f(-40dB)
Waveform does not go to -40dB
058-1
5
WS
10
HF SML 50MHz
Open PLH
11
HF SML f(-3dB)
12
HF SML f(-40dB)
060-1
5
WS
12
HF SML f(-40dB)
Distorted waveform
060-2
5
WS
7
HF SML 50MHz
Open PLH
9
HF SML f(-40dB)
060-4
5
WS
12
HF SML f(-40dB)
Distorted waveform
061-4
4
WS
12
HF SML f(-40dB)
F-7
-------
APPENDIX F
062-1
4
WS
12
HF SML f(-40dB)
Distorted waveform
062-4
4
ws
12
HF SML f(-40dB)
Waveform shifted
065-1
4
WS
12
HF SML f(-40dB)
High resistance
065-4
4
ws
12
HF SML f(-40dB)
Immersion Sn
026-4
9
LR
5
HSD PLH
Bad HSD PLH device
028-2
9
LR
10
HF SML 50MHz
Open etch
11
HF SML f(-3dB)
12
HF SML f(-40dB)
029-1
9
LR
1
HCLVPLH
029-2
9
LR
17
HF LLC RNR
030-4
9
LR
9
HF PLH f(-40dB)
Burnt etch (visual)
032-4
8
LR
7
HF PLH 50MHz
Open PLH
9
HF PLH f(-40dB)
033-2
8
LR
17
HF LLC RNR
037-2
9
LR
5
HSD PLH
Open etch
10
HF SML 50MHz
11
HF SML f(-3dB)
12
HF SML f(-40dB)
040-3
8
LR
9
HF PLH f(-40dB)
Distorted waveform
084-1
7
LR
10
HF SML 50MHz
Open PLH
11
HF SML f(-3dB)
12
HF SML f(-40dB)
084-2
7
LR
9
HF PLH f(-40dB)
Open PLH
10
HF SML 50MHz
11
HF SML f(-3dB)
12
HF SML f(-40dB)
084-4
7
LR
10
HF SML 50MHz
Open PLH
11
HF SML f(-3dB)
12
HF SML f(-40dB)
15
HF LLC 1GHz
086-2
7
WS
1
HCLVPLH
Distorted waveform
12
HF SML f(-40dB)
087-1
7
WS
12
HF SML f(-40dB)
087-3
7
ws
8
HF PLH f(-3dB)
Open PLH 2 places SML & PLH
10
HF SML 50MHz
11
HF SML f(-3dB)
12
HF SML f(-40dB)
087-4
7
WS
12
HF SML f(-40dB)
Distorted waveform
088-3
7
LR
10
HF SML 50MHz
Open PLH
11
HF SML f(-3dB)
12
HF SML f(-40dB)
089-1
7
WS
7
HF PLH 50MHz
Open PLH
8
HF PLH f(-3dB)
Waveform does not go to -40dB
9
HF PLH f(-40dB)
12
HF SML f(-40dB)
089-2
7
WS
10
HF SML 50MHz
Open PLH
11
HF SML f(-3dB)
12
HF SML f(-40dB)
089-4
7
WS
7
HF PLH 50MHz
Open PLH - 2 places
8
HF PLH f(-3dB)
10
HF SML 50MHz
11
HF SML f(-3dB)
12
HF SML f(-40dB)
090-2
7
WS
7
HF PLH 50MHz
Open PLH 2 places SML & PLH
8
HF PLH f(-3dB)
10
HF SML 50MHz
11
HF SML f(-3dB)
F-8
-------
APPENDIX F
12 HF SMT f(-40dB)
102-4 10 WS 17 HFTLCRNR
104-4 10 WS 12 HF SMT f(-40dB)
113-1 10 WS 10 HFSMT50MHz OpenPTH
11 HF SMT f(-3dB)
12 HF SMT f(-40dB)
Immersion Ag
072-1 11 LR 7
8
9
HF PTH 50MHz
HF PTH f(-3dB)
HF PTH f(-40dB)
Open PTH
072-2 11 LR 12 HF SMT f(-40dB) Waveform shifted
072-4 11 LR 12 HF SMT f(-40dB) Waveform does not go to-40dB
073-3 11 LR 7
8
9
HF PTH 50MHz
HF PTH f(-3dB)
HF PTH f(-40dB)
Open PTH
075-2 11 LR 12 HF SMT f(-40dB)
075-3 11 LR 13 HF TLC 50MHz Distorted waveform
082-2 11 WS 10 HF SMT 50MHz OpenPTH
12 HF SMT f(-40dB)
13 HF TLC 50MHz
082-3 11 WS 12 HF SMT f(-40dB) Open PTH, distorted waveform
085-1 12 WS 7
8
9
10
11
HF PTH 50MHz
HF PTH f(-3dB)
HF PTH f(-40dB)
HF SMT 50MHz
HF SMT f(-3dB)
Open PTH - 2 places
085-2 12 WS 1
7
8
9
10
11
12
HCLVPTH
HF PTH 50MHz
HF PTH f(-3dB)
HF PTH f(-40dB)
HF SMT 50MHz
HF SMT f(-3dB)
HF SMT f(-40dB)
Open PTH
091-4 12 WS 1
10
11
12
HCLVPTH
HF SMT 50MHz
HF SMT f(-3dB)
HF SMT f(-40dB)
Open etch
094-1 12 WS 7
8
9
10
11
12
13
HF PTH 50MHz
HF PTH f(-3dB)
HF PTH f(-40dB)
HF SMT 50MHz
HF SMT f(-3dB)
HF SMT f(-40dB)
HF TLC 50MHz
Open PTH - 2 places
094-3 12 WS 9 HF PTH f(-40dB) Waveform distorted
12 HF SMT f(-40dB)
13 HF TLC 50MHz
17 HFTLCRNR
094-4 12 WS 1
7
8
9
10
11
12
13
095-4 12 WS 1
HCLVPTH
HF PTH 50MHz
HF PTH f(-3dB)
HF PTH f(-40dB)
HF SMT 50MHz
HF SMT f(-3dB)
HF SMT f(-40dB)
HF TLC 50MHz
HCLVPTH
Open PTH - 2 places
Open etch
F-9
-------
APPENDIX F
Ni/Au
013-1
13
LR
6
HSD SMT
HSD device fail
015-2
14
LR
7
HF PTH 50MHz
Open etch
9
HF PTH f(-40dB)
051-2
13
WS
8
HF PTH f(-3dB)
054-4
13
ws
8
HF PTH f(-3dB)
055-1
13
WS
7
HF PTH 50MHz
Open etch
8
HF PTH f(-3dB)
9
HF PTH f(-40dB)
055-4
13
ws
12
HF SMT f(-40dB)
Waveform distorted
Ni/Pd/Au
036-2
16
ws
12
HF SMT f(-40dB)
F.3 HCLV Circuitry
Pre-test measurements and deltas were analyzed with the GLM in Equation F. 1 for the main
effects site and flux and their interactions. These data were also subjected to a second GLM analysis
based on Equation F.2 for the main effects surface finish and flux. The base case for the GLM in
Equation F. 1 is defined as HASL at Site 1 and processed with LR flux. The base case for the GLM in
Equation F.2 is defined as HASL processed with LR flux.
Tables F.4 and F.5 summarize the results of these GLM analyses for HCLV PTH and HCLV
SMT. The upper portion of these tables contain the GLM results for Equation F. 1 while the lower
portion of these tables contain the GLM results for Equation F.2. The rows labeled "Constant" in
these tables contain the least squares estimates of p0 in Equations F. 1 and F.2 for each test time. The
numbers in the columns beneath the "Constants" are the estimated coefficients of the terms in
Equations F. 1 and F.2 that are significantly different from the base case. Shaded cells signify that the
corresponding term in the GLM is not significantly different from the base case.
The rows labeled Model R2 in Tables F.4 and F.5 show the percent of variation in the voltage
measurements explained by the respective estimated model. This value can range from 0% to 100%.
The model R2s for Equations F. 1 and F.2 for the HCLV circuitry are summarized as follows for each
test time.
GLM
Circuit
Pre-test
85/85
TS
MS
Site and Flux
HCLV PTH
2.0%
2.3%
3.7%
19.1%
HCLV SMT
4.2%
7.7%
10.9%
2.1%
Surface Finish and Flux
HCLV PTH
0.7%
1.3%
1.7%
7.7%
HCLV SMT
1.5%
0.3%
9.8%
0.7%
High R2 values would indicate a strong cause and effect relationship between the parameters of
surface finish, site, flux, and the voltage measurements at pretest. However, these R2s are all quite
small, which indicates that the experimental parameters: surface finish, site, and flux do not
significantly affect the HCLV voltage measurements at Pre-test nor do they affect the changes in the
voltage after exposure to each of the three test environments. That is, the HCLV measurements are
robust with respect to surface finish, site, and flux. The results for the two GLMs used in the analysis
are now examined in more detail.
GLM Results for Site and Flux
The uppermost portion of Table F.4 for HCLV PTH shows that only two experimental factors
(Site 2 and Site 8) are significantly different from the base case for the GLM in Equation F. 1. The
F-10
-------
APPENDIX F
estimated GLM at Pre-test for Equation F. 1 is obtained from the estimated coefficients in the second
column of Table F.4 as:
Y = 7.14 + 0.06 Site2 + 0.07 Site 8
where Y represents the voltage response. The predicted voltage from this estimated model is 7.14V
for all site and flux combinations except Sites 2 and 8. The predictions for these two sites are 7.14V +
0.06V = 7.20V and 7.14V + 0.07V = 7.21V, respectively. Note that even though these two terms are
statistically significant, they represent very small changes from the base case voltage and, as such, are
not of practical interest. Moreover, the model R2 is only 2.0%, which has no practical value. Similar
comments hold for the GLM analyses at Pre-test for HCLV SMT.
Columns 3 to 5 in Tables F.4 and F.5 give the HCLV PTH and HCLV SMT GLM results for
Delta 1, 2, and 3, respectively. Note that these latter three analyses are based on changes in the voltage
measurements from Pre-test. The model R2 values after 85/85 and TS are also quite small, which
implies that the experimental parameters did not influence the HCLV measurements after exposure to
the 85/85, TS, and MS test environments.
In spite of the lack of significant experimental parameters in the HCLV GLMs, there is one very
interesting aspect of the model for HCLV SMT at Post MS. Note that the estimate of the constant term
in the last column of Table F.5 is 2.48, whereas, the estimated constants at Post 85/85 and Post TS
were 0.04 and 0.05, respectively. This is an increase of approximately 2.43 V. The explanation of this
increase requires a review of the HCLV circuit, which is given in Section F. 10. In particular, Section
F. 10 explains that the HCLV circuit has seven 10Q resistors, Ri, R2,..., R7 in parallel. The overall
circuit resistance, Rtotai, is the parallel combination of these seven resistors, which is given as:
1 1 1 1 1 7
= — + — + — + ••• + — = (F.3)
Rtotai Rl ^2 ^2 ^7 10Q
10Q /c /n
Rtotal =— (F-4)
Since a current (I) of 5 A was applied to the circuit, Ohm's Law gives the resulting voltage (V) as
V = IR = 5Ax^^ = 7.14F (F.5)
7
During the MS test, it was noted that one to three of the resistors frequently fell off the board. In fact,
158 of the 164 PWAs were missing at least one of these resistors. If a single resistor is missing,
Equation F.5 would be revised as follows:
V = IR=5Ax^-= 8.33V (F.6)
6
Likewise, two missing resistors increase the voltage to 10V. Next consider the following dotplot of
voltage measurements at Post MS.
F-l 1
-------
APPENDIX F
+ + + + + + Voltage
7.20 7.80 8.40 9.00 9.60 10.20
Note how the voltages are lumped around the points at 7.14V, 8.33 V, and 10V, which
corresponds to the loss of no, one, or two resistors. Thus, the constant term in the GLM represents an
average increase in voltage of 2.48V over the nominal expected value of 7.14V, which is between one
and two missing resistors.
GLM Results for Surface Finish and Flux
The lower portion of Table F.4 for HCLV PTH shows that only one experimental factor
(Ni/Pd/Au) is significantly from the base case at Pre-test for the GLM in Equation F.2. The estimated
model is:
Y = 7.15 -0.04 Ni/Pd/Au
where Y represents the voltage response. The predicted voltage from this estimated model is 7.15 V
for all surface finish and flux combinations except for Ni/Pd/Au processed with either flux, in which
case the prediction is decreased by 0.04 V or 7.15 V - 0.04V = 7.11V. As was just discussed with the
previous GLM, even though the coefficient for Ni/Pd/Au is statistically significant, it actually
represents a very small change from the base case and, as such, is not of practical interest. Moreover,
the model R2 is only 0.7%, which has no practical value. Similar comments hold for the GLM
analyses at Pre-test for HCLV SMT.
These low R2 values imply that the experimental parameters do not differ significantly from the
base case in terms of their impact on the voltage of the HCLV PTH and HCLV SMT circuits. That is,
there is no practical difference from the base case voltage measurements due to surface finish or flux
type. This result is to be expected since there were no difference among sites for these circuits in the
GLM analysis based on Equation F. 1.
Columns 3 to 5 in Tables F.4 and F.5 give the HCLV PTH and HCLV SMT GLM results for
Delta 1, 2, and 3, respectively. The model R2 values at Post 85/85, Post TS, and Post MS are also quite
small, which implies that the experimental parameters did not influence the HCLV measurements after
exposure to the 85/85 and TS test environments. However, as just explained for the Site and Flux
model, the constant term in the last column of Table F.5 is affected by the missing resistors.
F-12
-------
APPENDIX F
Table F.4 Significant Coefficients for the Two GLM Analyses by Test Time for HCLV PTH
GLM from Eq. F.l: Sites and Interactions with Flux
Experimental Factor
Pre-Test
85/85
(Delta 1)
Thermal Shock
(Delta 2)
Mech Shock
(Delta 3)
Constant
7.14
0.04
0.05
0.14
Flux
Site 2
0.06
-0.17
Site 3
Site 4
Site 5
Site 6
Site 7
Site 8
0.07
Site 9
Site 10
Site 11
0.13
Site 12
0.80
Site 13
Site 14
Site 15
Site 16
Site 4 * Flux
Site 5 * Flux
Site 7 * Flux
Site 11 * Flux
-0.16
Site 13 * Flux
Site 16 * Flux
Model R2
2.0%
2.3%
3.7%
19.1%
Standard Deviation
0.13
0.18
0.17
0.36
GLM from Eq. F.2: Surface Finishes and Flux
Experimental Factor
Pre-Test
85/85
(Delta 1)
Thermal Shock
(Delta 2)
Mech Shock
(Delta 3)
Constant
7.15
0.03
0.04
0.13
OSP
Immersion Sn
Immersion Ag
0.07
0.07
0.34
Ni/Au
Ni/Pd/Au
-0.04
Flux
Model R2
0.7%
1.3%
1.7%
7.7%
Standard Deviation
0.10
0.10
0.17
0.38
F-13
-------
APPENDIX F
Table F.5 Significant Coefficients for the Two GLM Analyses by Test Time for HCLV SMT
GLM from Eq. F.l: Sites and Interactions with Flux
Experimental Factor
Pre-Test
85/85
Thermal Shock
Mech Shock
(Delta 1)
(Delta 2)
(Delta 3)
Constant
7.26
0.04
0.05
2.48
Flux
Site 2
-0.48
Site 3
Site 4
Site 5
-0.10
Site 6
Site 7
Site 8
0.06
-0.09
Site 9
Site 10
-0.07
0.11
Site 11
Site 12
Site 13
Site 14
Site 15
Site 16
Site 4 * Flux
Site 5 * Flux
-0.14
Site 7 * Flux
Site 11 * Flux
Site 13 * Flux
-0.11
Site 16 * Flux
Model R2
4.2%
7.7%
10.9%
2.1%
Standard Deviation
0.09
0.12
0.13
0.70
GLM from Eq. F.2: Surface Finishes and Flux
Experimental Factor
Pre-Test
85/85
Thermal Shock
Mech Shock
(Delta 1)
(Delta 2)
(Delta 3)
Constant
7.26
0.03
0.07
2.49
OSP
-0.08
Immersion Sn
-0.15
Immersion Ag
-0.02
Ni/Au
-0.10
Ni/Pd/Au
Flux
-0.02
Model R2
1.5%
0.3%
9.8%
0.7%
Standard Deviation
0.09
0.1
0.13
0.70
F-14
-------
APPENDIX F
F.4 HVLC Circuitry
Results of the GLM analyses for HVLC PTH and HVLC SMT circuits are given in Tables F.6 and
F.7, respectively. Columns 3 to 5 in these tables give the GLM results for 85/85, TS, and MS,
respectively. The model R2s for Equations F. 1 and F.2 for the HVLC circuitry are summarized as
follows for each test time.
GLM
Circuit
Pre-test
85/85
TS
MS
Site and Flux
HVLC PTH
13.3%
5.2%
0.0%
3.2%
HVLC SMT
20.9%
14.0%
18.7%
NA
Surface Finish and Flux
HVLC PTH
7.6%
2.5%
2.6%
3.2%
HVLC SMT
14.0%
15.3%
12.9%
NA
These model R2 values are generally higher that those observed for the HCLV measurements.
However, the magnitudes of the coefficients were too small to be of practical significance relative to
the JTP acceptance criteria, which indicates that these parameters do not influence the HVLC
measurements. To further explain this point, consider the coefficients for site and flux in Table F.6 at
Pre-test where the constant term is 5.018|jA, The largest coefficient at Pre-test is -0.008|iA for the
interaction of Site 4 and Flux. Thus, this interaction can decrease the constant term to 5,018|iA -
0,008|iA = 5.010|iA, which is so far from the lower and upper limits of 4|iA and 6|iA that it is not of
practical interest. Note that there are no R values listed for HVLC SMT at Post MS. This is due to
resistors coming off the PWA during the MS test, which caused the HVLC SMT circuit to give a
constant response for reasons that will now be explained.
Boxplot Displays of Multiple Comparison Results
Figures F. 1 to F.8 give boxplots for the HVLC PTH and SMT circuits. It is important to keep the
vertical scale in mind relative to the acceptance criteria when viewing these boxplots. That is, the
acceptance criteria indicates that the current should be between 4|iA and 6|iA. These boxplots are
centered close to 5|iA and the total spread is on the order of 0.02|iA for the PTH circuits and
approximately 0,5|iA for SMT circuits. Hence, even though there are some statistically significantly
differences, they are not likely to be of practical concern. Note the boxplots in Figure F.8 for HCLV
SMT at Post MS. These values are all either 0|iA for very close to it, reflecting the fact that the
resistors came off the PWA during the MS test.
F-15
-------
APPENDIX F
Table F.6 Significant Coefficients for the Two GLM Analyses by Test Time for HVLC PTH
GLM from Eq. F.l: Sites and Interactions with Flux
Experimental Factor
Pre-Test
85/85
Thermal Shock
Mech Shock
Constant
5.018
5.004
4.999
4.998
Flux
Site 2
Site 3
Site 4
0.007
Site 5
Site 6
Site 7
Site 8
0.005
Site 9
0.004
Site 10
Site 11
Site 12
0.004
0.006
Site 13
Site 14
-0.005
Site 15
Site 16
Site 4 * Flux
-0.008
Site 5 * Flux
Site 7 * Flux
Site 11 * Flux
0.006
Site 13 * Flux
Site 16 * Flux
Model R2
13.3%
5.2%
0.0%
3.2%
Standard Deviation
0.005
0.006
0.006
0.006
GLM from Eq. F.2: Surface Finishes and Flux
Experimental Factor
Pre-Test
85/85
Thermal Shock
Mech Shock
Constant
5.018
5.004
4.998
4.998
OSP
Immersion Sn
0.003
0.002
Immersion Ag
0.003
0.003
Ni/Au
-0.003
Ni/Pd/Au
Flux
Model R2
7.6%
2.5%
2.6%
3.2%
Standard Deviation
0.005
0.006
0.006
0.006
F-16
-------
APPENDIX F
Table F.7 Significant Coefficients for the Two GLM Analyses by Test Time for HVLC SMT
GLM from Eq. F.l: Sites and Interactions with Flux
Experimental Factor
Pre-Test
85/85
Thermal Shock
Mech Shock
Constant
5.038
5.034
5.039
Flux
Site 2
Site 3
Site 4
Site 5
Site 6
Site 7
Site 8
0.172
0.173
0.170
Site 9
Site 10
0.111
0.111
0.109
Site 11
Site 12
0.122
0.125
0.120
Site 13
Site 14
Site 15
0.125
0.126
0.125
Site 16
Site 4 * Flux
Site 5 * Flux
Site 7 * Flux
Site 11 * Flux
Site 13 * Flux
Site 16 * Flux
Model R2
20.9%
21.5%
18.7%
Standard Deviation
0.100
0.100
0.112
GLM from Eq.
F.2: Surface Finishes and Flux
Experimental Factor
Pre-Test
85/85
Thermal Shock
Mech Shock
Constant
5.032
5.027
5.033
OSP
Immersion Sn
0.095
0.100
0.097
Immersion Ag
0.087
0.090
0.085
Ni/Au
Ni/Pd/Au
Flux
Model R2
14.0%
15.3%
12.9%
Standard Deviation
0.100
0.100
0.110
F-17
-------
APPENDIX F
F.5 HSD Circuitry
The complete results of the GLM analyses are given in Tables F.8 and F.9, respectively. Columns
3 to 5 in these tables give the GLM results for 85/85, TS, and MS, respectively. Note that these latter
three analyses are based on changes in total propagation delay from Pre-test. The model R2s for
Equations F. 1 and F.2 for the HSD circuitry are summarized as follows for each test time.
GLM
Circuit
Pre-test
85/85
TS
MS
Site and Flux
HSD PTH
5.1%
9.8%
4.3%
9.5%
HSD SMT
6.1%
6.4%
0.0%
2.3%
Surface Finish and Flux
HSD PTH
0.9%
1.6%
1.8%
6.7%
HSD SMT
1.0%
0.3%
0.8%
0.2%
All these model R2 values are quite small at each test time, which indicates that the experimental
parameters under evaluation do not influence the HSD total propagation delay measurements.
Boxplot Displays of Multiple Comparison Results
Figures F.9 and F.10 give boxplots of Pre-test measurements of total propagation delay for the
HSD PTH and HSD SMT circuits, respectively. Note that most total propagation delays in Figure F.9
for HSD PTH are a little over 17 ns with a range of about Ins. Figure F. 10 shows that the total
propagation delays for HSD SMT have a range of about 0.4ns and are centered about 9.2ns. The
percentage changes in the total propagation delay measurements were small and well within the
acceptance criteria so boxplot displays of these measurements are not presented.
F-18
-------
APPENDIX F
Table F.8 Significant Coefficients for the Two GLM Analyses by Test Time for HSD PTH
GLM from Eq. F.l: Sites and Interactions with Flux
Experimental Factor
Pre-Test
85/85
Thermal Shock
Mech Shock
(Delta 1)
(Delta 2)
(Delta 3)
Constant
17.13
0.55
0.98
0.37
Flux
-0.46
Site 2
Site 3
2.60
Site 4
0.14
Site 5
0.61
Site 6
-1.00
Site 7
Site 8
Site 9
1.89
Site 10
Site 11
-2.30
Site 12
-3.50
Site 13
Site 14
Site 15
Site 16
Site 4 * Flux
Site 5 * Flux
Site 7 * Flux
Site 11 * Flux
Site 13 * Flux
Site 16 * Flux
0.19
Model R2
5.1%
9.8%
4.3%
9.5%
Standard Deviation
0.19
1.30
1.33
3.52
GLM from Eq. F.2: Surface Finishes and Flux
Experimental Factor
Pre-Test
85/85
Thermal Shock
Mech Shock
(Delta 1)
(Delta 2)
(Delta 3)
Constant
17.13
0.88
0.88
0.52
OSP
0.05
Immersion Sn
Immersion Ag
-2.89
Ni/Au
Ni/Pd/Au
Flux
-0.35
-0.36
Model R2
0.9%
1.6%
1.8%
6.7%
Standard Deviation
0.20
1.00
1.30
3.5
F-19
-------
APPENDIX F
Table F.9 Significant Coefficients for the Two GLM Analyses by Test Time for HSD SMT
GLM from Eq. F.l: Sites and Interactions with Flux
Experimental Factor
Pre-Test
85/85
Thermal Shock
Mech Shock
(Delta 1)
(Delta 2)
(Delta 3)
Constant
9.23
0.94
1.16
-0.002
Flux
Site 2
-1.59
Site 3
Site 4
Site 5
Site 6
Site 7
Site 8
-1.60
Site 9
Site 10
Site 11
Site 12
-1.27
Site 13
Site 14
Site 15
0.12
Site 16
Site 4 * Flux
Site 5 * Flux
-() 10
Site 7 * Flux
Site 11 * Flux
Site 13 * Flux
Site 16 * Flux
Model R2
6.1%
6.4%
0.0%
2.3%
Standard Deviation
0.13
1.65
1.99
2.25
GLM from Eq. F.2: Surface Finishes and Flux
Experimental Factor
Pre-Test
85/85
Thermal Shock
Mech Shock
(Delta 1)
(Delta 2)
(Delta 3)
Constant
9.21
0.77
1.23
-0.04
OSP
Immersion Sn
Immersion Ag
-0.56
Ni/Au
-0.25
Ni/Pd/Au
0.35
Flux
0.03
Model R2
1.0%
0.3%
0.8%
0.2%
Standard Deviation
0.10
1.00
1.90
2.2
F-20
-------
APPENDIX F
F.6 HF LPF Circuitry
Pre-test measurements for all HF LPF circuits were subjected to GLM analyses, as were the deltas
after 85/85, TS, and MS. The results of the GLM analyses are given in Tables F. 10 to F. 15. Columns
3 to 5 in these tables give the GLM results for 85/85, TS, and MS, respectively.
Note that these latter three analyses are based on changes from Protest measurements. The model
R2s for Equations F. 1 and F.2 for the HF LPF circuitry are summarized as follows for each test time.
