United States
Environmental Protection
Agency
Office of Air Quality
Planning and Standards
Research Triangle Park, NC 27711
EPA - 454/R-99-040
Sentember 1999
Air
&EPA
Evaluation of the Water - Based
Coating Method (ATD-FID)
Round Robin Study
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FINAL SUMMARY REPORT
ON
EVALUATION OF THE WATER-BASED COATING METHOD (ATD-FID)
by
Patrick J. Callahan, Michael W. Holdren, Peter A. Chace
and G. William Keigley
Battelle Memorial Institute
505 King Avenue
Columbus, Ohio 43201-2693
September 29,1999
Contract No. 68-D-99-009
Work Assignment No. 1-01
Project Officer
Kathy Weant
Work Assignment Manager
Candace B. Sorrell
Emissions, Monitoring, and Analysis Division
Office of Air Quality Planning and Standards
U.S. Environmental Protection Agency
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This report is a work prepared for the United States Government by
Battelle. In no event shall either the United States Government or Battelle
have any responsibility or liability for any consequences of any use,
misuse, inability to use, or reliance upon the information contained
herein, nor does either warrant or otherwise represent in any way the
accuracy, adequacy, efficacy, or applicability of the contents hereof.
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GENERAL DISCLAIMER
This document may have problems that one or more of the following disclaimer
statements refer to:
• This document has been reproduced from the best copy furnished by the
sponsoring agency. It is being released in the interest of making
available as much information as possible.
• This document may contain data which exceeds the sheet parameters. It
was furnished in this condition by the sponsoring agency and is the best
copy available.
• This document may contain tone-on-tone or color graphs, charts and/or
pictures which have been reproduced in black and white.
• The document is paginated as submitted by the original source.
• Portions of this document are not fully legible due to the historical nature
of some of the material. However, it is the best reproduction available
from the original submission.
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TABLE OF CONTENTS
Page
Section 1. Introduction 1
Section 2. Summary and Conclusions 3
Section 3. Recommendations 6
Section 4. Procedures 8
Selection of Laboratories 8
Selection of Test Paints 11
Laboratory Kick-Off Meetings 13
Overview of ASTM E691 16
Section 5. Results and Discussion 19
Equipment Performance 19
Laboratory Performance 21
QA Activities 24
Problems Encountered With Draft Method 27
Comments from Laboratories 28
ASTM E691 Results 31
References 43
APPENDIX A. MSDS SHEETS FOR STUDY PAINTS AND AVERAGE
RELATIVE SENSITIVITY CALCULATIONS
APPENDIX B. LABORATORY KICK-OFF MEETING HANDOUT
APPENDIX C. ASTM STANDARD PRACTICE E691-92
APPENDIX D. LABORATORY DATA SHEETS
LIST OF TABLES
Table 4.1. Six Participating Laboratories 10
Table 4.2. Coatings Purchased for Intel-laboratory Study 12
Table 4.3. Wt% VOC Results for Paint Samples 12
iii
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LIST OF TABLES
(Continued)
Page
Table 4.4. Materials Supplied to Participating Laboratories 15
Table 5.1. GC and Integrator Systems Used in Interlaboratory Study 20
Table 5.2. Laboratory QC Check Results 22
Table 5.3. Average Paint Relative Sensitivities Used by Laboratories 24
Table 5.4 Comparison of Wt% VOCC Calculated Using Lab and Battelle RSavg 24
Table 5.5. Results of Audit Paint 1403-0100, Ultra Egshell White 26
Table 5.6. Results from M24 Audit Samples 26
Table 5.7. Laboratory Comments on Draft Method 28
Table 5.8. Paint 4020-1000 Wt% VOCC Results 32
Table 5.9. Paint 1403-0100 Wt% VOCC Results 33
Table 5.10. Paint 4206-0100 Wt% VOCC Results 33
Table 5.11. Paint MS1-6659A Wt% VOCC Results 34
Table 5.12. Precision Statistics 40
Table 5.13. Precision Statement 42
LIST OF FIGURES
Figure 5.1. Mean Wt% VOCC Results from Paint 4020-1000 by Laboratory 34
Figure 5.2. Mean