GLM
Circuit
Pre-test
85/85
TS
MS
Site and Flux
PTH 50MHz
20.6%
29.5%
24.1%
20.5%
PTH f(-3dB)
7.1%
10.8%
10.2%
23.4%
PTH f(-40dB)
14.3%
9.6%
7.6%
13.5%
SMT 50MHz
3.9%
10.3%
21.1%
32.2%
SMT f(-3dB)
8.8%
10.5%
19.1%
14.3%
SMT f(-40dB)
5.3%
2.3%
16.1%
29.4%
Surface Finish and Flux
PTH 50MHz
4.3%
2.3%
0.3%
8.1%
PTH f(-3dB)
7.8%
0.2%
1.6%
10.9%
PTH f(-40dB)
4.5%
1.8%
1.6%
10.9%
SMT 50MHz
2.7%
0.6%
0.8%
6.1%
SMT f(-3dB)
0.7%
1.5%
5.0%
3.0%
SMT f(-40dB)
5.2%
0.3%
4.9%
14.4%
The model R2 values are quite small at Pre-test, which indicates that the parameters under
evaluation do not influence the HF LPF measurements. The same is true at Post 85/85. The model R
values are also quite small at Post TS and Post MS. However, the test measurements contained many
extreme outlying observations at both of these later two test times, which greatly increases the sample
variance and in turn hinders the interpretation of the GLM results. As indicated in Tables F. 1, F.2, and
F.3 there were many anomalous HF LPF test measurements (171 at Post MS).
Boxplot Displays of Multiple Comparison Results
Boxplot displays of all test results for HF LPF circuits have been created to aid in the
interpretation of the results. Figures 4.9 to 4.15 in Chapter 4 show the boxplots for the analyses with
significant differences or values not meeting acceptance criteria. Figures F. 11 to F.27 show all
remaining boxplots associated with the HF LPF results.
F-21
-------
APPENDIX F
Table F.10 Significant Coefficients for the Two GLM Analyses by Test Time for HF PTH 50 MHz
GLM from Eq. F.l: Sites and Interactions with Flux
Experimental Factor
Pre-Test
85/85
(Delta 1)
Thermal Shock
(Delta 2)
Mech Shock
(Delta 3)
Constant
-0.721
-0.034
-0.002
-2.666
Flux
Site 2
Site 3
Site 4
Site 5
Site 6
Site 7
Site 8
Site 9
Site 10
Site 11
Site 12
-28.1
Site 13
-0.180
0.197
0.192
Site 14
-0.073
Site 15
Site 16
Site 4 * Flux
Site 5 * Flux
Site 7 * Flux
-18.5
Site 11 * Flux
Site 13 * Flux
0.160
-0.206
-0.180
Site 16 * Flux
Model R2
20.6%
29.5%
24.1%
20.5%
Standard Deviation
0.055
0.048
0.063
14.1
GLM from Eq. F.2: Surface Finishes and Flux
Experimental Factor
Pre-Test
85/85
(Delta 1)
Thermal Shock
(Delta 2)
Mech Shock
(Delta 3)
Constant
-0.720
-0.034
0.003
-3.28
OSP
-0.010
Immersion Sn
Immersion Ag
-13.6
Ni/Au
-0.034
0.023
Ni/Pd/Au
Flux
Model R2
4.3%
2.3%
0.3%
8.1%
Standard Deviation
0.060
0.050
0.072
15.00
F-22
-------
APPENDIX F
Table F.ll Significant Coefficients for the Two GLM Analyses by Test Time for HF PTH f(-3dB)
GLM from Eq. F.l: Sites and Interactions with Flux
Experimental Factor
Pre-Test
85/85
(Delta 1)
Thermal Shock
(Delta 2)
Mech Shock
(Delta 3)
Constant
283.0
-0.9
0.5
-1.05
Flux
Site 2
Site 3
Site 4
Site 5
Site 6
-2.2
Site 7
Site 8
Site 9
Site 10
Site 11
Site 12
-116
Site 13
-1.8
Site 14
Site 15
-1.5
Site 16
Site 4 * Flux
Site 5 * Flux
0.7
Site 7 * Flux
-1.2
-68
Site 11 * Flux
Site 13 * Flux
-79
Site 16 * Flux
Model R2
7.1%
10.8%
10.2%
23.4%
Standard Deviation
2.0
0.9
1.5
58.5
GLM from Eq. F.2: Surface Finishes and Flux
Experimental Factor
Pre-Test
85/85
(Delta 1)
Thermal Shock
(Delta 2)
Mech Shock
(Delta 3)
Constant
283.0
-1.0
0.5
4.19
OSP
0.1
-0.5
Immersion Sn
Immersion Ag
-53.0
Ni/Au
-1.6
Ni/Pd/Au
Flux
-23.8
Model R2
7.8%
0.2%
1.6%
10.9%
Standard Deviation
2.0
0.9
1.5
62.0
F-23
-------
APPENDIX F
Table F.12 Significant Coefficients for the Two GLM Analyses by Test Time for HF PTH f(-40dB)
GLM from Eq. F.l: Sites and Interactions with Flux
Experimental Factor
Pre-Test
85/85
(Delta 1)
Thermal Shock
(Delta 2)
Mech Shock
(Delta 3)
Constant
472.9
-0.2
-0.2
-11.7
Flux
Site 2
Site 3
Site 4
Site 5
-3.8
-1.8
Site 6
0.9
Site 7
Site 8
-1.5
Site 9
-5.7
Site 10
Site 11
Site 12
-140
Site 13
-5.1
Site 14
Site 15
-4.5
Site 16
Site 4 * Flux
Site 5 * Flux
2.6
Site 7 * Flux
Site 11 * Flux
Site 13 * Flux
Site 16 * Flux
Model R2
14.3%
9.6%
7.6%
13.5%
Standard Deviation
5.1
1.2
1.5
77.1
GLM from Eq. F.2: Surface Finishes and Flux
Experimental Factor
Pre-Test
85/85
(Delta 1)
Thermal Shock
(Delta 2)
Mech Shock
(Delta 3)
Constant
472.2
-0.1
-0.3
-8.41
OSP
Immersion Sn
-0.4
Immersion Ag
-83.0
Ni/Au
-3.2
Ni/Pd/Au
0.71
Flux
Model R2
4.5%
1.8%
1.6%
10.9%
Standard Deviation
5.0
1.0
1.5
78.0
F-24
-------
APPENDIX F
Table F.13 Significant Coefficients for the Two GLM Analyses by Test Time for HF SMT 50 MHz
GLM from Eq. F.l: Sites and Interactions with Flux
Experimental Factor
Pre-Test
85/85
(Delta 1)
Thermal Shock
(Delta 2)
Mech Shock
(Delta 3)
Constant
-0.733
-0.018
0.005
-3.1
Flux
Site 2
Site 3
-0.112
-19.2
Site 4
Site 5
-13.5
Site 6
Site 7
-0.126
-49.7
Site 8
Site 9
-0.049
Site 10
Site 11
Site 12
0.031
-31.4
Site 13
Site 14
Site 15
Site 16
Site 4 * Flux
0.021
Site 5 * Flux
Site 7 * Flux
25.0
Site 11 * Flux
-0.047
Site 13 * Flux
Site 16 * Flux
Model R2
3.9%
10.3%
21.1%
32.2%
Standard Deviation
0.039
0.037
0.069
17.2
GLM from Eq. F.2: Surface Finishes and Flux
Experimental Factor
Pre-Test
85/85
(Delta 1)
Thermal Shock
(Delta 2)
Mech Shock
(Delta 3)
Constant
-0.733
-0.023
-0.010
-5.62
OSP
0.017
Immersion Sn
-10.6
Immersion Ag
0.020
-10.7
Ni/Au
0.008
Ni/Pd/Au
Flux
Model R2
2.7%
0.6%
0.8%
6.1%
Standard Deviation
0.030
0.030
0.077
20.0
F-25
-------
APPENDIX F
Table F.14 Significant Coefficients for the Two GLM Analyses by Test Time for HF SMT f(-3dB)
GLM from Eq. F.l: Sites and Interactions with Flux
Experimental Factor
Pre-Test
85/85
(Delta 1)
Thermal Shock
(Delta 2)
Mech Shock
(Delta 3)
Constant
319.8
-1.3
0.7
-15.5
Flux
Site 2
1.0
108
Site 3
Site 4
Site 5
Site 6
Site 7
-15.3
Site 8
Site 9
-4.0
Site 10
Site 11
1.5
Site 12
-143
Site 13
3.7
Site 14
-3.9
Site 15
Site 16
Site 4 * Flux
Site 5 * Flux
-3.7
Site 7 * Flux
11.9
-102
Site 11 * Flux
-2.2
Site 13 * Flux
-4.4
Site 16 * Flux
Model R2
8.8%
10.5%
19.1%
14.3%
Standard Deviation
1.9
1.1
4.7
112
GLM from Eq. F.2: Surface Finishes and Flux
Experimental Factor
Pre-Test
85/85
(Delta 1)
Thermal Shock
(Delta 2)
Mech Shock
(Delta 3)
Constant
319.7
-1.3
0.4
-1.98
OSP
0.4
Immersion Sn
-2.8
Immersion Ag
0.5
Ni/Au
Ni/Pd/Au
Flux
-41.0
Model R2
0.7%
1.5%
5.0%
3.0%
Standard Deviation
2.0
1.0
5.0
11.0
F-26
-------
APPENDIX F
Table F.15 Significant Coefficients for the Two GLM Analyses by Test Time for HF SMT f(-40dB)
GLM from Eq. F.l: Sites and Interactions with Flux
Experimental Factor
Pre-Test
85/85
(Delta 1)
Thermal Shock
(Delta 2)
Mech Shock
(Delta 3)
Constant
865.5
1.7
-8.1
-80.3
Flux
Site 2
Site 3
-244
Site 4
Site 5
-10.7
-171
Site 6
Site 7
-430
Site 8
4.9
Site 9
Site 10
Site 11
2.2
Site 12
-19.7
-365
Site 13
Site 14
Site 15
Site 16
Site 4 * Flux
Site 5 * Flux
Site 7 * Flux
Site 11 * Flux
-23.7
Site 13 * Flux
Site 16 * Flux
Model R2
5.3%
2.3%
16.1%
29.4%
Standard Deviation
21.0
7.6
9.1
221
GLM from Eq. F.2: Surface Finishes and Flux
Experimental Factor
Pre-Test
85/85
(Delta 1)
Thermal Shock
(Delta 2)
Mech Shock
(Delta 3)
Constant
861.2
2.0
-6.8
-146.2
OSP
Immersion Sn
Immersion Ag
Ni/Au
13.4
1.0
192.0
Ni/Pd/Au
171.0
Flux
-4.4
-117.0
Model R2
5.2%
0.3%
4.9%
14.4%
Standard Deviation
21.0
7.0
9.7
24.0
F-27
-------
APPENDIX F
F.7 HF TLC Circuitry
Pre-test measurements for all HF TLC circuits except RNF were subjected to GLM analyses, as
were the deltas after 85/85, TS, and MS. The results of the GLM analyses are given in Tables F. 16 to
F.20. Columns 3 to 5 in those tables give the HF TLC PTH and HF TLC SMT GLM results for 85/85,
TS, and MS, respectively. Note that these latter three analyses are based on changes from Protest
measurements. The model R2s for Equations F. 1 and F.2 for the HF TLC circuitry are summarized as
follows for each test time, except for HF TLC RNF, which gave a constant response.
GLM
Circuit
Pre-test
85/85
TS
MS
Site and Flux
50MHz
62.3%
6.7%
0.0%
14.7%
500MHz
10.7%
8.1%
0.0%
8.1%
1GHz
13.2%
10.9%
6.1%
7.9%
RNF
RNR
2.7%
8.2%
2.4%
6.2%
Surface Finish and Flux
50MHz
48.1%
6.6%
5.0%
9.1%
500MHz
2.5%
0.9%
1.8%
1.4%
1GHz
0.9%
2,8%
4.1%
0.7%
RNF
RNR
3.6%
0.6%
3.5%
2.0%
The model R2 values for HF TLC are all quite small at Pre-test except for those at 50MHz, which
are of moderate size. The small R2 values indicate that the experimental parameters do not influence
the Pre-test HF TLC measurements. The moderate sized R values for the 50MHz case are examined
in further detail below (repeated from Chapter 4).
The predicted response at Pre-test for HF TLC 50MHz for the base case (HASL at Site 1
processed with LR flux) based on the Site & Flux GLM was -47.43dB. The predicted differences from
the base case are given in Appendix F in Table F.21. The results show that the sites that produced
Ni/Au and Ni/Au/Pd (#13-16) have predicted increases of less than 3dB. While statistically
significant, this change is rather small compared to the base case value and is probably not of practical
utility. Overall, some of the sites differ from the base case by approximately -1.5dB to 2.9dB. These
changes again may not have any practical significance since the important concept is not so much the
magnitude of the response, but rather its stability when subject to environmental stress conditions,
which is the basis for the acceptance criteria.
The predicted response at Pre-test for HF TLC 50MHz for the base case (HASL processed with
LR flux) based on the Surface Finish & Flux GLM was -46.73dB, which is almost identical to that for
the Site & Flux GLM. The predicted differences from the base case are given in Appendix F in Table
F.22. These predictions are consistent with those in Table F.21 and show that immersion Sn and
immersion Ag are approximately l.OdB lower than the base case and Ni/Au and Ni/Pd/Au are
approximately 1 to 2 dB higher than the base case. Again, these differences are most likely not of
practical utility.
Boxplot Displays of Multiple Comparison Results
HF TLC 50MHz. A boxplot display of the Post MS test results is given in Figure 4.16. Boxplots
for the other three test times are displayed in Figures F.28 to F.30.
HF TLC 500MHz. A boxplot display of the Post MS test results is given in Figure 4.17.
Boxplots for the other three test times are displayed in Figures F.31 to F.33.
F-28
-------
APPENDIX F
HF TLC 1GHz. Boxplots displays for are not given for the HF TLC 1GHz test results to
conserve space. The total variation at Pre-test for HF TLC 1GHz was only 2dB and there was only
one slight anomaly of -5dB at Post MS, which is not of concern.
HF TLC RNR. A boxplot display of the Post MS test results is given in Figure 4.18. Boxplots
for the other three test times are displayed in Figures F.34 to F.36.
Table F.16 Significant Coefficients for the Two GLM Analyses by Test Time for HF TLC 50 MHz Forward
GLM from Eq. F.l: Sites and Interactions with Flux
Experimental Factor
Pre-Test
85/85
Thermal Shock
Mech Shock
(Delta 1)
(Delta 2)
(Delta 3)
Constant
-47.43
0.22
-0.08
0.04
Flux
Site 2
Site 3
0.98
4.40
Site 4
Site 5
1.19
Site 6
1.48
Site 7
-1.51
Site 8
Site 9
Site 10
0.90
Site 11
3.20
Site 12
-1.40
7.60
Site 13
2.90
-1.17
Site 14
2.69
Site 15
2.05
Site 16
2.19
Site 4 * Flux
0.96
Site 5 * Flux
-1.37
Site 7 * Flux
Site 11 * Flux
Site 13 * Flux
1.41
Site 16 * Flux
-1.50
Model R2
62.3%
6.7%
0.0%
14.7%
Standard Deviation
1.00
1.0
1.01
4.80
GLM from Eq. F.2: Surface Finishes and Flux
Experimental Factor
Pre-Test
85/85
Thermal Shock
Mech Shock
(Delta 1)
(Delta 2)
(Delta 3)
Constant
-46.73
0.09
-0.30
0.29
OSP
Immersion Sn
-0.71
Immersion Ag
-0.97
4.7
Ni/Au
2.24
-0.45
Ni/Pd/Au
1.19
Flux
-0.59
0.48
0.45
Model R2
48.1%
6.6%
5.0%
9.1%
Standard Deviation
1.00
1.00
0.99
4.9
F-29
-------
APPENDIX F
Table F.17 Significant Coefficients for the Two GLM Analyses by Test Time for HF TLC 500 MHz Forward
GLM from Eq. F.l: Sites and Interactions with Flux
Experimental Factor
Pre-Test
85/85
(Delta 1)
Thermal Shock
(Delta 2)
Mech Shock
(Delta 3)
Constant
-17.48
0.06
-0.23
-0.14
Flux
Site 2
Site 3
0.64
Site 4
-1.32
Site 5
0.45
Site 6
0.53
Site 7
Site 8
Site 9
Site 10
0.56
Site 11
Site 12
-0.85
Site 13
-1.13
Site 14
Site 15
Site 16
Site 4 * Flux
1.50
Site 5 * Flux
Site 7 * Flux
Site 11 * Flux
Site 13 * Flux
1.35
Site 16 * Flux
Model R2
10.7%
8.1%
0.0%
8.1%
Standard Deviation
0.66
0.62
0.60
0.93
GLM from Eq. F.2: Surface Finishes and Flux
Experimental Factor
Pre-Test
85/85
(Delta 1)
Thermal Shock
(Delta 2)
Mech Shock
(Delta 3)
Constant
-17.41
0.02
-0.28
-0.09
OSP
0.27
Immersion Sn
0.20
Immersion Ag
Ni/Au
Ni/Pd/Au
0.23
Flux
-0.22
Model R2
2.5%
0.9%
1.8%
1.4%
Standard Deviation
0.60
0.60
0.59
0.96
F-30
-------
APPENDIX F
Table F.18 Significant Coefficients for the Two GLM Analyses by Test Time for HF TLC 1 GHz Forward
GLM from Eq. F.l: Sites and Interactions with Flux
Experimental Factor
Pre-Test
85/85
(Delta 1)
Thermal Shock
(Delta 2)
Mech Shock
(Delta 3)
Constant
-14.11
0.11
-0.39
-0.22
Flux
-0.16
Site 2
-0.30
Site 3
0.37
Site 4
Site 5
0.21
Site 6
Site 7
-1.26
Site 8
Site 9
Site 10
0.46
Site 11
-0.51
Site 12
Site 13
-0.46
Site 14
Site 15
-0.35
Site 16
Site 4 * Flux
Site 5 * Flux
Site 7 * Flux
1.00
Site 11 * Flux
Site 13 * Flux
0.59
Site 16 * Flux
Model R2
13.2%
10.9%
6.1%
7.9%
Standard Deviation
0.37
0.31
0.52
0.69
GLM from Eq. F.2: Surface Finishes and Flux
Experimental Factor
Pre-Test
85/85
(Delta 1)
Thermal Shock
(Delta 2)
Mech Shock
(Delta 3)
Constant
-14.16
0.11
-0.38
-0.30
OSP
0.09
0.14
Immersion Sn
Immersion Ag
-0.33
Ni/Au
-0.15
Ni/Pd/Au
Flux
Model R2
0.9%
2.8%
4.1%
0.7%
Standard Deviation
0.30
0.30
0.52
0.71
F-31
-------
APPENDIX F
Table F.19 Significant Coefficients for the Two GLM Analyses by Test Time for HF TLC Rev Null Freq
GLM from Eq. F.l: Sites and Interactions with Flux
Experimental Factor
Pre-Test
85/85
(Delta 1)
Thermal Shock
(Delta 2)
Mech Shock
(Delta 3)
Constant
Flux
Site 2
Site 3
Site 4
Site 5
Site 6
Site 7
Site 8
Site 9
Site 10
Site 11
Site 12
Site 13
Site 14
Site 15
Site 16
Site 4 * Flux
Site 5 * Flux
Site 7 * Flux
Site 11 * Flux
Site 13 * Flux
Site 16 * Flux
Model R2
Standard Deviation
GLM from Eq. F.2: Surface Finishes and Flux
Experimental Factor
Pre-Test
85/85
Thermal Shock
Mech Shock
(Delta 1)
(Delta 2)
(Delta 3)
Constant
OSP
Immersion Sn
Immersion Ag
Ni/Au
Ni/Pd/Au
Flux
Model R2
Standard Deviation
F-32
-------
APPENDIX F
Table F.20 Significant Coefficients for the Two GLM Analyses by Test Time for HF TLC Rev Null Resp
GLM from Eq. F.l: Sites and Interactions with Flux
Experimental Factor
Pre-Test
85/85
(Delta 1)
Thermal Shock
(Delta 2)
Mech Shock
(Delta 3)
Constant
-33.90
0.20
-0.05
0.02
Flux
Site 2
Site 3
Site 4
Site 5
1.13
Site 6
Site 7
Site 8
Site 9
Site 10
Site 11
-3.50
Site 12
-1.60
Site 13
-3.23
Site 14
Site 15
Site 16
Site 4 * Flux
Site 5 * Flux
-1.25
Site 7 * Flux
Site 11 * Flux
Site 13 * Flux
3.60
Site 16 * Flux
Model R2
2.7%
8.2%
2.4%
6.2%
Standard Deviation
1.40
1.70
2.20
3.56
GLM from Eq. F.2: Surface Finishes and Flux
Experimental Factor
Pre-Test
85/85
(Delta 1)
Thermal Shock
(Delta 2)
Mech Shock
(Delta 3)
Constant
-33.70
0.07
0.03
-0.74
OSP
Immersion Sn
-0.68
0.34
Immersion Ag
-1.26
Ni/Au
Ni/Pd/Au
Flux
1.03
Model R2
3.6%
0.6%
3.5%
2.0%
Standard Deviation
1.00
1.00
2.1
3.6
F-33
-------
APPENDIX F
Table F.21 Predicted Changes from the Base Case at Pre-test for HF TLC 50MHz for the GLM in
Equation F.l
LR Flux WS Flux
Site 2
Site 3
0.98
0.98
Site 4
Site 5
1.19
-0.18
Site 6
1.48
1.48
Site 7
-1.51
-1.51
Site 8
Site 9
Site 10
0.90
0.90
Site 11
Site 12
-1.40
-1.40
Site 13
2.90
2.90
Site 14
2.69
2.69
Site 15
2.05
2.05
Site 16
2.19
0.69
Table F.22 Predicted Changes from the Base Case at Pre-test for HF TLC 50MHz
for the GLM in Equation F.2
LR Flux WS Flux
OSP -0.59
Immersion Sn -0.71 -1.30
Immersion Ag -0.97 -1.56
Ni/Au 2.24 1.65
Ni/Pd/Au 1.19 0.60
F.8 Leakage Measurements
The results of the GLM analyses are given in Tables F.23 to F.26. Columns 3 to 5 in these tables
give the GLM results for 85/85, TS, and MS, respectively. The model R2s for Equations F. 1 and F.2
for the GLM analyses of the leakage measurements are summarized as follows.
GLM
Circuit
Pre-test
85/85
TS
MS
Site and Flux
10-Mil Pads
85.6%
22.7%
10.8%
8.6%
PGA-A
88.4%
3.9%
9.7%
9.0%
PGA-B
89.4%
5.6%
15.5%
12.5%
Gull Wing
55.4%
3.3%
2.8%
1.7%
Surface Finish and Flux
10-Mil Pads
74.8%
1.9%
3.4%
1.7%
PGA-A
81.3%
2.0%
9.7%
6.3%
PGA-B
88.7%
5.6%
16.0%
6.7%
Gull Wing
48.2%
1.9%
2.8%
2.6%
It is of interest to note that the model R2 values at Pre-test for all but the Gull Wing are all quite
large. However, these values decrease to close to zero after exposure to the 85/85 environment. These
results are now examined in detail for each of the four leakage circuits.
Tables F.27 and F.28 give the predicted changes from their respective base cases for all leakage
measurements at Pre-test for the GLMs in Equations F. 1 and F.2, respectively.
F-34
-------
APPENDIX F
Table F.23 Significant Coefficients for the Two GLM Analyses by Test Time for 10-Mil Pads
GLM from Eq. F.l: Sites and Interactions with Flux
Experimental Factor
Pre-Test
85/85
Thermal Shock
Mech Shock
Constant
12.20
13.29
14.45
14.76
Flux
0.74
Site 2
-0.97
Site 3
1.02
Site 4
0.93
Site 5
0.85
Site 6
Site 7
Site 8
Site 9
-1.24
-0.95
-0.84
Site 10
1.00
Site 11
Site 12
0.91
Site 13
-0.89
0.23
Site 14
-0.75
Site 15
0.98
0.55
Site 16
-0.76
Site 4 * Flux
Site 5 * Flux
Site 7 * Flux
0.85
Site 11 * Flux
1.06
Site 13 * Flux
1.95
Site 16 * Flux
1.74
Model R2
85.6%
22.7%
10.8%
8.6%
Standard Deviation
0.42
0.51
0.70
0.59
GLM from Eq. F.2: Surface Finishes and Flux
Experimental Factor
Pre-Test
85/85
Thermal Shock
Mech Shock
Constant
11.75
13.21
14.30
14.69
OSP
0.73
Immersion Sn
0.33
Immersion Ag
0.48
Ni/Au
0.21
Ni/Pd/Au
0.31
Flux
1.77
0.27
Model R2
74.8%
1.9%
3.4%
1.7%
Standard Deviation
0.50
0.50
0.72
0.61
F-35
-------
APPENDIX F
Table F.24 Significant Coefficients for the Two GLM Analyses by Test Time for PGA-A
GLM from Eq.
<\1: Sites and Interactions with Flux
Experimental Factor
Pre-Test
85/85
Thermal Shock
Mech Shock
Constant
11.88
12.50
13.66
13.69
Flux
1.58
0.348
0.22
Site 2
-1.19
Site 3
Site 4
-0.54
Site 5
Site 6
Site 7
Site 8
Site 9
-0.81
Site 10
Site 11
-0.34
Site 12
Site 13
-0.64
Site 14
-0.94
Site 15
Site 16
-1.14
Site 4 * Flux
-0.50
0.63
Site 5 * Flux
Site 7 * Flux
Site 11 * Flux
-0.64
Site 13 * Flux
0.91
Site 16 * Flux
1.34
Model R2
88.4%
3.9%
9.7%
9.0%
Standard Deviation
0.40
0.71
0.52
0.49
GLM from Eq.
7.2: Surface Finishes and Flux
Experimental Factor
Pre-Test
85/85
Thermal Shock
Mech Shock
Constant
11.38
12.41
13.66
13.66
OSP
0.35
Immersion Sn
0.25
Immersion Ag
Ni/Au
Ni/Pd/Au
-0.35
Flux
2.05
0.34
0.256
Model R2
81.3%
2.0%
9.7%
6.3%
Standard Deviation
0.5
0.70
0.51
0.49
F-36
-------
APPENDIX F
Table F.25 Significant Coefficients for the Two GLM Analyses by Test Time for PGA-B
GLM from Eq. F.l: Sites and Interactions with Flux
Experimental Factor
Pre-Test
85/85
Thermal Shock
Mech Shock
Constant
10.71
12.52
13.69
13.83
Flux
2.77
0.40
Site 2
-0.49
Site 3
Site 4
Site 5
-0.44
-0.63
Site 6
-0.41
-0.42
Site 7
Site 8
0.57
Site 9
Site 10
Site 11
Site 12
Site 13
Site 14
Site 15
Site 16
-0.34
-0.61
Site 4 * Flux
Site 5 * Flux
0.69
Site 7 * Flux
Site 11 * Flux
Site 13 * Flux
Site 16 * Flux
0.72
Model R2
89.4%
8.0%
15.5%
12.5%
Standard Deviation
0.47
0.53
0.56
0.50
GLM from Eq
. F.2: Surface Finishes and Flux
Experimental Factor
Pre-Test
85/85
Thermal Shock
Mech Shock
Constant
10.77
12.55
13.72
13.70
OSP
-0.23
-0.33
-0.21
Immersion Sn
Immersion Ag
Ni/Au
Ni/Pd/Au
-0.38
-0.40
Flux
2.71
0.39
0.20
Model R2
88.7%
5.6%
16.0%
6.7%
Standard Deviation
0.4
0.50
0.56
0.51
F-37
-------
APPENDIX F
Table F.26 Significant Coefficients for the Two GLM Analyses by Test Time for the Gull Wing
GLM from Eq
. F.l: Sites and
Interactions with
Flux
Experimental Factor
Pre-Test
85/85
Thermal Shock
Mech Shock
Constant
11.72
12.59
13.76
13.32
Flux
0.81
-0.37
Site 2
Site 3
Site 4
Site 5
0.37
Site 6
Site 7
Site 8
-0.64
Site 9
Site 10
0.47
Site 11
-0.65
Site 12
0.54
Site 13
Site 14
Site 15
0.67
Site 16
0.66
Site 4 * Flux
Site 5 * Flux
Site 7 * Flux
0.47
Site 11 * Flux
1.61
Site 13 * Flux
Site 16 * Flux
Model R2
55.4%
3.3%
2.8%
1.7%
Standard Deviation
0.54
1.1
1.10
1.06
GLM from Eq
. F.2: Surface Finishes and Flux
Experimental Factor
Pre-Test
85/85
Thermal Shock
Mech Shock
Constant
11.55
12.62
13.76
13.22
OSP
0.30
Immersion Sn
0.27
Immersion Ag
Ni/Au
0.46
Ni/Pd/Au
0.63
Flux
1.09
-0.37
Model R2
48.2%
1.9%
2.8%
2.6%
Standard Deviation
0.50
1.00
1.10
1.0
F-38
-------
APPENDIX F
Table F.27 Predicted Changes from the Base Case at Pre-test for the Leakage Measurements for the GLM in
Equation F.l
10-Mil Pads PGA-A PGA-B Gull Wing
LR Flux WS Flux LRFlux WS Flux LRFlux WS Flux LRFlux WS Flux
Site 2
-0.97
-0.23
-1.19
0.39
2.77
0.81
Site 3
1.02
1.76
1.58
2.77
0.81
Site 4
0.93
1.67
1.58
2.77
0.81
Site 5
0.85
1.59
1.58
2.77
0.37
1.18
Site 6
0.74
1.58
2.77
0.81
Site 7
1.59
1.58
2.77
1.28
Site 8
0.74
1.58
0.57
3.34
0.81
Site 9
0.74
-0.81
0.77
2.77
0.81
Site 10
1.74
1.58
2.77
0.47
1.28
Site 11
1.80
-0.34
1.24
2.77
-0.65
1.77
Site 12
0.91
1.65
1.58
2.77
0.54
1.35
Site 13
-0.89
1.80
-0.64
1.85
2.77
0.81
Site 14
-0.75
-0.01
-0.94
0.64
2.77
0.81
Site 15
0.98
1.72
1.58
2.77
0.81
Site 16
-0.76
1.72
-1.14
1.78
-0.34
2.43
0.81
Table F.28 Predicted Changes from the Base Case at Pre-test for the Leakage Measurements for the
GLM in Equation F.2
10-Mil Pads
PGA-A
PGA-B
Gull Wing
LR Flux
WS Flux
LR Flux
WS Flux
LR Flux
WS Flux
LR Flux
WS Flux
OSP
0.73
2.50
0.35
2.40
2.71
0.30
1.39
Imm Sn
0.33
2.10
2.05
2.71
0.27
1.36
Imm Ag
0.48
2.25
2.05
2.71
1.09
Ni/Au
1.77
2.05
2.71
1.09
Ni/Pd/Au
1.77
-0.35
1.70
-0.38
2.33
1.09
10-Mil Pads
Examination of the GLM results in Table F.27 for 10-mil pads shows an effect due to flux of
approximately 0.74 orders of magnitude (see column 1 in uppermost portion of Table F.23). There is
also evidence of site-to-site variation and some interaction between site and flux that affects resistance
either positively or negatively by up to an order of magnitude. Sites applying the OSP surface finish
(Sites 6, 7, 8, and 9) as will as Sites 10 and 11 with immersion Sn do not differ from the base case
when LR flux is used.
Table F.28 shows a flux effect of approximately 1.77 orders of magnitude when sites are dropped
from the GLM and replaced by surface finishes. These results show slight increases in resistance over
the base case for OSP, immersion Sn, and immersion Ag.
The differences in the model R s for both GLMS essentially disappear after exposure to the 85/85
test environment. This result is not unusual and may be due to a cleansing effect from the 85/85 test
environment that removes residues resulting from board fabrication, assembly, and handling. This
same phenomenon was observed for the other three leakage circuits.
Boxplot Displays of Multiple Comparison Results. Boxplot displays of the Pre-test and Post
85/85 test results are given in Figure 4.19 and 4.20. Boxplots for the other test times are displayed in
Figures F.37 and F.38. There are not great changes in the leakage measurements at Post TS and Post
MS as shown in the boxplots.
F-39
-------
APPENDIX F
PGA-A
Examination of the GLM results in Table F.27 for PGA-A shows an effect due to flux of
approximately 1.58 orders of magnitude. There is also evidence of site-to-site variation and some
interaction between site and flux that affects resistance either positively on negatively by up to an order
of magnitude. Nine of the sites do not differ from the base case when LR flux is used.
Table F.28 shows a flux effect of approximately 2.05 orders of magnitude when sites are dropped
from the GLM and replaced by surface finishes, but no meaningful differences due to surface finishes.
As was the case with the 10-mil pads, the differences in the model R2s for both GLMS essentially
disappear after exposure to the 85/85 test environment.
Boxplot Displays of Multiple Comparison Results. A boxplot display of the Pre-test results is
given in Figure 4.21. Boxplots for the other three test times are displayed in Figures F.39 to F.41.
PGA-B
Examination of the GLM results in Table F.27 for PGA-B shows a strong effect due to flux of
approximately 2.77 orders of magnitude. Thirteen of the sites do not differ from the base case when
LR flux is used and the other two only differ slightly. Table F.28 also shows a strong flux effect of
approximately 2.71 orders of magnitude when sites are dropped from the GLM and replaced by
surface finishes, but no meaningful differences due to surface finishes.
As was the case with the 10-mil pads and PGA-A, the differences in the model R s for both
GLMS essentially disappear after exposure to the 85/85 test environment.
Boxplot Displays of Multiple Comparison Results. A boxplot display of the Pre-test results is
given in Figure 4.22. Boxplots for the other three test times are displayed in Figures F.42 to F.44.
Gull Wing
Examination of the GLM results in Table F.27 for the Gull Wing shows a moderate effect due to
flux of approximately 0.81 orders of magnitude. There is evidence of modest site-to-site variation and
some interaction between site and flux. Eleven of the sites do not differ from the base case when LR
flux is used and the other two only differ slightly. Table F.28 shows a flux effect of approximately
1.09 orders of magnitude when sites are dropped from the GLM and replaced by surface finishes, but
no meaningful differences due to surface finishes.
As was the case with the 10-mil pads, PGA-A, and PGA-B the differences in the model R2s for
both GLMS essentially disappear after exposure to the 85/85 test environment.
Boxplot Displays of Multiple Comparison Results. A boxplot display of the Pre-test results is
given in Figure 4.23. Boxplots for the other three test times are displayed in Figures F.45 to F.47.
F-40
-------
APPENDIX F
F.9 Stranded Wires
Pre-test measurements for the stranded wire circuits were subjected to GLM analyses, as were the
deltas after 85/85, thermal shock, and mechanical shock. The results of the GLM analyses are given in
Tables F.29 and F.30. Columns 3 to 5 in these tables give the results for 85/85, TS, and MS,
respectively. Note that these latter three analyses are based on changes from Protest measurements.
The model R2s for Equations F. 1 and F.2 for the stranded wire circuitry are summarized as follows for
each test time.
GLM
Circuit
Pre-test
85/85
TS
MS
Site and Flux
St. Wire 1
3.6%
6.5%
12.5%
11.7%
St. Wire 2
8.6%
8.2%
8.2%
4.1%
Surface Finish and Flux
St. Wire 1
1.8%
1.6%
4.5%
2.1%
St. Wire 2
0.8%
0.9%
7.4%
2.2%
The model R2 values are all near zero at each test time, which indicates that the experimental
parameters do not influence the stranded wire voltage measurements.
Boxplot Displays of Multiple Comparison Results. Boxplots displays of the Pre-test voltage
measurements (mV) for both stranded wires are displayed in Figures F.48 and F.49.
F-41
-------
APPENDIX F
Table F.29 Significant Coefficients for the Two GLM Analyses by Test Time for Stranded Wire
GLM from Eq.
F.l: Sites and Interactions with
Flux
Experimental Factor
Pre-Test
85/85
(Delta 1)
Thermal Shock
(Delta 2)
Mech Shock
(Delta 3)
Constant
12.90
0.000
0.001
0.005
Flux
0.55
Site 2
Site 3
Site 4
-0.001
Site 5
-0.001
Site 6
Site 7
Site 8
Site 9
Site 10
Site 11
Site 12
0.024
0.042
Site 13
Site 14
Site 15
Site 16
Site 4 * Flux
Site 5 * Flux
0.002
Site 7 * Flux
Site 11 * Flux
Site 13 * Flux
-2.21
Site 16 * Flux
0.079
Model R2
3.6%
6.5%
12.5%
11.7%
Standard Deviation
2.57
0.002
0.014
0.041
GLM from Eq.
F.2: Surface Finishes and Flux
Experimental Factor
Pre-Test
85/85
(Delta 1)
Thermal Shock
(Delta 2)
Mech Shock
(Delta 3)
Constant
12.94
0.000
0.001
0.006
OSP
-0.001
Immersion Sn
Immersion Ag
1.06
0.010
0.019
Ni/Au
Ni/Pd/Au
Flux
Model R2
1.8%
1.6%
4.5%
2.1%
Standard Deviation
2.00
0.001
0.014
0.043
F-42
-------
APPENDIX F
Table F.30 Significant Coefficients for the Two GLM Analyses by Test Time for Stranded Wire 2
GLM from Eq. F.l: Sites and Interactions with Flux
Experimental Factor
Pre-Test
85/85
(Delta 1)
Thermal Shock
(Delta 2)
Mech Shock
(Delta 3)
Constant
23.44
-.000
0.011
0.033
Flux
Site 2
Site 3
0.003
Site 4
Site 5
Site 6
Site 7
Site 8
Site 9
Site 10
-1.56
Site 11
Site 12
0.077
Site 13
Site 14
Site 15
Site 16
Site 4 * Flux
Site 5 * Flux
-2.31
Site 7 * Flux
Site 11 * Flux
-0.002
0.074
Site 13 * Flux
Site 16 * Flux
0.130
Model R2
8.6%
8.2%
8.2%
4.1%
Standard Deviation
1.90
0.003
0.067
0.098
GLM from Eq. F.2: Surface Finishes and Flux
Experimental Factor
Pre-Test
85/85
(Delta 1)
Thermal Shock
(Delta 2)
Mech Shock
(Delta 3)
Constant
23.34
0.000
-0.001
0.021
OSP
-0.43
Immersion Sn
Immersion Ag
-0.001
0.038
Ni/Au
Ni/Pd/Au
Flux
0.026
0.029
Model R2
0.8%
0.9%
7.4%
2.2%
Standard Deviation
2.00
0.002
0.067
0.099
F-43
-------
APPENDIX F
Boxplots of HVLC PTH by SiteFlux
(means are indicated bysolid circles)
OSP ImmSn ImmAg Ni/Au Ni/Au/Pd
5.03 —
f 5.02 —
CL
O
_l
>
X
5.01 —
5.00 —
SiteFlux
WS WS WS WS WS WS WS WS WS WS WS
P re-Test
HVLC PTH
HASL
0
7 T
n
"i i i rn i i i pi i i i n i m i i n r
Figure F.l Boxplot Displays for HVLC PTH Measurements (|JA) at Pre-test by Surface Finish
(Acceptance Criterion = 4|jA< X <6|jA)
Post 85/85
HVLC PTH
X
H
CL
O
_l
>
X
CL
Q
5.03 —
5.02 ¦
5.01 —
5.00 ¦
4.99 ¦
SiteFlux
HASL
Boxplots of DPHVLC P by SiteFlux
(means are indicated bysolid circles)
OSP ImmSn ImmAg
Ni/Au Ni/Au/Pd
r
p r
(N CO
WS
\
r
WS
1 I
m to
WS
i r
CO O)
WS
o
\ r
CN CO
T x
WS
WS
n r
in co
WSWS
n p
CO O)
WS
i i i r
ws
WS
Figure F.2 Boxplot Displays for HVLC PTH Post 85/85 - Pre-test Measurements (|LLA) by Surface Finish
(Acceptance Criterion = 4|jA< X <6|jA)
F-44
-------
APPENDIX F
Post Thermal Shock
HVLC PTH
HASL
Boxplots of DTHVLC P by SiteFlux
(means are indicated bysolid circles)
OSP ImmSn ImmAg
Ni/Au Ni/Au/Pd
x
H
CL
O
_l
>
X
5.01 —
5.00 —
4.99 ¦
4.98 ¦
SiteFlux
T T T
n r
"i r
"i i i r
"i r
"i i i r
ws ws ws ws
ws
ws
wsws
i i ii r~
G) O ¦<- (N CO
¦<- (N (N (N (N
WS ws ws
Figure F.3 Boxplot Displays for HVLC PTH Post TS - Pre-test Measurements (|LLA) by Surface Finish
(Acceptance Criterion = 4|jA< X <6|jA)
Post Mechanical Shock
HVLC PTH
X
H
CL
O
_l
>
X
5.01 —
5.00 —
4.99 ¦
4.98 ¦
SiteFlux
HASL
Boxplots of DMHVLC P by SiteFlux
(means are indicated bysolid circles)
OSP ImmSn ImmAg
Ni/Au Ni/Au/Pd
i r
\ r
n r
ws ws ws ws
i r
ws
\ r
i r
i r
n r
ws
wsws
¦<- (N (N (N (N
WS ws ws
Figure F.4 Boxplot Displays for HVLC PTH Post MS - Pre-test Measurements (|LLA) by Surface Finish
(Acceptance Criterion = 4|jA< X <6|jA)
F-45
-------
APPENDIX F
P re-Test
HVLC SMT
5.4 ¦
5.3 —
5.2 —
H
2
51 -
O 3-' ^
_i
>
X
5.0 ¦
4.9 ¦
4.8 —
Site Flux
HASL
Boxplots of HVLC SMT by SiteFlux
(means are indicated bysolid circles)
OSP ImmSn ImmAg
Ni/Au Ni/Au/Pd
T v
D
i
$
"i i i i i i i i i i i i i i i i i i i i i i r~
¦<-(NCO'^-LOCDr~COG>0-<-(NCO'^-LOCDr~COG>0-<-(NCO
ws ws ws ws ws ws ws ws ws ws ws
Figure F.5 Boxplot Displays for HVLC SMT Measurements (|_lA) at Pre-test by Surface Finish
(Acceptance Criterion = 4|jA< X <6|jA)
Post 85/85
HVLC SMT
5.4 ¦
5.3 —
5.2 —
O 5.1
5.0 —
4.9 —
4.8 —
SiteFlux
HASL
Boxplots of DPHVLC S by SiteFlux
(means are indicated bysolid circles)
OSP ImmSn ImmAg
Ni/Au Ni/Au/Pd
D
d
i i i i i i i i i i i i i i i i i i i i i i n
¦<-(NCO'^-LOCDr~COG>0-<-(NCO'^-LOCDr~COG>0-<-(NCO
WS ws ws ws ws ws ws
ws ws ws ws
Figure F.6 Boxplot Displays for HVLC PTH Post 85/85 - Pre-test Measurements (|LLA) by Surface Finish
(Acceptance Criterion = 4|jA< X <6|jA)
F-46
-------
APPENDIX F
Post Thermal Shock
HVLC SMT
HASL
5.5 —
5.4 —
5.3 —
H
2
W 5.2 —
O
X 5.1 -
H
Q
5.0 —
4.9 —
4.8 —
Site Flux
Boxplots of DTHVLC S by SiteFlux
(means are indicated bysolid circles)
OSP ImmSn ImmAg
Ni/Au Ni/Au/Pd
D
¥
a
"i i i i i i i i i i i i i i i i i i i i i i r~
¦<-CNCO'^-LOCDr~COG)0-<-CNCO'^-LOCDr~COG)0-<-CNCO
ws ws ws ws ws ws ws
ws ws ws ws
Figure F.7 Boxplot Displays for HVLC PTH Post TS - Pre-test Measurements (|LLA) by Surface Finish
(Acceptance Criterion = 4|jA< X <6|jA)
Post Mechanical Shock
HVLC SMT
0.05 —
0.04 —
0.03 ¦
0.02 ¦
0.01
0.00 —
SiteFlux
HASL
Boxplots of DMHVLC S by SiteFlux
(means are indicated bysolid circles)
OSP ImmSn ImmAg
Ni/Au Ni/Au/Pd
CO
WS
ws
I
I
CD
WS
r
CO
WS
O)
o
I
CO
WS
\
r
WS
in
CD
wsws
I
CO
O)
WS
o
n
t- W CO
CN CN CN
WS ws
Figure F.8 Boxplot Displays for HVLC PTH Post MS - Pre-test Measurements by Surface Finish
(Acceptance Criterion = 4|jA< X <6|jA)
F-47
-------
APPENDIX F
P re-Test
HSD PTH
Q
(1.1
X
18.0 ¦
17.5 ¦
17.0 —
HASL
Boxplots of HSD PTH by SiteFlux
(means are indicated bysolid circles)
OSP ImmSn ImmAg
Ni/Au Ni/Au/Pd
SiteFlux
"I I I I I I I I I I I I I I I I I I I I I I T~
¦<-(NCO'^-LOCDr~COG>0-<-(NCO'^-LOCDr~COG>0-<-(NCO
ws ws ws ws ws ws ws
ws ws ws ws
Figure F.9 Boxplot Displays for HSD PTH Measurements (nsec) at Pre-test by Surface Finish
P re-Test
HSD SMT
iD
Q
(1.1
X
9.5 —
9.4 ¦
9.3 ¦
9.2 —
9.1
9.0 —
8.9
SiteFlux
HASL
Boxplots of HSD SMT by SiteFlux
(means are indicated bysolid circles)
OSP ImmSn ImmAg
Ni/Au Ni/Au/Pd
0
i
i i i i i i i i i i i i i i i i i i i i i i n
¦<-(NCO'^-LOCDr~COG>0-<-(NCO'^-LOCDr~COG>0-<-(NCO
WS ws ws ws ws ws ws
ws ws ws ws
Figure F.10 Boxplot Displays for HSD SMT Measurements (nsec) at Pre-test by Surface Finish
F-48
-------
APPENDIX F
Post 85/85
HF PTH 50MHz
0.5 —I
0.4
0.3 —
o no
LO U'^
X
H
CL 0.1
LL
X
CL 0.0
Q
-0.1 —
-0.2 ¦
-0.3 ¦
Site Flux
HASL
Boxplots of DPHF PTH by SiteFlux
(means are indicated bysolid circles)
OSP ImmSn ImmAg
Ni/Au Ni/Au/Pd
9 9 Q 5
I
* „
9 t 8
* s
J 0
"i i i i i i i i i i i i i i i i i i i i i i r~
¦<-CNCO'^-LOCDr~COG)0-<-CNCO'^-LOCDr~COG)0-<-CNCO
t-t-t-t-t-t-t-t-t-t-CNCNCNCN
ws ws ws ws ws ws ws
ws ws ws ws
Figure F.ll Boxplot Displays for HF PTH 50MHz Post 85/85 - Pre-test Measurements (dB) by Surf. Finish
(Acceptance Criterion = +5dB of Pre-test)
Post Thermal Shock
HF PTH 50MHz
0.5 —
o
LO
X
H
CL
LL
X
H
Q
0.0 ¦
-0.5 ¦
SiteFlux
HASL
Boxplots of DTHF PTH by SiteFlux
(means are indicated bysolid circles)
OSP ImmSn ImmAg
Ni/Au Ni/Au/Pd
A 0 4> *
~ r
CN CO
WS
0 ?
\ I r
^ LO CO
? s ^ Ij!
ws
ws
i i r
CO O) o
WS
h r
CN CO
n i r
in co
U A 0 t
i i i r
0 a
ws
ws
wsws
ws
ws
n r
ws
Figure F.12 Boxplot Displays for HF PTH 50MHz Post TS - Pre-test Measurements (dB) by Surface Finish
(Acceptance Criterion = +5dB of Pre-test)
F-49
-------
APPENDIX F
P re-Test
HF PTH f(-3dB)
HASL
Boxplots of HF PTH-3 by SiteFlux
(means are indicated bysolid circles)
OSP ImmSn ImmAg Ni/Au Ni/Au/Pd
285 —
CO
X
H
CL
LL 280 —
X
275 ¦
SiteFlux
"I I I I I I I I I I I I I I I I I I I I I I T~
¦<-CNCO'^-LOCDr~COG)0-<-CNCO'^-LOCDr~COG)0-<-CNCO
ws ws ws ws ws ws ws ws
ws ws ws
Figure F.13 Boxplot Displays for HF PTH f(-3dB) Measurements (MHz) at Pre-test by Surface Finish
(Acceptance Criterion = +50Mhz of Pre-test)
Post 85/85
HF PTH f(-3dB)
HASL
Boxplots of DPHF PTH by SiteFlux
(means are indicated bysolid circles)
OSP ImmSn ImmAg
Ni/Au Ni/Au/Pd
o —
CO
X
X
CL
Q
-5 —
-10 —I
SiteFlux
f 1 I |
I
CO
0 * 0
ws
r
ws
I
CD
ws
r
CO
WS
O)
o
I
CO
aa t
ws
ws
f
i i
n
CD
wsws
I
CO
O)
WS
o
f 8
WS
CO
CN
WS
Figure F.14 Boxplot Displays for HF PTH f(-3dB) Post 85/85 - Pre-test Measurements (MHz) by Surf. Finish
(Acceptance Criterion = +50Mhz of Pre-test)
F-50
-------
APPENDIX F
Post Thermal Shock
HF PTH f(-3dB)
HASL
Boxplots of DTHF PTH by SiteFlux
(means are indicated bysolid circles)
OSP ImmSn ImmAg
Ni/Au Ni/Au/Pd
5 —
*
1
1
1
CO
X °-
H
CL
LL
X
H
° -5-
^ B 4" i
8 * * J J
* 1
¦
i
i* fl £i ? t
i t
*
'9*
§ s ? ?
*
5 8
-10 —
i
i
i
i
i
i i i rn i i i pi i i i n i rn i i n r
SitpFluy T-cNco-^-Lncor~coG)0-<-cNco'^-LncDr~coG)0-<-cNco
ws ws ws ws ws ws ws ws ws ws ws
Figure F.15 Boxplot Displays for HF PTH f(-3dB) Post TS - Pre-test Measurements (Mhz) by Surface Finish
(Acceptance Criterion = +50Mhz of Pre-test)
P re-Test
HF PTH f(
485 —
475 —
o
X
H
CL
LL
X
465 —
455 —
SiteFlux
Figure F.16 Boxplot Displays for HF PTH f(-40dB) Measurements (MHz) at Pre-test by Surface Finish
(Acceptance Criterion = +50Mhz of Pre-test)
-40dB)
HASL
Boxplots of HFPTH-40 by SiteFlux
(means are indicated bysolid circles)
OSP ImmSn ImmAg
Ni/Au Ni/Au/Pd
0
T v *
~r
(N CO
n i r
i in
-------
APPENDIX F
Post 85/85
HF PTH f(-40dB)
HASL
Boxplots of DPHFPTH- by SiteFlux
(means are indicated bysolid circles)
OSP ImmSn ImmAg
Ni/Au Ni/Au/Pd
5 —
o
X
H
CL
LL
X
CL
Q
-5 —
-10 ¦
*
m a p h
• B 0 0
• T
*
!B 8 0 » ¥
¦
! 8 H
*
0 w f *
*
*
? i
*
SiteFlux
"I T
"i r
"i i i r
"i r
"i i i r
ws ws ws ws
ws
ws
wsws
"i i i r
G) O ¦<- (N CO
¦<- CN CN CN CN
WS ws ws
Figure F.17 Boxplot Displays for HF PTH f(-40dB) Post 85/85 - Pre-test Measurements (MHz) by Surf. Fin.
(Acceptance Criterion = +50Mhz of Pre-test)
Post Thermal Shock
HF PTH f(-40dB)
HASL
o
x
H
CL
LL
X
H
Q
0 —
-5 '
-10 —
tA'i
-15 —I
SiteFlux
Boxplots of DTHFPTH- by SiteFlux
(means are indicated bysolid circles)
OSP ImmSn ImmAg
Ni/Au Ni/Au/Pd
i r
CO
* *
S 6 ?
ws
ws
I
CD
ws
r
CO
WS
O)
t e 0
o
i r
i
CO
¦
0
WS
WS
• k
\
CD h-
WSWS
I
CO
O)
WS
o
$
8
WS
n r
ws
Figure F.18 Boxplot Displays for HF PTH f(-40dB) Post TS - Pre-test Measurements (MHz) by Surf. Finish
(Acceptance Criterion = +50Mhz of Pre-test)
F-52
-------
APPENDIX F
P re-Test
HF SMT 50MHz
-0.6 —I
-0.7 ¦
o
LO
LL
X
-0.9 ¦
Site Flux
HASL
Boxplots of HF SMT50 by SiteFlux
(means are indicated bysolid circles)
OSP ImmSn ImmAg Ni/Au Ni/Au/Pd
"i r
"i r
"i i i r
"i r
"i i i r
ws ws ws ws
ws
ws
wsws
i i ii r~
G) O ¦*— (N CO
¦*- CN
-------
APPENDIX F
Post Thermal Shock
HF SMT 50MHz
o
LO
iD
LL
X
H
Q
0.1
0.0 —
-0.1
-0.2 —
-0.3 —
-0.4 —
-0.5 —
-0.6 ¦
Site Flux
HASL
Boxplots of DTHF SMT by SiteFlux
(means are indicated bysolid circles)
OSP ImmSn ImmAg Ni/Au Ni/Au/Pd
0 ^
0 A 6
»y |
0 a 6
*
^ ? i
"i i i i i i i i i i i i i i i i i i i i i i r~
¦<-CNCO'^-LnCDr~COG)0-<-CNCO'^-LnCDr~COG)0-<-CNCO
t-t-t-t-t-t-t-t-t-t-CNCNCNCN
ws ws ws ws ws ws ws
ws ws ws ws
Figure F.21 Boxplot Displays for HF SMT 50MHz Post TS - Pre-test Measurements (dB) by Surface Finish
(Acceptance Criterion = +5 dB of Pre-test)
P re-Test
HF SMT f(-3dB)
HASL
Boxplots of HF SMT-3 by SiteFlux
(means are indicated bysolid circles)
OSP ImmSn ImmAg
Ni/Au Ni/Au/Pd
LL
X
340 —
330 —
320 ¦
310 ¦
SiteFlux
1
1
1
1
1
1
1
1
1
I
I
I
I
I
I
I
I
1
¦
M B ?!fi * f " ?
!b fl + M
- A i +
h a
*
I T
* '
1
*
1
"
*
1
1
i r
CN CO
ws
i i r
i in
-------
APPENDIX F
Post 85/85
HF SMT f(-3dB)
HASL
10 —I
5 —
0 —
-5 •
Site Flux
if 0 ?
Boxplots of DPHF SMT by SiteFlux
(means are indicated bysolid circles)
OSP ImmSn ImmAg
T
f ? $ k
4 ?
0
0
Ni/Au Ni/Au/Pd
1
"I I I I I I I I I I I I I I I I I I I I I I T~
¦<-CNCO'^-LOCDr~COG)0-<-CNCO'^-LOCDr~COG)0-<-CNCO
ws ws ws ws ws ws ws
ws ws ws ws
Figure F.23 Boxplot Displays for HF SMT f(-3dB) Post 85/85 - Pre-test Measurements (MHz) by Surf. Finish
(Acceptance Criterion = +50Mhz of Pre-test)
Post Thermal Shock
HF SMT f(-3dB)
HASL
Boxplots of DTHF SMT by SiteFlux
(means are indicated bysolid circles)
OSP ImmSn ImmAg Ni/Au Ni/Au/Pd
10 —
o —
iD
LL
X
H
Q
-10 ¦
-20 —
-30 ¦
SiteFlux
f S
?
i r
CO
B * - i P
WS
WS
I
CD
ws
r
CO
WS
O)
6 S
* ¦
o
i r
i
CO
WS
WS
i S *
n
co
wsws
I
CO
O)
WS
o
i
WS
n r
ws
Figure F.24 Boxplot Displays for HF SMT f(-3dB) Post TS - Pre-test Measurements (MHz) by Surface Finish
(Acceptance Criterion = +50Mhz of Pre-test)
F-55
-------
APPENDIX F
P re-Test
HF SMT f(-40dB)
HASL
o
iD
LL
x
950 ¦
900 ¦
850 —
800 ¦
Site Flux
Boxplots of HFSMT-40 by SiteFlux
(means are indicated bysolid circles)
OSP ImmSn ImmAg
Ni/Au Ni/Au/Pd
"i i i i i i i i i i i i i i i i i i i i i i r~
¦<-(NCO'^-mCDr~COG)0-<-(NCO'^-mCDr~COG)0-<-(NCO
ws ws ws ws ws ws ws
ws ws ws ws
Figure F.25 Boxplot Displays for HF SMT f(-40dB) Measurements (MHz) at Pre-test by Surface Finish
(Acceptance Criterion = +50Mhz of Pre-test)
Post 85/85
HF SMT f(-40dB)
HASL
50 —
40 —
30 —
20 —
10 ¦
0 —
-10 •
SiteFlux
Boxplots of DPHFSMT- by SiteFlux
(means are indicated bysolid circles)
OSP ImmSn ImmAg
~ r
-------
APPENDIX F
Post Thermal Shock
HF SMT f(-40dB)
HASL
40 —
30 —
20 ¦
10 ¦
D
T o-
» -10-
E -20 ¦
21
-30 ¦
-40 ¦
-50 ¦
-60 ¦
Site Flux
Boxplots of DTHFSMT- by SiteFlux
(means are indicated bysolid circles)
OSP ImmSn ImmAg
Ni/Au Ni/Au/Pd
9
~
0
n 8 £
B
"I I I I I I I I I I I I I I I I I I I I I I T~
¦<-(NCO'^-LOCDr~COG>0-<-(NCO'^-LOCDr~COG>0-<-(NCO
t-t-t-t-t-t-t-t-t-t-CNCNCNCN
ws ws ws ws ws ws ws
ws ws ws ws
Figure F.27 Boxplot Displays for HF SMT f(-40dB) Post TS - Pre-test Measurements (MHz) by Surf. Finish
(Acceptance Criterion = +50Mhz of Pre-test)
P re-Test
HF TLC 50MHz
-42 —
-43 —
-44
-45 —
0 -46 —
_l
1 "47
r
-48 —
-49
-50 —
-51 —
SiteFlux
HASL
Boxplots of HF TL 50 by SiteFlux
(means are indicated bysolid circles)
OSP ImmSn ImmAg
Ni/Au Ni/Au/Pd
~ r
(N CO
WS
n I r
i in
-------
APPENDIX F
Post 85/85
HF TLC 50MHz
5 —
4 —
3 —
2
0
LO
i 1 -H
H
1 0-
CL
~ -1
-2 —
-3
-4 —
Site Flux
HASL
Boxplots of DPHF TL by SiteFlux
(means are indicated bysolid circles)
OSP ImmSn ImmAg
Ni/Au Ni/Au/Pd
n r
s 5 „$ £
"i r
~
£ a & 0
"i i i r
"i r
"i i i r
T * 0
6
ws ws ws ws
ws
ws
wsws
i i ii r~
G) O ¦<- CN CO
¦<- CN CN CN CN
WS ws ws
Figure F.29 Boxplot Displays for HF TLC 50MHz Post 85/85 - Pre-test Measurements (dB) by Surf. Finish
(Acceptance Criterion = +5 dB of Pre-test)
Post Thermal Shock
HF TLC 50MHz
5 —
4 —
3 —
2 —
5 1 —
t «"
X
H -1 —
Q
-2 —
-3 —
-4 —
-5 —
SiteFlux
HASL
Boxplots of DTHF TL by SiteFlux
(means are indicated bysolid circles)
OSP ImmSn ImmAg
Ni/Au Ni/Au/Pd
? ¥ ?
8
~ r
CN CO
WS
£ 5 £
n i r
in co
WS
WS
l r
CO O)
ws
9 i
I
o
i r
CN CO
ni r
lo cd
o 4 a
i r
ws
ws
wsws
ws
ws
ir
ws
Figure F.30 Boxplot Displays for HF TLC 50MHz Post TS - Pre-test Measurements (dB) by Surface Finish
(Acceptance Criterion = +5 dB of Pre-test)
F-58
-------
APPENDIX F
Boxplots of HF TL500 by SiteFlux
(means are indicated bysolid circles)
OSP ImmSn ImmAg Ni/Au Ni/Au/Pd
-15 —
-16 —
o -17 —
o
LO
I
H
-19 —
-20 —
SiteFlux
Figure F.31 Boxplot Displays for HF TLC 500MHz Measurements (dB) at Pre-test by Surface Finish
P re-Test
HF TLC 500MHz
HASL
"I I I I I I I I I I I I I I I I I I I I I I T~
¦<-(NCO'^-LOCDr~COG>0-<-(NCO'^-LOCDr~COG>0-<-(NCO
t-t-t-t-t-t-t-t-t-t-CNCNCNCN
ws ws ws ws ws ws ws
ws ws ws ws
Boxplots of DPHF TL5 by SiteFlux
(means are indicated bysolid circles)
OSP ImmSn ImmAg Ni/Au Ni/Au/Pd
3 —
2 —
1 —
o
o
LO
I
I- 0 —
LL
X
CL
-2 —
-3 —
SiteFlux
WS WS WS WS WS WS WS WS WS WS WS
Post 85/85
HF TLC 500MHz
HASL
&
*
9
4 A Q
I e S
i S w
a a
5 9
i r
i i i r
ci ^ in 0
i i i r
l"~ CO O) o
n r
(N CO
1 I I r
in cd r-~
1 I I T
Figure F.32 Boxplot Displays for HF TLC 500MHz Post 85/85 - Pre-test Measurements (dB) by Surf. Finish
(Acceptance Criterion = +5 dB of Pre-test)
F-59
-------
APPENDIX F
Post Thermal Shock
HF TLC 500MHz
HASL
Boxplots of DTHF TL5 by SiteFlux
(means are indicated bysolid circles)
OSP ImmSn ImmAg
Ni/Au Ni/Au/Pd
2 —
1
1
*
* i
*
1
*
1 —
1
1 1 1
*
*
*
o o-
LO
I
H
£ -1-
H
Q
-2 —
W
1
1
1
1
1
0 9 M
¦
¦
T
^ p
¦
? o
f M
*
T
*
s s
-3 —
1
* 1
1
*
SiteFlux
"I I I II I I I II I I I II I II I I II T
CNCO'^-LOCDr~COG)0-<-CNCO'^-LOCDr~COG)0-<-CNCO
ws ws ws ws ws ws ws
ws ws ws ws
Figure F.33 Boxplot Displays for HF TLC 500MHz Post TS - Pre-test Measurements (dB) by Surface Finish
(Acceptance Criterion = +5 dB of Pre-test)
P re-Test
HF TLC RNR
HASL
-34 —
OH
-39 ¦
-44 —I
SiteFlux
Boxplots of HFTLRNul by SiteFlux
(means are indicated bysolid circles)
OSP ImmSn ImmAg Ni/Au Ni/Au/Pd
0
\ i i i i i r
¦<- (N CO LO CD h-
ws ws ws ws
l l r
CO o> o
i i r
t- W CO
ws
i §
n i r
^ LO CO
D £ (
£
$
1 I I I I I ~
^ CO G) O ¦<- CN CO
CN CN CN CN
WS ws ws ws ws ws
Figure F.34 Boxplot Displays for HF TLC RNR Measurements (dB) at Pre-test by Surface Finish
F-60
-------
APPENDIX F
Post 85/85
HF TLC RNR
10 ¦
5 —
0 —
-5 —
Site Flux
HASL
Boxplots of DPHFTLRN by SiteFlux
(means are indicated bysolid circles)
OSP ImmSn ImmAg
Ni/Au Ni/Au/Pd
i . « .
4
A * P
"I I I I I I I I I I I I I I I I I I I I I I T"
¦<-(NCO'^-LOCDr~COG>0-<-(NCO'^-LOCDr~COG>0-<-(NCO
ws ws ws ws ws ws ws
ws ws ws ws
Figure F.35 Boxplot Displays for HF TLC RNR at Post 85/85 - Pre-test Measurements (dB) by Surf. Finish
(Acceptance Criterion = <10 dB increase over Pre-test)
Post Thermal Shock D (nTUrTiDMk o * m
_ omd Boxplots of DTHFTLRN by SiteFlux
Hr I LO KNK
(means are indicated bysolid circles)
HASL OSP I mm Sn ImmAg Ni/Au Ni/Au/Pd
10 —
1
i i
*
1 1 1
i i
i i
1 1 1
1 1 * 1
i i
i * * i
* * 1 * 1 1
' ' rl,
* ' [!] ' ¦ ¦'
1 1 n
0 —
» • * f |H — • a • 1 • * * " — 1 — •
¦ i * * i
* 1 * 1 ¦
|B ' ¦ 'IS H
* * * !
1 1
i i i
r i
i * i i
i i i
i i
l i
10 —
i i i
1 l
i i i x x i i *
i i i i i i i i i i i i i i i i i i i i i i r
SitpFllJY ¦<-(NCO'^-LOCDr~COG>0-<-(NCO'^-LOCDr~COG>0-<-(NCO
oueriux
WS WS WS WS WS WS WS WS WS WS WS
Figure F.36 Boxplot Displays for HF TLC RNR Post TS - Pre-test Measurements (dB) by Surface Finish
(Acceptance Criterion = <10 dB increase over Pre-test)
F-61
-------
APPENDIX F
Post Thermal Shock
10-Mil Pads
T3
CO
CL
15 ¦
14 —
13 ¦
12 —
11
10 ¦
Site Flux
HASL
X 1
Boxplots of DTPads by SiteFlux
(means are indicated bysolid circles)
OSP ImmSn ImmAg
Ni/Au Ni/Au/Pd
"i r
"i r
"i i i r
"i r
T T
"i i i r
ws ws ws ws
ws
ws
wsws
i i ii r~
G) O ¦<- CN CO
¦<- CN CN CN CN
WS ws ws
Figure F.37 Boxplot Displays for 10-Mil Pad Post TS - Pre-test Measurements (logm ohms) by Surf. Finish
(Acceptance Criterion = Resistance > 7.7 logi0 ohms)
Post Mechanical Shock
10-Mil Pads
"O
03
Q_
HASL
Boxplots of DMPads by SiteFlux
(means are indicated bysolid circles)
OSP ImmSn ImmAg
Ni/Au Ni/Au/Pd
15 —
14 ¦
13 —
12 —
SiteFlux
H r
CN CO
i r
LO CD
i i i r
CO CD O
i r
CN CO
i ^ ^ r
^ LO CO h-
* T *
ws ws ws ws
ws
ws
wsws
n i i i i n
CO G> O ¦<- CN CO
¦5- CN CN CN CN
WS ws ws
Figure F.38 Boxplot Displays for 10-Mil Pad Post MS - Pre-test Measurements (logm ohms) by Surf. Finish
(Acceptance Criterion = Resistance > 7.7 logi0 ohms)
F-62
-------
APPENDIX F
Post 85/85
PGA-A
13 ¦
12 —
<
(?5
CL
CL 11
Q
10 —
Site Flux
HASL
Boxplots of DPPGA A by SiteFlux
(means are indicated bysolid circles)
OSP ImmSn ImmAg Ni/Au Ni/Au/Pd
n r
"i r
0' a
"i i i r
"i r
a A
n i i r
0 0
ws ws ws ws
ws
ws
wsws
i i ii r~
G) O ¦<- CN CO
¦<- CN CN CN CN
WS ws ws
Figure F.39 Boxplot Displays for PGA-A Post 85/85 - Pre-test Measurements (logio ohms) by Surface Finish
(Acceptance Criterion = Resistance > 7.7 logio ohms)
Post Thermal Shock
PGA-A
15 —
14 —
< 13 —
(?5
CL
I—
Q 12 ¦
11 —
10 ¦
SiteFlux
HASL
Boxplots of DTPGA A by SiteFlux
(means are indicated bysolid circles)
OSP ImmSn ImmAg
Ni/Au Ni/Au/Pd
0
\ r
(N CO
§ * B
\ r
in to
i i i r
r-~ co o> o
\ r
CN CO
ii i r
in co h-
WS WS WS WS
WS
WS
WSWS
n i i i i n
CO G) O CN CO
CN CN CN CN
WS ws ws
Figure F.40 Boxplot Displays for PGA-A Post TS - Pre-test Measurements (logio ohms) by Surface Finish
(Acceptance Criterion = Resistance > 7.7 logio ohms)
F-63
-------
APPENDIX F
Post Mechanical Shock
PGA-A
<
ei
CL
14 ¦
13 —
12 ¦
11
10 ¦
Site Flux
HASL
Boxplots of DMPGA A by SiteFlux
(means are indicated bysolid circles)
OSP ImmSn ImmAg Ni/Au
Ni/Au/Pd
P
*
"i r
s : b
1 r
~ IJ
"i i i r
"i r
"i i i r
a * ^
ws ws ws ws
ws
ws
wsws
i i ii r~
G) O ¦<- CN CO
¦<- (N (N (N (N
WS ws ws
Figure F.41 Boxplot Displays for PGA-A Post MS - Pre-test Measurements (logm ohms) by Surface Finish
(Acceptance Criterion = Resistance > 7.7 logi0 ohms)
Post 85/85
PGA-B
CO
ei
CL
CL
Q
13 —
12 —
11 —
10 —
SiteFlux
HASL
Boxplots of DPPGA B by SiteFlux
(means are indicated bysolid circles)
OSP ImmSn ImmAg Ni/Au Ni/Au/Pd
6
CO
0
ws
ws
I
CD
ws
r
CO
WS
I
O)
$ a
o
i r
CO
WS
ws
in
0
0
n
co
WSWS
CO
I
O)
WS
WS
ir
ws
Figure F.42 Boxplot Displays for PGA-A Post 85/85 - Pre-test Measurements (logm ohms) by Surface Finish
(Acceptance Criterion = Resistance > 7.7 logi0 ohms)
F-64
-------
APPENDIX F
Post Thermal Shock D . ,
_ Boxplots of DTPGA B by SiteFlux
roA-o
15 —
14 —
CO
<
CD 13-
CL
H
Q
12 —
11 —
SiteFlux
Figure F.43 Boxplot Displays for PGA-A Post TS - Pre-test Measurements (logm ohms) by Surface Finish
(Acceptance Criterion = Resistance > 7.7 logi0 ohms)
HASL
(means are indicated bysolid circles)
OSP ImmSn ImmAg
Ni/Au Ni/Au/Pd
s * b
~
0 b
0
"i i i i i i i i i i i i i i i i i i i i i i r~
¦<-(NCO'^-LOCDr~COG>0-<-(NCO'^-LOCDr~COG>0-<-(NCO
ws ws ws ws ws ws ws
ws ws ws ws
Post Mechanical Shock
PGA-B
15 —
14 —
CO
<
2 13-
12 ¦
11
SiteFlux
HASL
Boxplots of DMPGA B by SiteFlux
(means are indicated bysolid circles)
OSP ImmSn ImmAg
Ni/Au Ni/Au/Pd
0
B
« T
B
9 ¥
8B
0
i i i i i i i i i i i i i i i i i i i i i i n
¦<-(NCO'^-LOCDr~COG>0-<-(NCO'^-LOCDr~COG>0-<-(NCO
WS ws ws ws ws ws ws
ws ws ws ws
Figure F.44 Boxplot Displays for PGA-A Post MS - Pre-test Measurements (logm ohms) by Surface Finish
(Acceptance Criterion = Resistance > 7.7 logio ohms)
F-65
-------
APPENDIX F
Post 85/85
Gull Wing
14 —I
13
12
11
O 10-
CL
9 —
Site Flux
HASL
Boxplots of DPGulIWi by SiteFlux
(means are indicated bysolid circles)
OSP ImmSn ImmAg
Ni/Au Ni/Au/Pd
f
n r
"i r
9
"i i i r
"i r
"i i i r
9 0
ws ws ws ws
ws
ws
wsws
i i ii r~
G) O ¦<- (N CO
¦<- (N (N (N (N
WS ws ws
Figure F.45 Boxplot Displays for the Gull Wing Post 85/85 - Pre-test Measuremts. (logio ohms) by Surf. Fin.
(Acceptance Criterion = Resistance > 7.7 logio ohms)
Post Thermal Shock
Gull Wing
HASL
15—1 *
CD
H
Q
Boxplots of DTGulIWi by SiteFlux
(means are indicated bysolid circles)
OSP ImmSn ImmAg
Ni/Au Ni/Au/Pd
14
13 —
12 —
11
10 —
9 —
?
~ i
¦
*
f * ?
r
SiteFlux
1 I I I I I I I I I I I I I I I I I I I I I n
¦<-(NCO'^-LOCDr~COG>0-<-(NCO'^-LOCDr~COG>0-<-(NCO
WS ws ws ws ws ws ws
ws ws ws ws
Figure F.46 Boxplot Displays for the Gull Wing Post TS - Pre-test Measurements (logm ohms) by Surf. Fin.
(Acceptance Criterion = Resistance > 7.7 logio ohms)
F-66
-------
APPENDIX F
Post Mechanical Shock
Gull Wing
HASL
Boxplots of DMGulIWi by SiteFlux
(means are indicated bysolid circles)
OSP ImmSn ImmAg
Ni/Au Ni/Au/Pd
14 ¦
13 —
12 —
3 11 '
CD
2
Q 10 ¦
9 —
SiteFlux
"I T
0 |
~
"i r
"i i i r
"i r
"i i i r
ws ws ws ws
ws
ws
wsws
i i ii r~
G) O ¦<- (N CO
¦<- (N (N (N (N
WS ws ws
Figure F.47 Boxplot Displays for the Gull Wing Post MS - Pre-test Measurements (logm ohms) by Surf. Fin.
(Acceptance Criterion = Resistance > 7.7 logi0 ohms)
P re-Test
Stranded Wire 1
HASL
20 —I
15 —
iD
10 —
SiteFlux
1 T
Boxplots of StWire 1 by SiteFlux
(means are indicated bysolid circles)
OSP ImmSn ImmAg
Ni/Au Ni/Au/Pd
\ r
i r
1 1
ws ws ws ws
i r
ws
\ r
i r
i r
i r
ws
wsws
¦<- (N (N (N (N
WS ws ws
Figure F.48 Boxplot Displays for the Stranded Wire 1 Measurements (volts) at Pre-test by Surface Finish
F-67
-------
APPENDIX F
P re-Test
Stranded Wire 2
28
27 —
26 —
25 —
$ 24-
§ 23 —
22
21 —
20 —
19
Site Flux
HASL
Boxplots of StWire2 by SiteFlux
(means are indicated bysolid circles)
OSP ImmSn ImmAg
Ni/Au Ni/Au/Pd
T T
"i i i i i i i i i i i i i i i i i i i i i i r~
¦<-(NCO'^-LOCDr~COG>0-<-(NCO'^-LOCDr~COG>0-<-(NCO
ws ws ws ws ws ws ws
ws ws ws ws
Figure F.49 Boxplot Displays for the Stranded Wire 2 Measurements (volts) at Pre-test by Surface Finish
F-68
-------
APPENDIX F
F.10 Design and CCAMTF Baseline Testing of the Test PWA
F.10.1 Test PWA
As mentioned in Chapter 4, the primary test vehicle used in both the DfE project and in the
CCAMTF evaluation of low-residue technology was an electrically functional PWA. This assembly
was designed at Sandia National Laboratories in Albuquerque based on input from LRSTF members
and from military and industry participants during open review meetings held by the task force. The
PWA measures 6.05" x 5.8" x 0.062" and is divided into six sections, each containing one of the
following types of electronic circuits:
• High current low voltage (HCLV) • High frequency (HF)
• High voltage low current (HVLC) • Other networks (ON)
• High speed digital (HSD) • Stranded wire (SW)
The layout of the functional assembly is shown in Figure F.50. The components in the HCLV,
HVLC, HSD, and HF circuits represent two principal types of soldering technology:
• Plated through hole (PTH)—leaded components are soldered through vias in the circuit board
by means of a wave soldering operation
• Surface mount technology (SMT)—leadless components are soldered to pads on the circuit
board by passing the circuit board through a reflow oven.
The other networks (ON) are used for current leakage measurements: 10-mil pads, a socket for a
PGA, and a gull wing. The two stranded wires (SW) are hand soldered.
The subsections for PTH and SMT components form separate electrical circuits. The PWA
includes a large common ground plane, components with heat sinks, and mounted hardware.
Each subsection shown in Figure F.50 contains both functional and nonfunctional components
(added to increase component density). A 29-pin PTH edge connector is used for circuit testing. High
frequency connectors are used to ensure proper impedance matching and test signal fidelity as
required. Board fabrication drawings, schematics, and a complete listing of all components are
available by contacting the authors of this report. A discussion of each of the sections of the test PWA
is now given. This discussion is supplemented with baseline test results for each of the 23 electrical
responses listed in Table 4.1.
F.10.2 High Current Low Voltage
The HCLV section of the board is in the upper left-hand corner of PWA (see Figure F.50). The
upper left-hand portion of this quadrant contains PTH components with SMT components immediately
beneath.
Purpose of the HCLV Experiment
Performance of high-current circuits is affected by series resistance. Resistance of a conductor
(including solder joints) is determined by the following equation:
F-69
-------
APPENDIX F
pL
R = -^~ohms( Q)
(F.7)
where p = resistivity, the proportionality constant
L = length of the conductor
Ac = cross-sectional area of the conductor (solder joints)
Resistance is most likely to change due to cracking or corrosion of the solder joint that may be
related to the soldering process. These conditions decrease the cross-sectional area of the solder joints,
thus increasing resistance as shown in Equation F.7. Use of high current to test solder joint resistance
makes detection of a change in resistance easier. A 5 Amperes (A) current was selected as a value that
would cover most military applications. A change of resistance is most conveniently determined by
measuring the steady state performance of the circuit, which will now be discussed.
6.05"
Figure F.50 Layout of the PWA Illustrating the Four Major Sections and Subsections
F-70
-------
APPENDIX F
Steady State Circuit Performance
Overall circuit resistance, Rtotai, is the parallel combination of the seven resistors, Ri, R2,..., R7,
(all resistors = 10Q) used in the HCLV circuit:
_1 1_ J_ J_ J 7_
R^~R'1 + R^+R^ + "'+R^~~ioci
-------
APPENDIX F
immersion Ag, immersion Au/Pd and HASL with solder mask. Half the PWAs in each surface finish
group were processed with low-residue (LR) flux and the other half with water soluble (WS) flux.
Data modeling showed that surface finish and flux type did not significantly affect the voltage
measurements for HCLV PTH and HCLV SMT. Figures F.51 and F.52 provide dotplot displays of 4
x 120 = 480 voltage measurements for HCLV PTH and 480 voltage measurements for HCLV SMT,
respectively. The summary statistics HCLV PTH and HCLV SMT voltages are given in Table F.31.
— + + + + + + Volts
6.60 6.72 6.84 6.96 7.08 7.20
Figure F.51. Dotplot for 480 HCLV PTH Voltage Measurements
(each dot represents up to 10 points)
_ + + + + + + Volts
6.90 7.00 7.10 7.20 7.30 7.40
Figure F.52. Dotplot for 480 HCLV SMT Voltage Measurements
(each dot represents up to 16 points)
Table F.31. Summary Statistics for HCLV Circuitry Test Measurements
Circuitry Mean Median St. Dev. Min Max
HCLV PTH 6.88V 6.96 0.163 6.60 7.20
HCLV SMT 7.20V 7.20 0.106 6.88 7.44
F.10.3 High Voltage Low Current
The HVLC circuitry is immediately below the HCLV circuitry and above the high frequency
transmission lines in Figure F.50. The PTH circuitry is in the upper part of this subsection and the
SMT circuitry is in the lower part.
Purpose of the HVLC Experiment
Flux residues could decrease the insulation resistance between conductors. The impact of this
decrease could be significant in circuits with a high voltage gradient across the insulating region.
Decreased resistance can be detected by an increase in current when a high voltage is applied to the
circuit. A voltage of 250V was selected as the high potential for this test. The change in leakage
current is determined by measuring the steady-state performance of the circuit, which will now be
discussed.
F-72
-------
APPENDIX F
Steady State Circuit Performance
Steady-state operation of the HVLC circuit can be determined by considering only the resistors. The
total resistance of the series combination is the sum of the resistances.
Rtotai =Rl+R2+R?>+RA= Rs= 50MQ (F.12)
since all resistors are 10MQ each. From Ohm's law, the current flowing into the circuit with 250V
applied is
V 250V
/ = —= = 5 uA (F.13)
R 50MQ ^ V ;
Care was taken to not overstress the individual components in the circuits. The voltage stress across
each resistor-capacitor pair is one-fifth of the applied 250V, or 50V. The voltage ratings are 250V for
the PTH resistors, 200V for the SMT resistors, and 250V for all the capacitors. Power rating is not a
concern due to the low current.
Circuit Board Design
High voltage traces were placed next to ground potential traces by design. The spacings between
the high voltage and intermediate traces were selected using MIL-STD-275.
Voltage Spacing Between Traces (mils)
0-100 5
101 -300 15
301 -500 30
These guidelines were followed except the 5-mil spacing, where 10 mils was used to facilitate board
fabrication. Table F.32 lists the voltage on various board circuit traces and the spacing to the adjacent
ground trace.
Resistors and capacitors were selected to have readily available values—different values could have
been used to achieve particular experimental goals. For instance, higher resistance values could be
used with lower value capacitors. Reverse biased, low-leakage diodes could also be used for higher
sensitivity to parasitic leakage resistance.
Baseline Testing Results for HVLC
Data modeling showed that surface finish and flux type had very little effect on the voltage
measurements for HVLC PTH and HVLC SMT. Figures F.53 and F.54 provide dotplot displays of
480 voltage measurements for HVLC PTH and HVLC SMT, respectively. The summary statistics for
HVLC PTH and HVLC SMT voltages are given in Table F.33. Note that two sight outliers for HVLC
PTH are identified in Table F.33, but are not included in Figure F.53.
F-73
-------
APPENDIX F
Table F.32 HVLC Circuit Board Trace Potentials
Technology Trace Connected to: Potential (V) Trace Length at Spacing
Resistor Capacitor Potential (in) (mils)
PTH R15 C21 250 0.8 30
200 0.4 15
R16 C22 200 0.4 15
150 NA
R17 C23 150 NA
100 0.4 10
R18 C24 100 0.4 10
50 NA
R19 C25 50 NA
SMT
R20
C26
R21
C27
R22
C28
R23
C29
R24 C30
NA = not applicable since no 50V or 150 V traces
250
5.0
30
200
1.0
15
200
1.0
15
150
NA
150
NA
100
0.9
10
100
0.9
10
50
NA
50
NA
adj acent to ground potential
Table F.33 Summary Statistics for HVLC Circuitry Test Measurements (sans outliers)
Circuitry Mean Median St. Dev. Min Max Outliers
HVLC PTH 5.04|jA 5.04 0.024 4.972 5.148 5.203 5.232
HVLC SMT 4.95|xA 495 0.011 4.914 4.976
4.970 5.005 5.040 5.075 5.110 5.145
Figure F.53 Dotplot of 478 Voltage Measurements for HVLC PTH
(each dot represents up to 2 points)
F-74
-------
APPENDIX F
4.920 4.932 4.944 4.956 4.968 4.980
Figure F.54 Dotplot of 480 Voltage Measurements for HVLC SMT
(each dot represents up to 2 points)
F.10.4 High Speed Digital
The HSD circuitry is in the upper right hand corner of the LRSTF PWA shown in Figure F.50.
This subsection contains the PTH circuitry and consists of two 14-pin Dual In-line Package (DIP)
integrated circuits (ICs). The SMT subsection IC is a single 20-pin leadless chip carrier (LCC)
package. Each of these ICs is a "Fast" bi-polar digital "QUAD-DUAL-INPUT-NAND-GATE." Both
subsections contain two ceramic capacitors that bypass spurious noise on the power input line (VCC)
to the ICs and an output high-frequency connector. Inputs to both subsections are applied through the
edge-connector on the right side of the board. Figure F.55 shows a simplified schematic of the ICs.
5V
2.5 V
Pulse
1
VCC
Quad-Dual-lnput-NAND-Gate IC
Ground
Ground Plane
Figure F.55 Simplified Schematic of the ICs in the HSD Subsection
F-75
-------
APPENDIX F
Purpose of the HSD Experiment
The output signal of each gate in Figure F.55 is opposite in polarity to the input signal. If the
traces of these two signals are in close proximity on the printed circuit board (capacitively coupled),
the gate switching speed might be affected by the presence of flux residues. A 5VDC bias is applied to
the VCC inputs during environmental testing to accelerate aging. One PTHIC (U02) is hand soldered
during assembly to introduce hand solder flux residue in the experiment.
Circuit Description
The schematic in Figure F.55 represents the ICs in the PTH and SMT subsections. The ICs are
random logic circuits that are NAND (Not AND) gates. An AND gate's output is high only when all
inputs are high. The logic of a NAND gate is opposite the logic of an AND gate. Therefore, the
output of a NAND gate is low only when all inputs are high, otherwise the output is high. With the
two connected inputs, the output of each gate is opposite the input. Since the four gates are connected
in series, the output of the last gate is the same logic level (high or low) as the input, with a slight lag.
The output pulse does not change logic levels instantaneously, but the switching times from low to
high (rise time) and from high to low (fall time) should be less than Ins. ICs should perform within
these criteria if the VCC input is 5±0.5V DC, the output load does not exceed specifications, and the
circuit has a proper ground plane as shown in Figure F.55. The HSD circuits also provide an
intermediate test for high frequencies, with switching time dictating a high frequency spectrum. The
frequency spectrum of switching circuits can be expressed in terms of bandwidth (BW). For a
switching circuit, the respective BWs (in Hertz) for rise (tr) and fall (tf) times are:
0.35 0.35
BWr = Hz and BWf = Hz (F.14)
t 3 1
ir if
Bipolar technology was used rather than a complementary metal oxide semiconductor (CMOS)
since it is not as vulnerable to electrostatic discharge (ESD) damage. Available military bipolar
technologies have the following typical switching speeds and bandwidths:
Technology Typical trol.f(ns) Bandwidth (MHz)
5404 TTL
12
29
54LS04 Low
Power Schottky
9
39
54S04 Schottky
3
117
54F04 Advanced
Schottky (Fast)
2.5
140
The Fast technology was selected since it had the shortest switching time and largest bandwidth,
which provides the widest frequency spectrum for this test.
Circuit Board Design
Ground planes were provided for proper circuit operation of the ICs. The PTH subcircuit utilized
the large common ground plane on layer 3 since most of the input and output traces are on layer 4.
Since the SMT circuit traces are on the top layer, a smaller ground plane was added on layer 2. The
"QUAD-DUAL-INPUT-NAND-GATE" was selected since other solder studies of national attention
have used that particular type of IC, which makes direct comparisons with these studies possible.
F-76
-------
APPENDIX F
Baseline Testing Results for HSD
Data modeling showed that surface finish and flux type had very little effect on the total
propagation delay measurements (msec) for HSD PTH and HSD SMT. Figures F.56 and F.57 provide
dotplot displays of 480 voltage measurements for HSD PTH and HSD SMT, respectively. The
summary statistics HSD PTH and HSD SMT total propagation delay are given in Table F.34 (Note one
slight outlier for HSD PTH).
+ + + + + + _ u sec
12.64 12.80 12.96 13.12 13.28 13.44
Figure F.56 Dotplot of 480 Measurements of Total Propagation Delay for HSD PTH
(each dot represents up to 2 points)
+ + + + + + _u sec
4.80 4.92 5.04 5.16 5.28 5.40
Figure F.57 Dotplot of 480 Measurements of Total Propagation Delay for HSD SMT
(each dot represents up to 2 points)
Table F.34 Summary Statistics for HSD Circuitry Total Propagation Delay (usee)
Test Measurements (sans outliers)
Circuitry Mean Median St. Dev. Min Max Outliers
HSD PTH 13.04(0, sec 13.04 0.124 12.56 13.44 14.40
HSD SMT 5.02n sec 5X)2 0.086 475 5.39 4.20 4.29
F-77
-------
APPENDIX F
F.10.5 High Frequency
The HF section shown in the lower right-hand corner of Figure F.50 contains two major
subsections, the low-pass filters (LPF) and the transmission line coupler (TLC). The TLC traces on
layer 4 of the board are on the backside of the board. The LPF/PTH subsection is above the LPF/SMT
subsection. Each of these subsections has discrete ceramic capacitors and three inductor-capacitor
(LC) filters, with the inductor printed on the circuit board in a spiral pattern. The HF circuits allow
evaluation of circuit performance up to 1 GHz (1000MHz).
Purpose of the High Frequency Experiment
Flux residues may affect the performance of LPF printed circuit inductors and transmission lines
due to parasitic resistances and parasitic capacitances. Since the transmission lines are separated by
only 10 mils, flux residues between the lines may affect their performance.
LPF Circuit Description
An inductor-capacitor (LC) LPF consists of a series inductor followed by a shunt capacitor. A
low-frequency signal passes through the LPF without any loss since the inductor acts as a short circuit
and the capacitor acts as an open circuit for such signals. Conversely, a high-frequency signal is
blocked by the LPF since the inductor acts as an open circuit and the capacitor acts as a short circuit
for such signals.
When a sine wave test signal is passed through an LPF, its amplitude is attenuated as a function of
frequency. The relationship between the output and input voltage amplitudes can be expressed as a
transfer function. The transfer function, Vout / Vjn, was measured to determine any effects of the 1 ow-
residue fluxes.
The transfer function is measured in decibels (dB) as a function of frequency. A decibel can be
expressed in terms of voltage as follows:
The PTH transfer function differs from the SMT transfer function due to the self inductance of the
capacitor through-hole leads.
LPF Circuit Board Design
The three LC LPFs for each of the SMT and PTH circuits were designed to have the following
cutoff frequencies: 800, 400, and 200 MHz. Cutoff frequency is that frequency for which the transfer
function is -3 dB. The respective component values chosen for the LC filters are 16 nH (nano-Henries)
and 6.4pF (pico-Farads), 32 nH and 13 pF, and 65 nH and 24pF. Most LPF circuitry was placed on
Layer 1, with Layer 2 used as a ground plane. Crossovers needed to connect the LPF circuits are on
The LPF circuits were designed to operate with a 50Q test system, so all interconnect traces
longer than 0.10 in were designed as 50Q transmission lines to avoid signal distortion. The LPF
circuits were predicted to have less than 2 dB loss below 150 MHz, approximately 6 dB loss near 235
dB = 20 log
(F.15)
Layer 4.
F-78
-------
APPENDIX F
MHz, and greater than 40 dB loss at 550 MHz and beyond. The measured response of the LPF/SMT
circuit is close to that predicted except that the transfer function decreases more rapidly than predicted
above 350 MHz. As stated previously, the PTH circuit transfer function did not perform similarly to
the SMT, particularly at frequencies above 150 MHz.
-0.325 -0.300 -0.275 -0.250 -0.225 -0.200
Figure F.58 Dotplot of 473 Measurements of the Response for HF PTH at 50 MHz
(each dot represents up to 2 points)
_ + + + + + + MHz
240.0 244.0 248.0 252.0 256.0 260.0
Figure F.59 Dotplot of 472 Measurements of the Frequency for HF PTH at-3dB
(each dot represents up to 2 points)
_ + + + + + + MHz
424.0 432.0 440.0 448.0 456.0 464.0
Figure F.60 Dotplot of 474 Measurements of the Frequency for HF PTH at —HklB
(each dot represents up to 2 points)
F-79
-------
APPENDIX F
Baseline Testing Results for HF LPF
Data modeling showed that surface finish and flux type had slights effects on the HF LPF
frequencies and responses for HF PTH 50 MHz, HF PTH f(-3dB), HF PTH f(-40dB), HF SMT 50
MHz, and HF SMT f(-3dB). The response, HF SMT f(-40dB), was 5 to 12 MHz lower for PWA with
OSP, immersion Ag, or immersion Au/Pd surface finishes. However, the range of frequencies for this
response was only from 630.7 MHz to 680.60 MHz, so the changes in frequency are relatively small.
Figures F.58 to F.59 provide dotplot displays of 480 measurements for the six HF LPF responses. The
summary statistics for these responses are given in Table F.35 (Note there are several outliers
identified in this table).
-0.315 -0.280 -0.245 -0.210 -0.175 -0.140
Figure F.61 Dotplot of 473 Measurements of the Response for HF SMT at 50 MHz
(each dot represents up to 2 points)
_ + + + + + + MHz
273.6 275.2 276.8 278.4 280.0 281.6
Figure F.62 Dotplot of 469 Measurements of the Frequency for HF SMT at-3dB
(each dot represents up to 7 points)
_ + + + + + + MHz
630 640 650 660 670 680
Figure F.63 Dotplot of 469 Measurements of the Frequency for HF SMT at-40dB
(each dot represents up to 2 points)
The distribution in Figure F.59 is different from the other 22 electrical responses in that it displays
a bimodal distribution for HF PTH f(-3dB) with one group of frequencies centered at approximately
245MHz and the other group at 256MHz. Data modeling showed that the differences between these
F-80
-------
APPENDIX F
two groups were not related to any of the experimental parameters (surface finish or flux) nor were
they related to fixture or time of test. A possible explanation for the bimodal distribution is differences
in date lots for the components. However, date lot information were not recorded prior to processing
and thus, the date lot hypothesis cannot be confirmed. Since the JTP acceptance criterion is based on
change after exposure to environmental conditions, the bimodal distribution could potentially be
important if the measurements were not repeatable. Twenty board serial numbers were randomly
selected for retestto see if the measurements were repeatable with 10 boards from the distribution
centered at 245MHz and 10 boards from the distribution centered at 256MHz. These two groups of 10
were equally split between fixtures A and B on the CCAMTF ATS. Table F.36 gives the differences
between the initial baseline measurements and those from the repeat test. The differences in this table
are all quite small. The correlation of the measurements on fixture A is 0.995 and on fixture B it is
0.982, which indicates excellent repeatability. Thus, other than being a curiosity, the bimodal
distribution for HF PTH f(-3dB) will have no practical effect on the test results.
Table F.35 Summary Statistics for 393 Test Measurements for Response (dB) or Frequency (MHz)
for HF LPF (sans outliers)
Circuitry Mean Median St. Dev. Min Max Outliers
HF PTH 50 MHz
-0.254 dB
-0.252
0.022
-0.319
-0.194
-0.351
-0.148
-0.130
-0.096
-0.150
-0.138
-0.107
HF PTH -3dB
250.6 MHz
250.7
5.65
240.0
260.8
227.4
305.3
307.1
308.3
230.5
306.5
307.7
308.9
HF PTH -40 dB
440.7 MHz
440.1
6.01
425.3
464.4
506.6
507.8
513.7
507.2
513.1
514.3
HF SMT 50 MHz
-0.242 dB
-0.242
0.023
-0.329
-0.144
-0.447
-0.066
-0.061
-0.074
-0.062
HF SMT -3dB
278.3 MHz
278.6
1.20
273.8
282.2
225.2
299.4
302.9
355.2
383.1
389.6
295.8
301.8
302.9
381.9
384.3
HF SMT -40dB
660.2 MHz
661.0
7.66
630.7
680.6
694.8
708.5
721.5
862.8
877.7
701.9
719.8
758.3
872.3
890.2
924.6
F-81
-------
APPENDIX F
Table F.36 Results from Repeat Testing of the HF PTH f(-3dB) Circuit
Fixture A
Fixture B
Test
Baseline
Repeat
Difference
Baseline
Repeat
Difference
1
244.2
243.0
1.23
242.4
243.0
-0.57
2
245.3
244.8
0.55
244.2
245.3
-1.14
3
246.5
246.5
-0.03
245.3
245.9
-0.64
4
247.1
247.1
-0.03
246.5
244.2
2.34
5
253.1
254.3
-1.15
248.9
250.1
-1.19
6
255.4
255.4
-0.04
253.7
255.4
-1.74
7
256.0
256.0
-0.03
254.8
255.4
-0.64
8
257.2
257.8
-0.61
256.0
258.4
-2.41
9
259.0
259.0
0.00
257.8
258.4
-0.61
10
259.6
259.0
0.60
259.0
259.0
0.00
TLC Circuit Description
Figure F.64 shows a diagram of the TLC subsection. The LPFs described above are lumped
element circuits since the capacitors are discrete components. The TLC lines are distributed element
circuits with the resistors, inductors, and capacitors distributed along the lines. A circuit model for the
lines is shown in Figure F.65.
J9
\.
J7
J10 / \ J8
Figure F.64 Diagram of the HF/TLC Subsection
-Wr
Rtrace L|_
Vir
R
leakage
— rrm.
Rtrace Ll
cl r
leakage
-WV—
Rtrace
CL
R
JTTTL.
Ll
leakage
Vout
CL
Figure F.65 HF/TLC Distributed Element Model
The inductance and capacitance for a transmission line with a ground plane are, respectively:
Ll = 0.0%5RQ^£^nH I in
85
Cl =-j^4z~rPF! ™
(F.16)
(F.17)
F-82
-------
APPENDIX F
where Ro = characteristic resistance and er = dielectric constant of the board material.
The TLC Ro was designed to be 50Q for operation with a 50Q test system. For FR-4 epoxy
(board substrate material), Ll is about 9.6 nHUn and Cl is about 3.8pF/in.
The TLC was tested with a sine wave signal similar to the one used in testing the LPFs. The
source resistance was 50Q and the three output terminals were connected to 50Q loads.
TLC Circuit Board Design
The transmission line coupler (TLC) circuit has a pair of coupled 50 Q transmission lines with
required measurable performance frequencies less than 1000 MHz. Layer 4 of the printed wiring board
(PWB) was used to route the TLC circuit, with Layer 3 used as the ground plane. The TLC circuit is a
5 in long pair of 0.034 in wide 50Q transmission lines spaced 0.010 in apart. The circuit design
incorporated the board dielectric constant of about 3.8 and the .020 in spacing between copper layers.
A computer-aided circuit design tool (Libra) was used to model the TLC circuit. Performance
measured on a test PWB agreed very closely with the forward and reverse coupling predictions
between 45 MHz and 1000 MHz.
Baseline Testing Results for HF TLC
Data modeling showed that surface finish and flux type had very slight effect on the HF TLC
frequencies and responses for HF TLC 50 MHz, HF TLC 500 MHz, HF TLC 1000 MHz, HF TLC
Reverse Null Frequency, and HF TLC Reverse Null Response. Figures F.66 to F.70 provide dotplot
displays of 480 measurements for the five HF TLC responses. Summary statistics for these responses
are given in Table F.37 (Note the outliers identified in this table).
-42.0 -40.0 -38.0 -36.0 -34.0 -32.0
Figure F.66 Dotplot of 479 Measurements of the Response for HF TLC at 50 MHz
(each dot represents up to 4 points)
-18.90 -18.20 -17.50 -16.80 -16.10 -15.40
Figure F.67 Dotplot of 479 Measurements of the Response for HF TLC at 500 MHz
(each dot represents up to 3 points)
F-83
-------
APPENDIX F
-13.20 -12.80 -12.40 -12.00 -11.60 -11.20
Figure F.68 Dotplot of 478 Measurements of the Response for HF TLC at 1000 MHz
(each dot represents up to 2 points)
+ + + + + + MHz
636.0 642.0 648.0 654.0 660.0 666.0
Figure F.69 Dotplot of 479 Measurements of the HF TLC Reverse Null Frequency
(each dot represents up to 2 points)
-66.0 -60.0 -54.0 -48.0 -42.0 -36.0
Figure F.70 Dotplot of 479 Measurements of the HF TLC Reverse Null Response
(each dot represents up to 2 points)
Table F.37 Summary Statistics for 480 Test Measurements for Response (dB) or Frequency (MHz) for HF TLC
(sans outliers)
Circuitry
Mean
Median
St. Dev.
Min
Max
Outliers
HF TLC 50 MHz
-37.57 dB
-37.34
0.974
-42.74
-33.05
-6.13
HF TLC 500 MHz
-18.34 dB
-18.43
0.403
-19.29
-15.57
-6.90
HF TLC 1000 MHz
-12.56 dB
-12.60
0.258
-13.15
-11.07
-7.05
-8.94
HF TLC RNF
649.6 MHz
649.1
4.77
636.6
665.1
935.3
HF TLC RNR
-44.82 dB
-44.01
5.25
-64.89
-34.12
-9.67
F-84
-------
APPENDIX F
F.10.6 Other Networks (Leakage Currents)
The test PWA also contains three test patterns to provide tests for current leakage: (1) the pin grid
array (PGA), (2) the gull wing (GW), and (3) 10-mil spaced pads. A 100V source was used to
generate leakage currents.
Purpose of the Experiments
The PGA, GW, and 10-mil pads allow leakage currents to be measured on test patterns that are
typical in circuit board layouts. These patterns contain several possible leakage paths and the leakage
could increase with the presence of flux residues and environmental exposure. In addition, solder
mask was applied to portions of the PGA and GW patterns to evaluate its effect on leakage currents
and the formation of solder balls.
Pin Grid Array
The PGA hole pattern has four concentric squares that are electrically connected by traces on the
top layer of the board as shown in Figure F.71. The pattern also has four vias just inside the corners of
the innermost square that are connected to that square. Four vias were placed inside the innermost
square to trap flux residues. Two leakage current measurements were made: (1) between the two inner
squares (PGA-A) and (2) between the two outer squares (PGA-B), as shown in Figure F.71. Solder
mask covers the holes of the two outer squares on the bottom layer, allowing a direct comparison of
similar patterns with and without solder mask.
Rather than an actual PGA device, a socket was used since it provided the same soldering
connections as a PGA device. Also, obtaining leakage measurements on an actual PGA is nearly
impossible due to complexity of its internal semiconductor circuits.
Gull Wing
The upper half of the topmost GW lands and the lower half of the bottom most GW lands were
covered with solder mask to create a region that is susceptible to the formation of solder balls. The
lands were visually inspected to detect the presence of solder balls. A nonfunctional GW device is
installed with every other lead connected to a circuit board trace forming two parallel paths around the
device. Total leakage current measurements were made on adjacent lands of the GW device
10-mil Pads
The 10-mil pads were laid out in two rows of five pads each. The pads within each row were
connected on the bottom layer of the board and leakage between the rows was measured.
Baseline Testing Results for Leakage Currents
The leakage currents are converted to resistance (ohms) through the basic equation R = V/I. Since
the applied voltage is 100 V and the current is measured in nanoamps, this equation can be expressed
as logio R = 11 - logio I.
F-85
-------
APPENDIX F
PGA-B
PGA-A
^Solder
Mask
Figure F.71 PGA Hole Pattern with Solder Mask
Table F.38 Significant Coefficients for the GLM Analyses of Leakage Currents
Experimental Variables
10-Mil Pad
PGA A
PGA B
Gull Wing
Constant
11.43
10.63
9.88
11.57
OSP
0.68
0.92
1.22
0.61
Immersion Ag
0.59
0.84
1.22
0.67
Immersion Au/Pd
0.28
0.49
1.52
0.40
Flux
1.61
1.77
2.74
0.89
OSP*Flux
-0.33
-0.60
Ag*Flux
-0.37
-0.26
-0.90
Au/Pd*Flux
-0.90
-0.31
Model R2
60.99
74.52
88.12
35.04
Standard Deviation
0.606
0.542
0.432
.681
General linear modeling (GLM) results for logio R are given in Table F.38. The GLM results
show that surface finish and flux type strongly affect leakage currents. To illustrate these effects,
dotplot displays of 480 measurements for the four leakage responses are given by surface finish and
flux in Figures F.72 to F075 and by flux in Figure F.76. The summary statistics for these responses are
given in Tables F.39 and F.40.
F-86
-------
APPENDIX F
+ + + + OSP LR
+ + + + OSP WS
+ + + + Ag LR
+ + + + Ag yiS
+ + + + Au/Pd LR
+ + + + Au/Pd WS
+ + + + HASL LR
+ + + + HASL WS
10.0 11.0 12.0 13.0 14.0
Figure F.72 Dotplots for 480 Measurements of Leakage on 10-Mil Pads by Surface Finish and Flux
F-87
-------
APPENDIX F
+ + + + OSP LR
+ + + + OSP WS
+ + + + Ag LR
+ + + + Ag yiS
+ + + + Au/Pd LR
+ + + + Au/Pd WS
+ + + + HASL LR
+ + + + HASL WS
10.0 11.0 12.0 13.0 14.0
Figure F.73 Dotplots for 480 Measurements of Leakage on PGA A by Surface Finish and Flux
F-88
-------
APPENDIX F
+ + + + OSP LR
+ + + + OSP WS
+ + + + Ag LR
+ + + + Ag WS
+ + + + Au/Pd LR
+ + + + Au/Pd WS
+ + + + HASL LR
+ + + + HASL WS
10.0 11.0 12.0 13.0 14.0
Figure F.74 Dotplots for 480 Measurements of Leakage on PGA B by Surface Finish and Flux
F-89
-------
APPENDIX F
+ + + + OSP LR
+ + + + OSP WS
+ + + + Ag LR
+ + + + Ag yiS
+ + + + Au/Pd LR
+ + + + Au/Pd WS
+ + + + HASL LR
+ + + + HASL WS
10.0 11.0 12.0 13.0 14.0
Figure F.75 Dotplots for 480 Measurements of Leakage on the Gull Wing by Surface Finish and Flux
F-90
-------
APPENDIX F
Table F.39 Summary Statistics for Leakage Currents Test Measurements by Surface Finish
and Flux
Circuitry
Surface Finish
Flux
Mean
Median
St. Dev.
Min
Max
10-Mil Pads
OSP
LR
WS
12.11
13.39
11.94
13.52
0.77
0.55
10.91
11.12
15.00
14.00
Immersion Ag
LR
WS
12.02
13.26
11.90
13.30
0.76
0.38
10.73
12.48
15.00
14.00
Immersion Au/Pd
LR
WS
11.81
13.22
11.73
13.22
0.54
0.60
10.47
11.91
14.00
15.00
HASL
LR
WS
11.29
13.15
11.29
13.40
0.33
0.67
10.34
11.57
12.30
15.00
PGA A
OSP
LR
11.59
11.62
0.67
10.38
13.15
WS
13.28
13.30
0.26
12.12
13.70
Immersion Ag
LR
11.47
11.39
0.66
10.16
13.22
WS
12.98
12.94
0.33
12.18
14.00
Immersion Au/Pd
LR
11.23
11.20
0.56
10.18
13.15
WS
12.78
12.80
0.62
11.67
15.00
HASL
LR
10.45
10.46
0.28
9.94
11.10
WS
12.56
12.66
0.58
11.29
13.40
PGA B
OSP
LR
11.10
11.11
0.43
9.91
12.09
WS
13.23
13.30
0.25
11.85
13.52
Immersion Ag
LR
11.10
11.12
0.47
10.13
12.40
WS
12.94
13.00
0.27
12.19
13.30
Immersion Au/Pd
LR
11.47
11.44
0.50
10.09
13.15
WS
13.16
13.10
0.39
12.51
15.00
HASL
LR
9.74
9.75
0.29
9.11
10.35
WS
12.70
12.70
0.35
11.65
13.40
Gull Wing
OSP
LR
WS
12.15
13.10
12.40
13.22
0.90
0.65
9.01
11.44
13.52
16.00
Immersion Ag
LR
WS
12.23
13.14
12.32
13.46
0.60
0.70
10.66
10.91
13.52
14.00
Immersion Au/Pd
LR
WS
11.99
12.53
12.02
12.66
0.57
0.64
10.35
10.69
13.22
14.00
HASL
LR
WS
11.57
12.44
11.52
12.70
0.39
0.86
10.26
9.48
12.62
13.52
F-91
-------
APPENDIX F
+ + + + lOmilPad LR
+ + + + lOmilPad WS
+ + + + PGA A LR
Each dot represents up to 2 points
: : : .
• • •
• • • •
+ + + + pga A WS
10.0 11.0 12.0 13.0 14.0
Figure F.76 Dotplots for 480 Leakage Measurements by Flux
F-92
-------
APPENDIX F
+ + + + PGA B LR
Each dot represents up to 3 points
+ + + + pga B WS
+ + + + GullWing LR
+ + + + GullWing WS
10.0 11.0 12.0 13.0 14.0
Figure F.76 Continued
F-93
-------
APPENDIX F
F.10.7 Stranded Wires
Two 22-gauge stranded wires were hand soldered just to the left of the edge connector. One wire
was soldered directly into the board through holes and the other were soldered to two terminals, El7
and E18. Each wire is 1.5 in long, is silver coated, and has white PTFE insulation. All wires were
stripped, tinned, and cleaned in preparation for the soldering process.
Purpose of the Stranded Wire Experiment
Stranded wires were used to evaluate flux residues and subsequent corrosion.
Table F.40 Summary Statistics for Leakage Currents Test Measurements by Flux
Circuitry
Flux
Mean
Median
St. Dev.
Min
Max
10-Mil Pads
LR
11.80
11.68
0.70
10.34
15.00
WS
13.25
13.30
0.56
11.12
15.00
PGA A
LR
11.18
11.10
0.72
9.94
13.22
WS
12.90
13.00
0.54
11.29
15.00
PGA B
LR
10.85
11.00
0.79
9.11
13.15
WS
13.01
13.07
0.38
11.65
15.00
Gull Wing
LR
11.99
12.02
0.68
9.01
13.52
WS
12.80
12.94
0.78
9.48
16.00
Circuit Description
The 5 A 100|is pulse used to test the HCLV circuit was injected into each of the stranded wires for
electrical test. A separate PWB trace was connected to each end of the stranded wire. Test wires were
connected to the separate traces allowing to provide the means to measure the voltage drop across the
stranded wires. In this manner, the voltage drop was measured independently from any voltage drop in
the test wires conducting the 5 A pulse to the stranded wires.
Baseline Testing Results for Stranded Wires
Surface finish and flux type had very little effect on the HF TLC frequencies and responses for HF
TLC 50 MHz, HF TLC 500 MHz, HF TLC 1000 MHz, HF TLC Reverse Null Frequency, and HF
TLC Reverse Null Response. Figures F.77 and F.78 provide dotplot displays of480 measurements for
the two stranded wire voltages. The summary statistics for these responses are given in Table F.41.
8.0 10.0
12.0
14.0
16.0
18.0
mV
Figure F.77 Dotplots for 480 Voltage Measurements for Stranded Wire 1
(each dot represents up to 11 points)
F-94
-------
APPENDIX F
20.0 22.0 24.0 26.0 28.0 30.0
Figure F.80 Dotplots for 476 Voltage Measurements for Stranded Wire 2
(each dot represents 8 points)
Table F.41 Summary Statistics for Stranded Wires Voltage Test Measurements
Circuitry Mean Median St. Dev. Min Max Outliers
Stranded Wire 1 11.75mV 12.00 1.60 8.00 18.00
Stranded Wire 2 24.82mV 25.00 2.41 19.00 30.00 42,43,45,45
F.10.8 Summary Statistics for All Baseline Measurements
For ease of reference, Table F.42 gives the summary statistics for all 23 electrical responses from
the test PWA.
F.10.9 Listing of Components
All functional component types conformed to commercial specifications and were ordered pre -
tinned (to the extent possible). Components were not pre-cleaned before use. A listing of all
components is given in the Table F.43.
F-95
-------
APPENDIX F
Circuitry
Table F.42 Summary Statistics for All Baseline 480 Measurements (sans outliers)
Mean
Median
St. Dev.
Min
Max
Outliers
Hi
gh Current Low Voltage
HCLV PTH
HCLVSMT
6.88V
7.20V
6.92
7.20
0.16
0.10
6.60
6.88
7.20
7.44
Hi
gh Voltage Low Current
HVLC PTH
HVLCSMT
5.04mA
4.95mA
5.04
4.95
0.024
0.011
4.972
4.914
5.148
4.976
5.203 5.232
High Speed Digital
HSD PTH
HSD SMT
13.04m sec
5.02m sec
0.12
0.08
13.04
5.02
12.56
4.75
13.44
5.39
14.40
High Frequency Low Pass Filter
HF PTH 50 MHz
HF PTH -3dB
HF PTH -40dB
HF SMT 50 MHz
HF SMT -3dB
HF SMT -40dB
-0.254 dB
-0.253
0.024
-0.319
-0.194
-0.351 -0.150
-0.148 -0.138
-0.130 -0.107
-0.096
250.5 MHz
249.2
5.74
230.5
260.8
227.6 230.5
305.3 306.5
307.2 307.7
308.3 308.9
440.5 MHz
440.1
5.96
425.3
464.4
506.6 507.2
507.8 513.1
513.7 514.3
-0.242 dB
-0.241
0.022
-0.329
-0.173
-0.447 -0.164
-0.144 -0.074
-0.066 -0.062
-0.061
278.4 MHz
278.6
1.21
273.8
282.2
225.2 295.8
299.4 301.8
302.9 302.9
355.2 381.9
383.1 384.3
389.6
660.7 MHz
661.6
7.46
639.0
680.6
694.8 701.9
708.5 719.8
721.5 758.3
862.8 872.3
877.7 890.2
924.6
High Frequency Transmission Line Coupler
HF TLC 50 MHz
HF TLC 500 MHz
HF TLC 1000 MHz
HF TLC RNF
HF TLC RNR
-37.61 dB
-18.31 dB
-12.55 dB
649.5 MHz
-44.68 dB
-37.38
-18.40
-12.58
649.1
-43.96
0.957
0.389
0.254
4.87
5.208
-42.74
-19.29
-13.15
636.6
-64.89
-33.05
-15.57
-11.07
665.1
-34.12
-6.13
-6.90
-7.05 -8.94
935.3
-9.67
Lcakajj
e (resistance in log 10 ohms)
10-Mil Pads (LR)
10-Mil Pads (WS)
PGA A (LR)
PGA A (WS)
PGA B (LR)
PGA B (WS)
Gull Wing (LR)
Gull Wing (WS)
11.79
13.27
11.17
12.89
10.84
13.01
12.03
12.81
11.69
13.40
11.11
13.05
11.04
13.10
12.05
12.96
0.64
0.56
0.70
0.52
0.80
0.34
0.66
0.71
10.63
11.12
10.01
11.29
9.11
11.65
10.15
10.52
15.00
15.00
13.15
14.00
12.46
13.52
13.52
14.00
Stranded Wire
Stranded Wire 1
Stranded Wire 2
11.75mV
24.71mV
12.00
25.00
1.50
2.38
8.00
19.00
18.00
30.00
42, 43, 45, 45
F-96
-------
APPENDIX F
MFGP/N
Table F.43 Listing of Components for the Test PWA
„ . Quantity per
Description . ,,
Supplier
ACC916228-2
PGA Socket, 18X18 (223 PINS)
1
AMP
350-60-2
6 Split washer
3
Barnhill Bolt
402-632-38-0110
6-32 UNC Mach Screw
3
Barnhill Bolt
231-632-A-2
6-32 UNC Mach Screw Nut
3
Barnhill Bolt
RWR89N10R0FR
Resistor, 10 Ohm, Axial
7
Dale
M55342M09B10MOM
Resistor, 10 Ohm, Surface Mnt
7
Dale
RLR07C1005FR
Resistor, 1 OMeg Axial
5
Dale
M55342M09B10POM
Resistor, lOMeg Surface Mount
5
Dale
2309-2-00-44-00-07-0
Swage pin
17
Harrison HEC
KA29/127BPMCTH
29 Pin Connector,Pretin
1
Hypertonics
C1825N474K5XSCxxxx
CAP, .47 UF, Surf Mnt
7
Kemet
C0627104K1X5CS7506
CAP, 0.1 UF, Radial
7
Kemet
C1825N104K1XRC
CAP, 0.1 UF, Surf Mnt
7
Kemet
C062T105K5X5CSxxxx
CAP, 1 UF, Radial
7
Kemet
C052G130J2G5CR
CAP, 13 PF, Radial
1
Kemet
CDR31 BP 130B JWR
CAP, 13 PF, Surf Mnt
1
Kemet
C052G240J2G5CRxxxx
CAP, 24 PF, Radial
1
Kemet
C0805N240J1GRC37317537
CAP, 24 PF, Surf Mnt
1
Kemet
C0805N629B1GSC37317535
CAP, 6.2 PF +0.5%, Surf Mnt
1
Kemet
C052G629D2G5CR7535
CAP, 6.2 PF, +0.5%, Radial
1
Kemet
JM3 8510/3 3001B2A
20 Pin LCC
1
TI (808810.1001)
JM38510/33001BCA
14 Pin Dual-In-Line
2
TI (808810.1)
QFP80T25
80 Pin SQ Flat Pack
1
Top Line
CS1
Cap
1
Top Line
CKR06
Cap
2
Top Line
SC1210E7Axxxx
Cap
13
Top Line
D034
Diode
13
Top Line
RN65
Resistor
1
Top Line
RN55(sub for CS1, Qty 800)
Resistor
5
Top Line
SR1210E7A
Resistor
18
Top Line
T05
Transistor
4
Top Line
TO220M-3
Transistor
3
Top Line
5162-5013-09
Connector, RF, OMNI Spec
10
TTI
131-3701-201
Sub for 5162-5013-09
10
Penstock
F-97
-------
APPENDIX F
F.ll Design for the Environment Printed Wiring Board Project Performance
Demonstration Methodology for Alternative Surface Finishes
Note: This methodology is based on input from members of a Performance Demonstration Technical
Workgroup, which includes representatives of the printed wiring board (PWB) industry manufacturers,
assemblers, and designers; industry suppliers; public interest group; Environmental Protection Agency
(EPA); the University of Tennessee Center for Clean Products and Clean Technologies; and other
stakeholders. As the testing continues, there may be slight modifications to this methodology.
I. OVERVIEW
A. Goals
The U.S. Environmental Protection Agency's (EPA=s) Design for the Environment (DfE) Printed
Wiring Board (PWB) Project is a cooperative partnership among EPA, the PWB industry, public
interest groups, and other stakeholders. The project encourages businesses to incorporate
environmental concerns into their decision-making processes, along with the traditional parameters of
cost and performance, when choosing which technologies and processes to implement. To accomplish
this goal, the DfE PWB Project collects detailed data on the performance, cost, and risk aspects of one
Ause cluster@ or manufacturing operation, and makes it available to all interested parties. This use
cluster focuses on surface finishes used in PWB manufacturing. Analyses on the performance, cost,
and risk of several alternative surface finishes will be conducted throughout this project, and the results
will be documented in the final project report, titled the Cleaner Technologies Substitutes Assessment
or CTSA. This methodology provides the general protocol for the performance demonstration portion
of the DfE PWB Project. The CTSA is intended to provide manufacturers and designers with detailed
information so that they can make informed decisions, taking environmental and health risks into
consideration, on what process is best suited for their own facility.
Surface finishes are applied to PWBs to prevent oxidation of exposed copper on the board, thus
ensuring a solderable surface when components are added at a later processing stage . Specifically, the
goals of the DfE PWB Surface Finishes Project are:
1) to standardize existing information about surface finish technologies;
2) to present information about surface finish technologies not in widespread use, so PWB
manufacturers and designers can evaluate the environmental and health risks, along with the cost and
performance characteristics, among different technologies; and
3) to encourage PWB manufacturers and designers to follow the example of this project and evaluate
systematically other technologies, practices, and procedures in their operations that affect the
environment.
B. General Performance Demonstration Plan
The most widely used process for applying surface finishes in commercial PWB shops is hot air solder
leveling (HASL). In this process, tin-lead is fused onto exposed copper surfaces. This process was
selected as the focus of the Design for the Environment Project because HASL is a source of lead
waste in the environment and because there are several alternative surface finishes available on the
market. A comprehensive evaluation of these technologies, including performance, cost, and risk,
however, has not been conducted. In addition, a major technical concern is that the HASL process
F-98
-------
APPENDIX F
does not provide a level soldering surface for components.
The general plan for the performance demonstration portion of the Project is to collect data on
alternative surface finish processes during actual production runs at sites where the processes are
already in use. Demonstration facilities will be nominated by suppliers. These sites may be customer
production facilities, customer testing facilities (beta sites), or supplier testing facilities, in that order of
preference. Each demonstration site will receive standardized test boards which they will run through
their surface finish operation during their normal production operation.
The test vehicle design will be tested on the test board designed by the Sandia National Laboratory
Low-Residue Soldering Task Force (LRSTF). The same test vehicle was used by the Circuit Card
Assembly and Materials Task Force (CCAMTF). CCAMTF is a joint industry and military program
evaluating several alternative technologies including Organic Solderability Preservative (OSP),
Immersion Silver, Electroplated Palladium/Immersion Gold, Electroless Nickel/Immersion Gold, and
Electroplated Palladium. CCAMTF conducted initial screening tests on coupons for each of these
surface finishes, however, they will conduct functionality tests only for the OSP (thick), Electroplated
Palladium/Immersion Gold, and Immersion Silver technologies.
II. PERFORMANCE DEMONSTRATION PROTOCOL
A. Technologies to be Tested
The technologies that the DfE Project plans to test include:
1. HASL (baseline)
2. OSP - Thick
3. Immersion Tin
4. Immersion Silver
5. Electroless Nickel/Immersion Gold
6. Nickel/Palladium/Gold
B. Step One: Identify Suppliers and Test Sites/Facilities
Performance Demonstration Technical Workgroup members identified suppliers of the above product
lines. Any supplier of these technologies who wanted to participate was eligible to submit its product
line, provided that it agreed to comply with the testing methodology and submit the requested
information, including chemical formulation data. All proprietary information submitted is bring
handled as Confidential Business Information. For each product line submitted, the supplier
completed a Supplier Data Sheet detailing information on the chemicals used, equipment requirements,
waste treatment recommendations, any limitations of the technology, and other information on the
product line.
Performance demonstration sites were nominated by suppliers. They identified sites that are currently
using their alternative surface finish product line in the following order of preference:
customer production facilities (first preference)
beta sites - customer testing facilities (second preference)
supplier testing facilities (third preference)
The final number of product lines evaluated for each type of alternative surface finish was determined
based on the number of suppliers interested in participating and on the resources available. Each
F-99
-------
APPENDIX F
accepted product line was tested at one or two sites. If a supplier has more than one substantially
different product line within a technology, the supplier was allowed to submit names of test facilities
for each of the products.
C. Step Two: Fabricate Test Vehicles
Test board were fabricated based on the Sandia National Laboratory Low-Residue Soldering Task
Force (LRSTF) test board design. This general design was also used in the CCAMTF testing. For the
DfE Project, uncoated test boards with comb pattern spacing of 8 mil, 12 mil, 16 mil, and 20 mil will
be used.
All test boards are of the same design, and were fabricated at a single shop to minimize the variables
associated with board production. All manufacturing steps, up to but not including the soldermask
application, were completed by the test board fabricator. For each supplier's product line, 24 boards
were shipped to the demonstration site where the alternative surface finish was applied, beginning with
the soldermask application step.
The design of the LRSTF PWB was based on input from a large segment of the manufacturing
community, and thus reflects the multiple requirements of the commercial sector. Each quadrant of the
LRSTF PWA contain one of the following types of circuity:
High-current low-voltage (HCLV)
High-voltage low current (HVLC)
High speed digital (HSD)
High frequency (HF)
The components in each quadrant represent two principal types of soldering technology:
Plated through hole (PTH) - leaded components are soldered through vias in the circuit board by
means of a wave soldering operation.
Surface mount technology (SMT) - components manufactured with solder tips on two of their
opposite ends are temporarily attached to the substrate with an adhesive and then they are soldered to
pads on the circuit board by passing the circuit board through a reflow oven to reflow the solder tips.
The LRSTF PWA also has two stranded wires (SW) that are secured to the circuit board with hand
soldering, such as used in repair operations. This assembly also contains other networks that are used
to monitor current leakage.
D. Step Three: Collect Background Information
After the suppliers identified appropriate test facilities and completed a supplier data sheet, an
independent observer contacted the designated facilities. The observer scheduled a date for the on-site
performance demonstration. A questionnaire was sent to each facility prior to the site visit to collect
information on the surface finish technology used and background information on the facility, such as
the size and type of product produced. On the day of the performance demonstration, the observer
reviewed the background questionnaire and discussed any ambiguities with the facility contect.
F-100
-------
APPENDIX F
E. Step Four: Conduct the Surface Finish Performance Demonstration
After test boards were distributed to the demonstration sites, the surface finish performance
demonstrations were conducted. The surface finish was applied to the test boards as part of the normal
production run at the facility. The test boards were placed in the middle of the run to reflect actual
production conditions. The facility applied the solder mask it normally uses in production. The usual
process operator operated the line to minimize error due to unfamiliarity with the technology. All test
boards were processed in the same production run.
On the day of the performance demonstration, the observer collected data on the surface finish process.
During the demonstration, the observer recorded information on surface finish technology
performance, including information on chemicals, equipment, and waste treatment methods used. In
addition, other information needed for the performance, cost, or risk analyses, as described below, was
collected.
1. Product Cost: A cost per square foot of panel processed will be calculated. This number will be
based on information provided by product suppliers, such as purchase price, recommended bath
life and treatment/disposal methods, and estimated chemical and equipment costs per square foot
panel per day. Any "real world" information from PWB manufacturers, such as actual dumping
frequencies, treatment/disposal methods, labor requirements, and chemical and equipment costs,
will be collected during performance demonstrations, as required for use in the cost analysis. The
product cost may differ for difference shop throughput categories.
2. Product Constraints: Information on any incompatibilities such as soldermask, flux, substrate
type, or assembly process will be included. This information will be submitted by the suppliers
and may also be identified as a result of the performance demonstrations.
3. Special storage, safety, and disposal requirements: Information on flammability or special
storage requirements of the chemicals used in the process will be requested from the suppliers.
Suppliers will provide recommendations on disposal or treatment of wastes associated with the use
of their product lines. Information on these issues was also collected from participating facilities
during the performance demonstrations. The storage and disposal costs will be a factor in
determining the adjusted cost of the product. This project does not entail a life cycle analysis for
disposal of the boards.
4. Ease of use: During the performance demonstration, the physical effort required to use the various
surface finishes effectively will be qualitatively assessed based on the judgement of the operator in
comparison to the baseline technology, HASL. Specific questions such as the following will be
asked: What process operating parameters are needed to ensure good performance? What are the
ranges of those parameters, and is there much flexibility in the process steps? How many hours of
training are required to use this type of surface finish?
5. Duration of Production Cycle: The measured time of the surface finish application process and
the number of operators required will be recorded during the performance demonstration. This
information will be used to measure the labor costs associated with the use of the product line.
Labor costs will be based on the operator time required to run the process using an industry
standard worker wage. The process cycle has been defined as the activities following soldermask
application up to, but not including, gold tab plating. The facilities participating in the
performance demonstration will use the same soldermask they typically use in production
conditions. The observer recorded the type of soldermask used, and information on the facilities'
experiences with other soldermasks to determine if any known incompatibilities exist.
F-101
-------
APPENDIX F
6. Effectiveness of Technology, Product Quality: The performance characteristics of the
assembled boards will be tested after all demonstrations are complete and the boards are assembled
with the functional components. Circuit electrical Performance will be tested to assess the circuit
performance of the functional test vehicle under applicable environmental stress. Circuit
Reliability Testing (functional tests) conditions will include Thermal Shock and Mechanical
Shock. These tests are described in greater detail in Step 5. Qualitative information on shelf life
considerations were collected through the performance demonstrations, where applicable.
7. Energy and Natural Resource Data: Information will be collected from the suppliers and during
the performance demonstrations to evaluate the variability of energy consumption for the use of
different surface finishes. The analysis will also address material use rates and how the rates vary
with the different surface finishes.
8. Exposure Data: Exposure data will be used to characterize chemical exposures associated with
the technologies. Exposure information collected during the performance demonstration may be
supplemented with data from other sources, where available.
F. Step Five: Assemble and Test the Boards
After the surface finish was applied to the test boards at each demonstration facility, the facility sent
the processed boards to one site for assembly. Two different assembly processes were used: a halide-
free, low-residue flux and a halide-containing, water-soluble flux. Table 1 shows the different
assembly methods, and number of test vehicles used for each method. The boards were not assembled
as originally planned, resulting in the uneven distribution of assembly methods.
Table 1: Test Vehicle Distribution by Site and Flux
Site#
Surface Finishes*
# of Boards
Assembled with Low
Residue Flux
# of Boards
Assembled with
Water Soluble Flux
Total Boards by
Site and by Surface
Finish
1
HASL
8
8
16
2
HASL
0
8
8
6
HASL
8
0
8
HASL Totals
16
16
32
3
OSP-Thick
4
8
12
13
OSP-Thick
8
8
16
16
OSP-Thick
8
0
8
OSP Totals
20
16
36
4
Immersion Tin
0
8
8
5
Immersion Tin
4
8
12
10
Immersion Tin
8
0
8
11
Immersion Tin
8
0
8
Immersion Tin Totals
20
16
36
8
Immersion Silver
0
8
8
9
Immersion Silver
8
4
12
Immersion Silver Totals
8
12
20
7
Electroless Ni/Immersion Au
0
8
8
12
Electroless Ni/Immersion Au
8
0
8
14
Electroless Ni/Immersion Au
4
8
12
NI/Au Totals
12
16
28
Subtotals
84
80
Total test boards: 164
* Corresponding board identification numbers are listed in Appendix A.
Following assembly, the performance characteristics of the assembled boards will be tested. Testing
will include Circuit Electrical Performance testing and Circuit Reliability Testing.
F-102
-------
APPENDIX F
Circuit Electrical Performance
This test assesses the circuit performance of a functional test vehicle under applicable environmental
stress. The assembled test vehicles will be exposed to 85 0 C at 85% relative humidity for 3 weeks.
The assemblies will be tested prior to exposure, and at the end of three weeks of exposure. Good
experimental design practices will be followed to control extraneous sources of variation. For
example, the assemblies will be placed randomly in the test chamber. If all assemblies cannot be
accommodated in the test chamber at the same time, they will be randomized to maintain balance
among the experimental factors at each test time. A staggered ramp will be used to prevent
condensation (during ramp-up, the temperature will be raised to test level before the humidity is raised
and the procedure will be reversed during ramp-down). The pre-tests and post-tests will be identical.
Circuit Reliability Testing
The same test vehicles used to test circuit electrical performance will be used for the circuit reliability
tests, which include:
Thermal Shock
Mechanical Shock
The electrical functionality of the LRSTF PWA will be evaluated through 23 electrical responses, as
follows:
HCLVPTH voltage
HCLV SMT voltage
Stranded wire 1 voltage
Stranded wire 2 voltage
HVLC PTH current
HVLC SMT current
10-mil spaced pads current leakage
PGA A current leakage
PGA B current leakage
Gull wing current leakage
HSD PTH total propagation delay
HSD SMT total propagation delay
Table 2 shows the total number of electrical
HF LPF PTH 50 MHz response
HF LPF PTH frequency response at -3 dB
HF LPF PTH frequency response at -40 dB
HP LPF SMT 50 MHz response
HF LPF SMT frequency response at -3 dB
HF LPF SMT frequency response at -40 dB
HF TLC 50 MHz forward response
HF TLC 500 MHz forward response
HF TLC 1000 MHz forward response
HF TLC reverse null frequency
HF TLC reverse null response
that will be measured.
Table 2. Number of Tests to be Conducted
Test Environment
Number of
Number of Test
Number of
Number of Electrical
PWBs
Times
Tests
Responses Measured
85/85
164
2
164x2 = 328
164x2x23 = 7,544
Thermal Shock
1
164x1 = 164
164x 1 x23 = 3,772
Mechanical Shock
1
164 x 1 = 164
164x 1 x23 = 3,722
Totals
164
4
656
15,088
F-103
-------
APPENDIX F
G. Analyze Data and Present Results
The details of the data analysis and results are presented in the "Technical Proposal for this project, in
Appendix B.
III. PERFORMANCE DEMONSTRATION PARTICIPANT REQUIREMENTS
A. From the Facilities/Process Operators:
1. Participating facilities were contacted by the project observer to arrange a convenient data for the
performance demonstration. The observer sent a fact sheet describing the facility's role in the
project.
2. Each facility was asked to complete a background questionnaire prior to the scheduled date of the
performance demonstration and return it to the observer.
3. Each facility was asked to make its process line/process operators available to run the 24 test
boards on the agreed upon date.
4. The process operator met with the independent observer before running the test boards through the
line to explain the unique aspects of the line to the observer. The process operator was asked to be
available to assist the independent observer in collecting information about the line.
B. From the Suppliers of the Process Line Alternatives:
1. Suppliers were asked to submit product data sheets, on which they provided information on
product formulations, product constraints, recommended disposal/treatment etc. The information,
including chemical formulation information, was requested prior to testing. Any proprietary
information was submitted to the University of Tennessee as Confidential Business Information.
2. Suppliers were asked to identify and contact the demonstration sites.
3. Suppliers were asked to attend the on-site performance demonstration if they wishes to do so, but
they were not required to attend.
Attachment A to this Methodology lists "Identification Numbers for Assembled Boards." To
conserve space this information as not been reprinted as part of the CTSA.
Attachment B to this Methodology is the "Technical/Management Proposal for Validation of
Alternatives to Lead Containing Surface Finishes." This Attachment contains the testing and analysis
methodology submitted by Dr. Ronald L. Inman, President, Southwest Technology Consultants in
Albuquerque, MN. Dr. Inman's methodology and results are presented in Chapter 6 of the CTSA and
in Appendix F, and therefore, Attachment B of the Methodology is not repeated here.
F-104
-------
Appendix G
Supplemental Cost Analysis Information
-------
G-l Example Graphic Representation of Cost Simulation Model
G-2 Bath Replacement Criteria for Surface Finishing Processes
G-3 Bills of Activities for Surface Finishing Processes
G-4 Simulation Model Outputs for Surface Finishing Processes
G-5 Chemical Costs by Bath for Individual Surface Finishing Processes
G-6 Total Materials Cost for Surface Finishing Processes
G-l
-------
G-l. Example Graphic Representation of Cost Simulation Model
G-2
-------
G-2 Bath Replacement Criteria for Surface Finishing Processes
'rocess: HASL
Chemical liatli
liatli Replacement Criteria
(ssl7»al)
Cleaner
750
Microetch
570
Flux
NAb
Solder
NAb
" Values were selected by averaging the replacement criteria for similar bath types from other alternatives.
b This bath is refilled or continuously maintained through chemical additions rather than replaced. The number of bath
replacements was set at one to reflect the initial bath make-up for the purposes of the computer simulation.
'rocess: Electroless Nickel/Immersion Gold
Chemical liatli
liatli Replacement Criteria
(ssl7»al)
Cleaner
750
Microetch
570
Catalyst
830
Acid Dip
1,500
Electroless Nickel
130
Immersion Gold
890
" Values were determined from data provided by two electroless nickel/immersion gold suppliers. To convert to units of racks per
bath replacement for non-conveyorized processes, multiply by 51.1 gallons and divide by 84.4 ssf/rack.
'rocess: Electroless Nickel/Electroless Palladium/Immersion Gold
Chemical liatli
liatli Replacement Criteria
(ssl7»al)
Cleaner
750
Microetch
570
Catalyst
830
Acid Dip
1,500
Electroless Nickel
130
Preinitiator
1,200
Electroless Palladium
150
Immersion Gold
890
" Values were determined from data provided by two electroless nickel/immersion gold suppliers and one electroless
nickel/palladium/immersion gold supplier. To convert to units of racks per bath replacement for non-conveyorized processes,
multiply by 51.1 gallons and divide by 84.4 ssf/rack.
G-3
-------
'rocess: OSP
Chemical Bath
Bath Replacement Criteria'
(ssf/gal)
Cleaner
750
Microetch
570
OSP
NAb
" Values were determined from data provided by two OSP suppliers. To convert to units of racks per bath replacement for non-
conveyorized processes, multiply by 51.1 gallons and divide by 84.4 ssf/rack. To convert to units of panels per bath replacement
for conveyorized process, multiply by the size of the bath in gallons and divide by 5.66 ssf/panel.
' This bath is refilled or continuously maintained through chemical additions rather than replaced. The number of bath
replacements was set at one to reflect the initial bath make-up for the purposes of the computer simulation.
'rocess: Immersion Silver
Chemical Bath
Bath Replacement Criteria'
(ssf/gal)
Cleaner
750
Microetch
570
Predip
1,000
Immersion Silver
NAb
" Values were determined from data provided by two OSP suppliers. To convert to units of panels per bath replacement for
conveyorized process, multiply by the size of the bath in gallons and divide by 5.66 ssf/panel.
' This bath is refilled or continuously maintained through chemical additions rather than replaced. The number of bath
replacements was set at one to reflect the initial bath make-up for the purposes of the computer simulation.
'rocess: Immersion Tin
Chemical Bath
Bath Replacement Criteria'
(ssf/gal)
Cleaner
750
Microetch
570
Predip
1,250
Immersion Tin
NAb
" Values were determined from data provided by two OSP suppliers. To convert to units of racks per bath replacement for non-
conveyorized processes, multiply by 51.1 gallons and divide by 84.4 ssf/rack. To convert to units of panels per bath replacement
for conveyorized process, multiply by the size of the bath in gallons and divide by 5.66 ssf/panel.
' This bath is refilled or continuously maintained through chemical additions rather than replaced. The number of bath
replacements was set at one to reflect the initial bath make-up for the purposes of the computer simulation.
G-4
-------
G-3 Bills of Activities for Surface Finishing Processes
Activities Associated with the Bath Setup
\ili\il\ Ih-a'iplioii
( iin| Driwr
(
-------
Activities Associated with the Tank Cleanup
\ili\il\ Ih-a'iplioii
( iin| |)mfi-
(
-------
Activities Associated with Sampling and Testing
\ili\il\ Ih-a'iplioii
( iin| |)mfi-
(
-------
Activities Associated with Filter Replacement
\ili\il\ Ih-a'iplioii
( iin| |)mfi-
(
-------
Activities Associated with Transportation
\ili\il\ Ih-a'iplioii
( iin| |)mfi-
(
-------
G-4 Simulation Model Outputs for Surface Finishing Processes
NAME:
Throughput:
HASL, non-conveyorized
260,000K ssf
ARENA Simulation Results
Replication ended at time: 17831.4 min.
Tally Variables
Identifier Average Half Width Minimum
Maximum
Observations
Takt Time
Time in system
Counters
Identifier
Parts Done
Frequencies
Identifier
5.7866
19.957
Count
3081
(Corr)
4.8613
Limit
Infinite
1.4700
7.9560
141.10
168.71
3080
3081
Category
Number
AvgTime
Percent
Percent
STATE (Microetch3_R)
STATE (Cleaner3_R)
STATE (flux3_R)
STATE (solder3_R)
BUSY
IDLE
FAILED
BUSY
IDLE
FAILED
BUSY
IDLE
FAILED
BUSY
IDLE
FAILED
3075
3075
9
2251
2250
7
3081
3082
1
3081
3082
1
1.4728
3.9279
136.00
4.7494
2.7503
136.00
.18000
5.5615
136.00
.12600
5.6155
136.00
25.40
67.74
6.86
59.96
34.70
5.34
3.11
96.13
0.76
2.18
97.06
0.76
25.40
67.74
6.86
59.96
34.70
5.34
3.11
96.13
0.76
2.18
97.06
0.76
G-10
-------
NAME:
Throughput:
HASL, non-conveyorized
60,000K ssf
ARENA Simulation Results
Replication ended at time: 2876.64 min.
Tally Variables
Identifier Average Half Width Minimum
Maximum
Observations
Takt Time
Time in system
Counters
Identifier
Parts Done
Frequencies
Identifier
3.8531
89.058
Count
711
.69813
(Corr)
Limit
Infinite
3.4700
7.9560
139.47
279.95
710
711
Category
Number
AvgTime
Percent
Percent
STATE (Microetch3_R)
STATE (Cleaner3_R)
STATE (flux3_R)
STATE (solder3_R)
BUSY
IDLE
FAILED
BUSY
IDLE
FAILED
BUSY
IDLE
FAILED
BUSY
IDLE
FAILED
577
575
3
3
1
2
711
712
1
711
712
1
1.8113
2.4756
136.00
822.39
137.47
136.00
.18000
3.6694
136.00
.12600
3.7233
136.00
36.33
49.48
14.18
85.77
4.78
9.46
4.45
90.82
4.73
3.11
92.16
4.73
36.33
49.48
14.18
85.77
4.78
9.46
4.45
90.82
4.73
3.11
92.16
4.73
G-ll
-------
NAME:
Throughput:
HASL, conveyorized
60,000K ssf
ARENA Simulation Results
Replication ended at time: 2348.82 min.
Tally Variables
Identifier Average Half Width Minimum
Maximum
Observations
Takt time
Time in system
Counters
Identifier
Depart 33_C
Frequencies
Identifier
.19281
19.009
Count
10601
.02704
(Corr)
Limit
Infinite
.16654
4.9888
136.00
140.82
10600
10601
Category
Number
AvgTime
Percent
Percent
STATE (Cleaner R)
STATE (solder R)
STATE (flux R)
STATE (Microetch R)
BUSY
IDLE
FAILED
BUSY
IDLE
FAILED
BUSY
IDLE
FAILED
BUSY
IDLE
FAILED
9825
9823
2
10601
10601
1
10601
10601
1
10601
10601
1
.00539
.17549
136.00
.00500
.17544
136.00
.00500
.17544
136.00
.00500
.17544
136.00
2.59
84.14
13.28
2.59
90.77
6.64
2.59
90.77
6.64
2.59
90.77
6.64
2.59
84.14
13.28
2.59
90.77
6.64
2.59
90.77
6.64
2.59
90.77
6.64
G-12
-------
NAME:
Throughput:
HASL, conveyorized
260,000K ssf
ARENA Simulation Results
Replication ended at time: 8908.24 min.
Tally Variables
Identifier
Average
Half Width Minimum
Maximum
Observations
Time in system
Takt time
Counters
Identifier
Depart 33_C
Frequencies
Identifier
21.188
.18000
Count
45936
10.277
(Corr)
Limit
Infinite
4.9888
.16654
140.91
136.00
45936
45935
Category
Number
AvgTime
Percent
Percent
STATE (Cleaner R)
STATE (solder R)
STATE (Microetch R)
STATE (flux R)
BUSY
IDLE
FAILED
BUSY
IDLE
FAILED
BUSY
IDLE
FAILED
BUSY
IDLE
FAILED
42056
42051
6
45936
45936
1
45936
45932
6
45936
45937
1
.00546
.17506
136.00
.00500
.17506
136.00
.00500
.16027
136.00
.00500
.17506
136.00
2.73
87.56
9.71
2.73
95.65
1.62
2.73
87.56
9.71
2.73
95.65
1.62
2.73
87.56
9.71
2.73
95.65
1.62
2.73
87.56
9.71
2.73
95.65
1.62
G-13
-------
NAME:
Throughput:
Nickel/Palladium/Gold, non-conveyorized
260,000K ssf
ARENA Simulation Results
Replication ended at time: 114576.0 min.
Tally Variables
Identifier Average Half Width Minimum
Maximum
Observations
Time in system
Takt Time
Counters
Identifier
Parts Done
Frequencies
116.79
38.848
Count
3081
1.0484
(Corr)
Limit
Infinite
106.86
17.830
278.21
131.33
308
3080
Identifier
Category
Number
AvgTime
Percent
Percent
STATE (Acid Dip R)
BUSY
3073
1.6342
4.19
4.19
IDLE
3070
37.226
95.43
95.43
FAILED
4
113.00
0.38
0.38
STATE (Catalyst R)
BUSY
3075
3.7372
9.60
9.60
IDLE
3070
35.045
89.84
89.84
FAILED
6
113.00
0.57
0.57
STATE (Cleaner R)
BUSY
3069
3.4835
8.93
8.93
IDLE
3062
35.362
90.41
90.41
FAILED
7
113.00
0.66
0.66
STATE (Electroless Palla
BUSY
3008
4.7321
11.89
11.89
IDLE
2975
34.179
84.91
84.91
FAILED
34
113.00
3.21
3.21
STATE (Immersion Gold R
BUSY
2803
19.598
45.87
45.87
IDLE
2798
22.926
53.56
53.56
FAILED
6
113.00
0.57
0.57
STATE (Preinitiator R)
BUSY
3081
2.3000
5.92
5.92
IDLE
3082
36.375
93.61
93.61
FAILED
5
113.00
0.47
0.47
STATE (Electroless Nicke
BUSY
2872
19.663
47.16
47.16
IDLE
2833
20.743
49.07
49.07
FAILED
40
113.00
3.77
3.77
STATE (Microetch R)
BUSY
3064
1.4781
3.78
3.78
IDLE
3056
37.373
95.37
95.37
FAILED
9
113.00
0.85
0.85
G-14
-------
NAME:
Throughput:
Nickel/Palladium/Gold, non-conveyorized
60,000K ssf
ARENA Simulation Results
Replication ended at time: 25807.8 min.
Tally Variables
Identifier Average Half Width Minimum
Maximum
Observations
Time in system
Takt Time
Counters
Identifier
Parts Done
Frequencies
115.87
38.929
Count
711
1.7495
(Corr)
Limit
Infinite
106.86
17.830
199.39
131.33
711
710
Identifier
Category
Number
AvgTime
Percent
Percent
STATE (Acid Dip R)
BUSY
711
1.6300
4.17
4.17
IDLE
712
37.269
95.43
95.43
FAILED
1
113.00
0.41
0.41
STATE (Cleaner R)
BUSY
709
3.4797
8.87
8.87
IDLE
707
35.522
90.32
90.32
FAILED
2
113.00
0.81
0.81
STATE (Catalyst R)
BUSY
707
3.7511
9.54
9.54
IDLE
706
35.311
89.65
89.65
FAILED
2
113.00
0.81
0.81
STATE (Electroless Palla
BUSY
695
4.7263
11.81
11.81
IDLE
688
34.329
84.94
84.94
FAILED
8
113.00
3.25
3.25
STATE (Immersion Gold R
BUSY
652
19.443
45.59
45.59
IDLE
651
22.895
53.60
53.60
FAILED
2
113.00
0.81
0.81
STATE (Preinitiator R)
BUSY
711
2.3000
5.88
5.88
IDLE
711
36.651
93.71
93.71
FAILED
1
113.00
0.41
0.41
STATE (Electroless Nicke
BUSY
670
19.451
46.87
46.87
IDLE
663
20.751
49.48
49.48
FAILED
9
113.00
3.66
3.66
STATE (Microetch R)
BUSY
707
1.4783
3.76
3.76
IDLE
706
37.427
95.02
95.02
FAILED
3
113.00
1.22
1.22
G-15
-------
NAME:
Throughput:
Nickel/Gold, non-conveyorized
260,000K ssf
ARENA Simulation Results
Replication ended at time: 86437.5 min.
Tally Variables
Identifier Average Half Width Minimum
Maximum
Observations
Takt Time
Time in system
Counters
Identifier
Parts Done
Frequencies
Identifier
27.062
98.948
Count
3081
1.2220E-14
2.0602
Limit
Infinite
17.830
86.100
134.33
286.16
3080
3081
Category
Number
AvgTime
Percent
Percent
STATE (Microetch2_R)
STATE (Acid Dip2_R)
BUSY
IDLE
FAILED
BUSY
IDLE
FAILED
STATE (Electroless Nickel) BUSY
IDLE
FAILED
STATE (Cleaner2_R)
STATE (Catalyst2_R)
BUSY
IDLE
FAILED
BUSY
IDLE
FAILED
STATE (Immersion Gold2_ BUSY
IDLE
FAILED
3056
3048
9
3068
3065
4
2448
2409
40
3063
3056
7
3067
3062
6
2966
2961
6
1.4820
25.546
116.00
1.6369
25.432
116.00
23.069
9.2664
116.00
3.4903
23.538
116.00
3.7470
23.268
116.00
18.521
9.3911
116.00
5.43
93.32
1.25
6.02
93.42
0.56
67.69
26.75
5.56
12.81
86.21
0.97
13.77
85.39
0.83
65.84
33.33
0.83
5.43
93.32
1.25
6.02
93.42
0.56
67.69
26.75
5.56
12.81
86.21
0.97
13.77
85.39
0.83
65.84
33.33
0.83
G-16
-------
NAME:
Throughput:
Nickel/Palladium/Gold, non-conveyorized
60,000K ssf
ARENA Simulation Results
Replication ended at time: 19427.7 min.
Tally Variables
Identifier Average Half Width Minimum
Maximum
Observations
Takt Time
Time in system
Counters
Identifier
Parts Done
Frequencies
Identifier
27.150
95.321
Count
711
(Corr)
4.1505
Limit
Infinite
17.830
86.100
134.33
193.43
710
711
Category
Number
AvgTime
Percent
Percent
STATE (Electroless Nicke
STATE (Acid Dip2_R)
STATE (Microetch2_R)
STATE (Cleaner2_R)
STATE (Catalyst2_R)
BUSY
IDLE
FAILED
BUSY
IDLE
FAILED
BUSY
IDLE
FAILED
BUSY
IDLE
FAILED
BUSY
IDLE
FAILED
STATE (Immersion Gold2_ BUSY
IDLE
FAILED
605
597
9
711
712
1
705
704
3
708
706
2
711
710
2
684
683
2
21.541
8.9632
116.00
1.6300
25.495
116.00
1.4825
25.617
116.00
3.4847
23.694
116.00
3.7300
23.300
116.00
18.533
9.5440
116.00
67.08
27.54
5.37
5.97
93.44
0.60
5.38
92.83
1.79
12.70
86.11
1.19
13.65
85.16
1.19
65.25
33.55
1.19
67.08
27.54
5.37
5.97
93.44
0.60
5.38
92.83
1.79
12.70
86.11
1.19
13.65
85.16
1.19
65.25
33.55
1.19
G-17
-------
NAME:
Throughput:
OSP, non-conveyorized
260,000K ssf
ARENA Simulation Results
Replication ended at time: 14371.9 min.
Tally Variables
Identifier Average Half Width Minimum
Maximum
Observations
Takt Time
Time in System
Counters
Identifier
Depart 7_C
Frequencies
Identifier
4.7599
399.53
Count
3081
.59985
(Corr)
Limit
Infinite
4.6200
21.330
150.67
513.90
3080
3081
Category
Number
AvgTime
Percent
Percent
STATE (Cleaner R)
STATE (Osp R)
STATE (Microetch R)
BUSY
IDLE
FAILED
BUSY
IDLE
FAILED
BUSY
IDLE
FAILED
2301
2294
7
3081
3081
1
2711
2703
9
4.6462
1.2850
149.00
1.6700
3.0469
149.00
1.6706
3.2600
149.00
72.82
20.08
7.10
35.04
63.94
1.01
30.85
60.02
9.13
72.82
20.08
7.10
35.04
63.94
1.01
30.85
60.02
9.13
G-18
-------
NAME:
Throughput:
OSP, non-conveyorized
60,000K ssf
ARENA Simulation Results
Replication ended at time: 3731.92 min.
Tally Variables
Identifier Average Half Width Minimum
Maximum
Observations
Takt Time
Time in System
Counters
Identifier
Depart 7_C
Frequencies
Identifier
5.0236
172.58
Count
711
.57885
(Corr)
Limit
Infinite
4.6200
21.330
150.47
322.15
710
711
Category
Number
AvgTime
Percent
Percent
STATE (Cleaner R)
STATE (Osp R)
STATE (Microetch R)
BUSY
IDLE
FAILED
BUSY
IDLE
FAILED
BUSY
IDLE
FAILED
581
579
2
711
711
1
619
618
3
4.2464
1.6696
149.00
1.6700
3.3692
149.00
1.6884
3.6241
149.00
66.11
25.90
7.99
31.82
64.19
3.99
28.01
60.02
11.98
66.11
25.90
7.99
31.82
64.19
3.99
28.01
60.02
11.98
G-19
-------
NAME:
Throughput:
OSP, conveyorized
260,000K ssf
ARENA Simulation Results
Replication ended at time: 6568.83 min.
Tally Variables
Identifier Average Half Width Minimum
Maximum
Observations
Takt time
Time in system
Counters
Identifier
Depart 22_C
Frequencies
Identifier
.14724
30.442
Count
45937
.01562
14.465
Limit
Infinite
.13961
5.1777
149.00
154.12
45936
45937
Category
Number
AvgTime
Percent
Percent
STATE (Microetch2_R)
STATE (Cleaner2_R)
STATE (osp_R)
BUSY
IDLE
FAILED
BUSY
IDLE
FAILED
BUSY
IDLE
FAILED
45937
45932
6
40587
40582
6
45937
45937
1
.00500
.12290
149.00
.00566
.13910
149.00
.00500
.13911
149.00
3.39
83.40
13.21
3.39
83.40
13.21
3.39
94.41
2.20
3.39
83.40
13.21
3.39
83.40
13.21
3.39
94.41
2.20
G-20
-------
NAME:
Throughput:
OSP, conveyorized
60,000K ssf
ARENA Simulation Results
Replication ended at time: 2002.0 min.
Tally Variables
Identifier Average Half Width Minimum
Maximum
Observations
Takt Time
Time in System
Counters
Identifier
Depart 22_C
Frequencies
Identifier
.15805
27.077
Count
10601
.03019
(Corr)
Limit
Infinite
.1356
5.1777
149.00
154.07
1060
10600
Category Number AvgTime Percent
Percent
STATE (Microetch2_R)
STATE (Cleaner2_R)
STATE (OSP R)
BUSY
IDLE
FAILED
BUSY
IDLE
FAILED
BUSY
IDLE
FAILED
10601
10601
1
9531
9530
2
10601
10601
1
.00500
.16979
149.00
.00556
.17324
149.00
.00500
.16979
149.00
2.65
89.91
7.44
2.65
82.47
14.89
2.65
89.91
7.44
2.65
89.91
7.44
2.65
82.47
14.89
2.65
89.91
7.44
G-21
-------
NAME:
Throughput:
Immersion Silver, conveyorized
60,000K ssf
ARENA Simulation Results
Replication ended at time: 5425.08 min.
Tally Variables
Identifier
Average
Half Width Minimum
Maximum
Observations
Time in System
Takt time
Counters
Identifier
depart 44_C
Frequencies
Identifier
14.998
.51074
Count
10601
5.9815
(Corr)
Limit
Infinite
11.189
.48953
125.07
113.99
10601
10600
Category
Number
AvgTime
Percent
Percent
STATE (Microetch3_R)
STATE (Cleaner3_R)
STATE (Immersion Silver)
STATE (prodip R)
BUSY
IDLE
FAILED
BUSY
IDLE
FAILED
BUSY
IDLE
FAILED
BUSY
IDLE
FAILED
10601
10601
1
10372
10370
2
10601
10601
1
10601
10600
2
.00500
.49600
114.00
.00511
.49605
114.00
.00500
.49600
114.00
.00500
.48529
114.00
0.98
96.92
2.10
0.98
94.82
4.20
0.98
96.92
2.10
0.98
94.82
4.20
0.98
96.92
2.10
0.98
94.82
4.20
0.98
96.92
2.10
0.98
94.82
4.20
G-22
-------
NAME:
Throughput:
Immersion Silver, conveyorized
260,000K ssf
ARENA Simulation Results
Replication ended at time: 26206.7 min.
Tally Variables
Identifier Average Half Width Minimum
Maximum
Observations
Time in System
Takt Time
Counters
Identifier
depart 44_C
Frequencies
Identifier
18.921
.50495
Count
45937
4.1632
(Corr)
Limit
Infinite
11.189
.48995
238.69
114.03
45937
45936
Category
Number
AvgTime
Percent
Percent
STATE (Microetch3_R)
STATE (Cleaner3_R)
STATE (Immersion Silver)
STATE (prodip R)
BUSY
IDLE
FAILED
BUSY
IDLE
FAILED
BUSY
IDLE
FAILED
BUSY
IDLE
FAILED
45937
45932
6
44792
44786
6
45937
45937
1
45021
45017
5
.00500
.48535
114.00
.00513
.49777
114.00
.00500
.49770
114.00
.00510
.49775
114.00
0.99
96.06
2.95
0.99
96.06
2.95
0.99
98.52
0.49
0.99
96.55
2.46
0.99
96.06
2.95
0.99
96.06
2.95
0.99
98.52
0.49
0.99
96.55
2.46
G-23
-------
NAME:
Throughput:
Immersion Tin, non-conveyorized
260,000K ssf
ARENA Simulation Results
Replication ended at time: 30669.2 min.
Tally Variables
Identifier Average Half Width Minimum
Maximum
Observations
Takt Time
Time in System
Counters
Identifier
Depart 7_C
Frequencies
Identifier
9.8516
40.215
Count
3081
(Corr)
4.5278
Limit
Infinite
8.5500
26.010
93.550
185.18
3080
3081
Category
Number
AvgTime
Percent
Percent
STATE (Cleaner R)
STATE (predip R)
BUSY
IDLE
FAILED
BUSY
IDLE
FAILED
STATE (Immersion Tin R) BUSY
IDLE
FAILED
STATE (Microetch R)
BUSY
IDLE
FAILED
3009
3002
7
3049
3045
5
2003
2003
1
3008
3000
9
3.5530
6.3568
85.000
1.1822
8.6500
85.000
13.151
1.9678
85.000
1.5056
8.3583
85.000
35.20
62.84
I.96
II.87
86.73
1.40
86.74
12.98
0.28
14.91
82.57
2.52
35.20
62.84
I.96
II.87
86.73
1.40
86.74
12.98
0.28
14.91
82.57
2.52
G-24
-------
NAME:
Throughput:
Immersion Tin, non-conveyorized
60,000K ssf
ARENA Simulation Results
Replication ended at time: 7144.18 min.
Tally Variables
Identifier Average Half Width Minimum
Maximum
Observations
Takt Time
Time in System
Counters
Identifier
Depart 7_C
Frequencies
Identifier
9.9108
36.380
Count
711
.36935
7.8297
Limit
Infinite
8.5500
26.010
88.470
104.68
710
711
Category
Number
AvgTime
Percent
Percent
STATE (Cleaner R)
STATE (Predip R)
BUSY
IDLE
FAILED
BUSY
IDLE
FAILED
STATE (Immersion Tin R) BUSY
IDLE
FAILED
STATE (Microetch R)
BUSY
IDLE
FAILED
699
697
2
711
712
1
527
527
1
693
692
3
3.5295
6.4663
85.000
I.1700
8.7462
85.000
II.535
1.8598
85.000
1.5081
8.4451
85.000
34.53
63.09
2.38
11.64
87.17
1.19
85.09
13.72
1.19
14.63
81.80
3.57
34.53
63.09
2.38
11.64
87.17
1.19
85.09
13.72
1.19
14.63
81.80
3.57
G-25
-------
NAME:
Throughput:
Immersion Tin, conveyorized
260,000K ssf
ARENA Simulation Results
Replication ended at time: 43501.6 min.
Tally Variables
Identifier Average Half Width Minimum
Maximum
Observations
Takt Time
Time in System
Counters
Identifier
Depart 22_C
Frequencies
Identifier
.95367
21.375
Count
45937
(Corr)
(Corr)
Limit
Infinite
.93728
12.350
85.005
160.23
45936
45937
Category Number AvgTime Percent
Percent
STATE (Microetch2_R)
STATE (Cleaner2_R)
STATE (Predip R)
BUSY
IDLE
FAILED
BUSY
IDLE
FAILED
BUSY
IDLE
FAILED
STATE (Immersion Tin R) BUSY
IDLE
FAILED
45936
45931
6
45487
45481
6
45576
45572
5
45937
45937
1
.00500
.91794
85.000
.00505
.92702
85.000
.00504
.92704
85.000
.00500
.92707
85.000
0.54
98.28
1.19
0.54
98.28
1.19
0.54
98.47
0.99
0.54
99.27
0.20
0.54
98.28
1.19
0.54
98.28
1.19
0.54
98.47
0.99
0.54
99.27
0.20
G-26
-------
NAME:
Throughput:
Immersion Tin, conveyorized (Tin h 60)
60,000K ssf
ARENA Simulation Results
Replication ended at time: 10029.78 min.
Tally Variables
Identifier Average Half Width Minimum
Maximum
Observations
Takt Time
Time in Systerrm
Counters
Identifier
Depart 22_C
Frequencies
Identifier
.95796
23.910
Count
10601
(Corr)
(Corr)
Limit
Infinite
.93728
12.364
85.260
110.71
10600
10601
Category Number AvgTime Percent
Percent
STATE (Microetch2_R)
STATE (Cleaner2_R)
STATE (Predip R)
BUSY
IDLE
FAILED
BUSY
IDLE
FAILED
BUSY
IDLE
FAILED
STATE (Immersion Tin R) BUSY
IDLE
FAILED
10601
10601
1
10476
10475
2
10601
10600
2
10601
10601
1
.26000
.67102
85.000
.26310
.67098
85.000
.26000
.66307
85.000
.26000
.67102
85.000
27.69
71.46
0.85
27.69
70.60
1.71
27.69
70.60
1.71
27.69
71.46
0.85
27.69
71.46
0.85
27.69
70.60
1.71
27.69
70.60
1.71
27.69
71.46
0.85
G-27
-------
G-5 Chemical Costs by Bath for Individual Surface Finish Processes
G-28
-------
*rocess: Hot Air Solder Leveling (HASL)a
Bath
Volume in Bath
Volume in Bath
Supplier
Unit Vol.
Avg.
Total Cost of
Total Cost of
(in gallons)
Horizontal
(in gallons)
Vertical
ID
Chemical
Cost
Chemical
Cost
the Bath
(Horizontal)
the Bath
(Vertical)
Cleaner
66.5
51.1
#1
$14.4/gal
$3.67/gal
$244
$188
#2
$5,42/gal
#3
$1.38/gal
#4
$1.13/gal
#5
$2.50/gal
#6
$1.00/gal
#7
$1.02/gal
#8
$2.50/gal
Microetch
86.6
51.1
#1
$1.43/gal
$3.86/gal
$344
$197
#2
$2.14/gal
#3
$0.757/gal
#4
$9.88/gal
#5
$5,20/gal
#6
$5,20/gal
#7
$1.05/gal
#8
$5,20/gal
Flux
NA
NA
$12.50/gal
$12.50/galb
$12.50/gal b
a No suppliers of HASL were identified. Chemical costs for baths similar to other alternatives were calculated by averaging the individual bath costs from other
alternatives.
b Flux is refilled as it is consumed. The flux cost per gallon was obtained by industry estimate. (Personal communication with Mark Carey, February, 2000.)
G-29
-------
Process: Immersion Silver
Supplier #1
Bath
Volume in Bath
(in gallons)
Horizontal
Volume in Bath
(in gallons)
Vertical
Chemical
Name
Percentage of
Chemical in
Bath
Cost of
Chemicals
Multiplying
Factor
Total Cost
of the Bath
(Horizontal)
Total Cost
of the Bath
(Vertical)
Cleaner
66.5
No data
A
100
$14.4/gal
1
$958
No data
Microetch
86.6
No data
B
5
$26.6/gal
1
$124
No data
C
0.25
$1.20/gal
1
D
10
$1.00/gal
1
Predip
46.2
No data
E
100
$26.0/gal
1
$1,200
No data
Immersion Silver
NA
No data
F
90
$26.0/gal
1
$30.9/gala
No data
G
10
$75.0/gal
1
a The silver bath is not replaced, but rather maintained as it becomes depleted. The total material cost of the silver bath required to produce 260,000 ssf of PWB
will be calculated directly from the price per gallon of bath solution and the total gallons of bath solution required.
G-30
-------
Process: Immersion Tin
Supplier #2
Bath
Volume in Bath
(in gallons)
Horizontal
Volume in Bath
(in gallons)
Vertical
Chemical
Name
Percentage of
Chemical in
Bath
Cost of
Chemicals
Multiplying
Factor
Total Cost
of the Bath
(Horizontal)
Total Cost
of the Bath
(Vertical)
Cleaner
66.5
51.1
A
7
$20.0/L
1
$360
$277
B
10
$1.20/gal
1
Microetch
86.6
51.1
C
1.25 lb/gal
$1.7 0/lb
1
$185
$109
D
1
$1.20/gal
1
Predip
46.2
51.1
E
0.5
$40.0/L
1
$34.9
$38.7
Immersion Tin
NA
NA
F
5
$1.20/gal
1
$166/gaP
$166/gaP
G
200 g/L
$40.0/kg
2.24
H
10
$40.0/L
3.48
I
5
$40.0/L
5.94
a The tin bath is not replaced, but rather maintained as it becomes depleted. The total material cost of the tin bath required to produce 260,000 ssf of PWB will be
calculated directly from the price per gallon of bath solution and the total gallons of bath solution required.
G-31
-------
Process: Immersion Tin
Supplier #3
Bath
Volume in Bath
(in gallons)
Horizontal
Volume in Bath
(in gallons)
Vertical
Chemical
Name
Percentage of
Chemical in
Bath
Cost of
Chemicals
Multiplying
Factor
Total Cost
of the Bath
(Horizontal)
Total Cost
of the Bath
(Vertical)
Cleaner
66.5
51.1
A
12.5
$11.0/gal
1
$91.4
$70.3
Microetch
86.6
51.1
B
60 g/L
$1.49/lb
1
$65.6
$38.7
C
1
$1.20/gal
1
Predip
46.2
51.1
D
25
$100/gal
1
$1,160
$1,280
Immersion
Tin
NA
NA
E
100
$100/gal
1
$100/gaP
$100/gaP
a The tin bath is not replaced, but rather maintained as it becomes depleted. The total material cost of the tin bath required to produce 260,000 ssf of PWB will be
calculated directly from the price per gallon of bath solution and the total gallons of bath solution required.
G-32
-------
Process: Electroless Nickel/Immersion Gold
Supplier #4
Bath
Volume in
Bath (in
gallons)
Horizontal
Volume in
Bath (in
gallons)
Vertical
Chemical
Name
Percentage of
Chemical in
Bath
Cost of
Chemicals
Multiplying
Factor
Total Cost
of the Bath
(Horizontal)
Total Cost
of the Bath
(Vertical)
Cleaner
No data
51.1
A
15
$7.50/gal
1
No data
$57.5
Microetch
No data
51.1
B
1.88 lb/gal
$5.25/lb
1
No data
$505
C
1
$1.20/gal
1
Catalyst
No data
51.1
D
10
$40.0/gal
1
No data
$467
E
17
$8.00/L
1
Acid Dip
No data
51.1
F
40
$8.00/L
1
No data
$619
Electroless Nickel
No data
51.1
G
5
$14.5/gal
5
No data
$574
H
15
$20.0/gal
1
J
5
$23.0/gal
4
Immersion Gold
No data
51.1
K
0.250 unit/gal
(225 mL/gal)
$344/unit
1
No data
$58,500a
L
8 oz/gal
$3.25/lb
1
a Immersion gold replacement cost was calculated differently than other baths because of the wide disparity in costs and throughput between product lines. The
overall cost for the gold bath was calculated for each product line and then averaged together to give the gold cost for the process.
G-33
-------
Process: Electroless Nickel/Immersion Gold
Supplier #5
Bath
Volume in
Volume in
Chemical
Percentage of
Cost of
Multiplying
Total Cost
Total Cost
Bath (in
Bath (in
Name
Chemical in
Chemicals
Factor
of the Bath
of the Bath
gallons)
Horizontal
gallons)
Vertical
Bath
(Horizontal)
(Vertical)
Cleaner
No data
51.1
A
10
$25.0/gal
1
No data
$128
Microetch
No data
51.1
B
3
$5,66/gal
1
No data
$266
C
3
$9.39/gal
1
D
45 g/L
$27.3/kg
1
E
8.5
$1.20/gal
1
Catalyst
No data
51.1
F
30
$127/gal
1
No data
$2,810
G
20
$54.0/gal
1
H
12
$51.0/gal
1
Acid Dip
No data
51.1
I
2 g/L
$29.1/kg
1
No data
$11.3
Electroless Nickel
No data
51.1
J
6.6
$24.1/gal
6
No data
$2,390
K
15
$30.9/gal
6
L
6.6
$28.4/gal
5
Immersion Gold
No data
51.1
M
50
$21.4/gal
1
No data
$57,350a
N
3 g/L
$40.0/g
3
a Immersion gold replacement cost was calculated differently than other baths because of the wide disparity in costs and throughput between product lines. The
overall cost for the gold bath was calculated for each product line and then averaged together to give the gold cost for the process.
G-34
-------
Process: OSP
Supplier #6
Bath
Volume in Bath
(in gallons)
Horizontal
Volume in Bath
(in gallons)
Vertical
Chemical
Name
Percentage of
Chemical in
Bath
Cost of
Chemicals
Multiplying
Factor
Total Cost
of the Bath
(Horizontal)
Total Cost
of the Bath
(Vertical)
Cleaner
66.5
51.1
A
10
$10.0/gal
1
$66.5
$51.1
Microetch
86.6
51.1
B
3
$5.66/gal
1
$451
$261
C
3
$9.39/gal
1
D
45.0 g/L
$27.3/kg
1
E
8.5
$1.20/gal
1
OSP
NA
NA
F
6
$324/gal
1
$93.6/gala
$93.6/gala
G
23
$321/gal
1
a The OSP bath is not replaced, but rather maintained as it becomes depleted. The total material cost of the OSP bath required to produce 260,000 ssf of PWB
will
be calculated directly from the price per gallon of bath solution and the total gallons of bath solution required.
G-35
-------
Process: OSP
Supplier #7
Bath
Volume in Bath
(in gallons)
Horizontal
Volume in Bath
(in gallons)
Vertical
Chemical
Name
Percentage of
Chemical in
Bath
Cost of
Chemicals
Multiplying
Factor
Total Cost
of the Bath
(Horizontal)
Total Cost
of the Bath
(Vertical)
Cleaner
66.5
51.1
A
10
$10.2/gal
1
$67.8
$52.1
Microetch
86.6
51.1
B
2.5
$7.62/gal
1
$91.0
$53.7
C
7
$9.12/gal
1
D
18.5
$1.20/gal
1
OSP
NA
NA
E
100
$117/gal
1
$117/gal3
$117/gal3
a The OSP bath is not replaced, but rather maintained as it becomes depleted. The total material cost of the OSP bath required to produce 260,000 ssf of PWB
will
be calculated directly from the price per gallon of bath solution and the total gallons of bath solution required.
G-36
-------
Process: Electroless Nickel/Electroless Palladium/Immersion Gold
Supplier #8
Bath
Volume in
Volume in
Chemical
Percentage
Cost of
Multiplying
Total Cost
Total Cost
Bath (in
Bath (in
Name
of Chemical
Chemicals
Factor
of the Bath
of the Bath
gallons)
Horizontal
gallons)
Vertical
in Bath
(Horizontal)
(Vertical)
Cleaner
No data
51.1
A
10
$25.0/gal
1
No data
$128
Microetch
No data
51.1
B
3
$5,66/gal
1
No data
$266
C
3
$9.39/gal
1
D
45 g/L
$27.3/kg
1
E
8.5
$1.20/gal
1
Catalyst
No data
51.1
F
30
$127/gal
1
No data
$2,810
G
20
$54.0/gal
1
H
12
$51.0/gal
1
Acid Dip
No data
51.1
I
2 g/L
$29.1/kg
1
No data
$11.3
Electroless Nickel
No data
51.1
J
6.6
$24.1/gal
6
No data
$2,390
K
15
$30.9/gal
6
L
6.6
$28.4/gal
5
Preinitiator
No data
51.1
M
20
$160/gal
1
No data
$2,430
N
10
$152/gal
1
0
1.4
$8.00/L
1
Electroless Palladium
No data
51.1
P
2.5
$943/gal
3
No data
$3,980
Q
20
$23.8/gal
1
R
2.5
$48.2/gal
2
S
0.05
$ 13.3/gal
3
Immersion Gold
No data
NA
T
50
$21.4/gal
1
No data
$57,900a
U
3 g/L
$40.0/g
3
a Immersion gold replacement cost was calculated differently than other baths because of the wide disparity in costs and throughput between product lines. The
overall cost for the gold bath was calculated for each product line and then averaged together to give the gold cost for the process.
G-37
-------
G-6 Total Materials Cost for Surface Finishing Processes
Process: HASL, non-conveyorized
Throughput: 260K ssf of PWB
Bath
Chemical Cost/Bath
Replacement'
Number of Bath
Replacements 1
Total Chemical Cost
Cleaner
$188
7
$1,320
Microetch
$197
9
$1,770
Flux
$16,250 c
1
$16,250
Solder
$55,460 d
1
$55,460
Total Materials Cost
$74,800
" Reported chemical cost per bath replacement reflects the average bath cost of all processes submitted for evaluation in this
surface finishing category.
' Number of bath replacements required to process 260,000 ssf as determined by process simulation.
' Flux bath is not replaced, but rather refilled as flux is consumed. Cost of flux was calculated at $12.50/gal and is consumed at
200 ssf/gal.
1 Solder is not replaced, but rather refilled as solder is consumed. Cost of solder was calculated using a solder cost of $2.57/lb
and an average solder consumption rate, including solder wastage, of 0.083 lb/ssf which was obtained from three PWB facilities.
Process: HASL, conveyorized
Throughput: 260K ssf of PWB
Bath
Chemical Cost/Bath
Replacement'
Number of Bath
Replacements 1
Total Chemical Cost
Cleaner
$244
6
$1,460
Microetch
$344
6
$2,060
Flux
$16,250 c
1
$16,250
Solder
$55,460 d
1
$55,460
Total Materials Cost
$75,200
" Reported chemical cost per bath replacement reflects the average bath cost of all processes submitted for evaluation in this
surface finishing category.
' Number of bath replacements required to process 260,000 ssf as determined by process simulation.
' Flux bath is not replaced, but rather refilled as flux is consumed. Cost of flux was calculated at $12.50/gal and is consumed at
200 ssf/gal.
1 Solder is not replaced, but rather refilled as solder is consumed. Cost of solder was calculated using a solder cost of $2.57/lb
and an average solder consumption rate, including solder wastage, of 0.083 lb/ssf which was obtained from three PWB facilities.
G-38
-------
Process: Electroless Nickel/Immersion Gold, non-conveyorized
Throughput: 260K ssf of PWB
liatli
Chemical Cost/liath
Replacement
Number of lialli
Replacements
Total Chemical Cost
Cleaner
$92.8
7
$649
Microetch
$386
9
$3,470
Catalyst
$1,640
6
$9,830
Acid Dip
$315
4
$1,260
Electroless Nickel
$890
40
$35,500
Immersion Gold
NAC
6
$57,900
Total Materials Cost
$108,600
" Reported chemical cost per bath replacement reflects the average bath cost of all processes submitted for evaluation in this
surface finishing category.
b Number of bath replacements required to process 260,000 ssf as determined by process simulation.
c Immersion gold replacement cost was calculated differently than other baths because of the wide disparity in costs and
throughput between product lines. The overall cost for the gold bath was calculated for each product line and then averaged
together to give the gold cost for the process.
Process: Electroless Nickel/Electroless Palladium/Immersion Gold, non-conveyorized
Throughput: 260K ssf of PWB
lialli
Chemical Cost/liath
Replacement
Number of lialli
Replacements
Total Chemical Cost
Cleaner
$128
7
$900
Microetch
$266
9
$2,390
Catalyst
$2,810
6
$16,860
Acid Dip
$11.3
4
$45
Electroless Nickel
$2,390
40
$95,600
Preinitiator
$2,430
5
$12,150
Electroless Palladium
$3,980
34
$135,300
Immersion Gold
NAC
6
$57,900
Total Materials Cost
$321,000
" Reported chemical cost per bath replacement reflects the average bath cost of all processes submitted for evaluation in this
surface finishing category.
b Number of bath replacements required to process 260,000 ssf as determined by process simulation.
c Immersion gold replacement cost was calculated differently than other baths because of the wide disparity in costs and
throughput between product lines. The overall cost for the gold bath was calculated for each product line and then averaged
together to give the gold cost for the process.
G-39
-------
Process: OSP, non-conveyorized
Throughput: 260K ssf of PWB
liatli
Chemical Cost/liath
Number of liatli
Total Chemical Cost
Replacement
Replacements
Cleaner
$51.6
7
$361
Microetch
$157
9
$1,420
OSP
$16,750 c
1
$16,750
Total Materials Cost
$18,500
" Reported chemical cost per bath replacement reflects the average bath cost of all processes submitted for evaluation in this
surface finishing category.
b Number of bath replacements required to process 260,000 ssf as determined by process simulation.
c OSP bath is not replaced, but rather refilled as the OSP is consumed. Cost of OSP was calculated at $105/gal and is consumed
at 1,630 ssf/gal.
Process: OSP, conveyorized
Throughput: 260K ssf of PWB
liatli
Chemical Cost/liath
Replacement
Number of liatli
Replacements
Total Chemical Cost
Cleaner
$67.2
6
$403
Microetch
$271
6
$1,630
OSP
$16,750 c
1
$16,800
Total Materials Cost
$18,800
" Reported chemical cost per bath replacement reflects the average bath cost of all processes submitted for evaluation in this
surface finishing category.
b Number of bath replacements required to process 260,000 ssf as determined by process simulation.
c OSP bath is not replaced, but rather refilled as the OSP is consumed. Cost of OSP was calculated at $105/gal and is consumed
at 1,630 ssf/gal.
G-40
-------
Process: Immersion Silver, conveyorized
Throughput: 260K ssf of PWB
Bath
Chemical Cost/Bath
Replacement'
Number of Bath
Replacements 1
Total Chemical Cost
Cleaner
$958
6
$5,750
Microetch
$124
6
$744
Predip
$1,200
5
$6,000
Immersion Silver
$40,170 c
1
$40,200
Total Materials Cost
$52,700
" Reported chemical cost per bath replacement reflects the average bath cost of all processes submitted for evaluation in this
surface finishing category.
' Number of bath replacements required to process 260,000 ssf as determined by process simulation.
' Silver bath is not replaced, but rather maintained as the silver bath is depleted. Hie cost of the silver bath was calculated at
$30.9/gal and is consumed at 200 ssf/gal.
Process: Immersion Tin, non-conveyorized
Throughput: 260K ssf of PWB
Bath
Chemical Cost/Bath
Replacement'
Number of Bath
Replacements 1
Total Chemical Cost
Cleaner
$174
7
$1,220
Microetch
$74
9
$665
Predip
$659
5
$3,300
Immersion Tin
$23,850 c
1
$23,850
Total Materials Cost
$29,000
" Reported chemical cost per bath replacement reflects the average bath cost of all processes submitted for evaluation in this
surface finishing category.
' Number of bath replacements required to process 260,000 ssf as determined by process simulation.
' Tin bath is not replaced, but rather maintained as the tin bath is depleted. The cost of the tin bath was calculated at $133/gal and
is consumed at 1,450 ssf/gal.
Process: Immersion Tin, conveyorized
Throughput: 260K ssf of PWB
Bath
Chemical Cost/Bath
Replacement'
Number of Bath
Replacements 1
Total Chemical Cost
Cleaner
$226
6
$1,350
Microetch
$125
6
$752
Predip
$597
5
$2,990
Immersion Tin
$23,850 c
1
$23,850
Total Materials Cost
$28,900
" Reported chemical cost per bath replacement reflects the average bath cost of all processes submitted for evaluation in this
surface finishing category.
' Number of bath replacements required to process 260,000 ssf as determined by process simulation.
' Tin bath is not replaced, but rather maintained as the tin bath is depleted. The cost of the tin bath was calculated at $133/gal and
is consumed at f ,450 ssf/gal.
G-41
-------
Appendix H
Environmental Hazard Assessment and Ecological
Risk Assessment Methodology
-------
H-l. HAZARD PROFILE
The environmental hazard assessment of chemicals consists of the identification of the
effects that a chemical may have on organisms in the environment. An overview of this
assessment process has been reported by, for example, Smrchek and Zeeman (1998) and by
Zeeman and Gilford (1993). The effects are expressed in terms of the acute and chronic toxicity
of a chemical on the exposed organisms. These are generally given as either the lethal
concentration (LC) or as the effective concentration (EC) that describe the type and seriousness
of the effect for a known concentration of a chemical. When the effective concentrations for a
range of species for a chemical are tabulated, the tabulation is called a hazard profile or toxicity
profile. A more detailed discussion of a comprehensive hazard profile has been presented by
Nabholz (1991). The most frequently used hazard profile for the aquatic environment consists of
a set of six effective concentrations as reported by Nabholz et al. (1993a). These are:
• Fish acute value (usually a fish 96-hour LC50 value)
• Aquatic invertebrate acute value (usually a daphnid 48-hour LC50 value)
• Green algal toxicity value (usually an algal 96-hour EC50 value)
• Fish chronic value (usually a fish 28-day chronic value [ChV])
• Aquatic invertebrate chronic value (usually a daphnid 21-day ChV)
• Algal chronic value (usually an algal 96-hour NEC or GMATC value for biomass)
For the acute values, the LC50 (lethality or mortality) (EC50) (non-lethal/lethal effects)
refers to the concentration that results in 50 percent of the test organisms affected at the end of
the specified exposure period in a toxicity test. The chronic values represent the concentration of
the chemical that results in no statistically significant sublethal effects on the test organism
following an extended or chronic exposure.
The hazard profile can be constructed using effective concentrations based on toxicity test
data (with measured test chemical concentrations) or estimated toxicity values based on structure
activity relationships (SARs). The measured values are preferred because they are based on
actual test data, but in the absence of test data SAR estimates, if available for the chemical class,
can be used. Thus the hazard profile may consist of only measured data, only predicted values,
or a combination of both. Also, the amount of data in the hazard profile may range from a
minimum of one acute or chronic value to the full compliment of three acute values and three
chronic values.
In the absence of measured toxicity values, estimates of these values can be made using
SARs. SAR methods include quantitative structure activity relationships (QSARs), qualitative
SARs, or use of the chemical analogs. The use of SARs by OPPT has been described (Clements,
1988; Clements, 1994). The use and application of QSARs specifically for the hazard assessment
of TSCA new chemicals has been presented (Clements et al., 1993a). The development,
validation, and application of SARs in OPPT have been presented by OPPT staff (Zeeman et al.,
1993b; Boethling, 1993; Clements et al., 1993b; Nabholz et al., 1993b; Newsome et al., 1993 and
Lipnick, 1993).
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The predictive equations (QSARs) are used in lieu of actual test data to estimate a toxicity
value for aquatic organisms within a specific chemical class. A total of 140 have been listed
(Clement et al., 1995; Smrchek and Zeeman, 1998). Although the equations are derived from
correlation and linear regression analysis based on measured data, the confidence intervals
associated with the equation are not used to provide a range of toxicity values. Even with
measured test data, the use of the confidence limits to determine the range of values is not used.
H-2. DETERMINATION OF CONCERN CONCENTRATION
Upon completion of a hazard profile, a concern concentration (CC) is determined. A
concern concentration is that concentration of a chemical in the aquatic environment, which, if
exceeded, may cause a significant risk to aquatic organisms. Conversely, if the CC is not
exceeded, the assumption is made that probability of a significant risk occurring is low and no
regulatory action is required. The CC for each chemical is determined by applying assessment
factors (AsF) (U.S. EPA, 1984) or uncertainty factors (UF) (Smrchek et al., 1993) to the effect
concentrations in the hazard profile.
These factors incorporate the concept of the uncertainty associated with: 1) toxicity data,
laboratory tests versus field tests, and measured versus estimated data; and 2) species sensitivity.
For example, if only a single LC50 value for a single species is available, there are several
uncertainties to consider. First, how reliable is the value itself? If the test were to be done again
by the same laboratory or a different laboratory, would the value differ and, if so, by how much?
Second, there are differences in sensitivity (toxicity) among and between species that have to be
considered. If the species tested the most or the least sensitive? In general, if only a single
toxicity value is available, there is a large uncertainty about the applicability of this value to other
organisms in the environment and a large assessment factor, i.e., 1000, is applied to cover the
breadth of sensitivity known to exist among and between organisms in the environment.
Conversely, the more information that is available results in more certainty concerning the
toxicity values and requires the use of smaller factors. For example, if toxicity values are derived
from field tests, then an assessment factor of 1 is used because tests measure chemical effects on
field organisms.
Four factors are used by OPPT to set a CC for chronic risk: 1, 10, 100, and 1000. The
factor used is dependent on the amount and type of toxicity data contained in the hazard profile
and reflects the amount of uncertainty about the potential effects associated with a toxicity value.
In general, the more complete the hazard profile and the higher the quality of the generated
toxicity data, the smaller a factor that is used. The following discussion describes the use and
application of uncertainty or assessment factors.
1. If the hazard profile only contains one or two acute toxicity values, the concern
concentration is set at 1/1000 of the acute value.
2. If the hazard profile contains three acute values (called the base set), the concern
concentration is set at 1/100 of the lowest acute value.
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3. If the hazard profile contains one chronic value, the concern concentration is set at 1/10 of
the chronic value if the value is for the most sensitive species. Otherwise, it is 1/100 of the
acute value for the most sensitive species.
4. If the hazard profile contains three chronic values, the concern concentration is set at 1/10
of the lowest chronic value.
5. If the hazard profile contains a measured chronic value from a field study, then an
assessment factor of 1 is used.
11-3. HAZARD RANKING
Chemicals can be also ranked by their hazard concern levels for the aquatic environment.
This ranking can be based upon the acute toxicity values expressed in milligrams per liter (mg/L).
The generally accepted scoring used by OPPT is as follows (Smrchek et al., 1993; Wagner et al.,
1995):
High Concern (H) < 1
Moderate (or Medium) Concern (M) > 1 and <100
Low Concern (L) >100
This ranking can also be expressed in terms of chronic values as follows:
High Concern (H) <0.1
Moderate (or Medium) Concern (M) >0.1 and < 10.0
Low Concern (L) > 10.0
Chronic toxicity ranking takes precedent over the acute ranking.
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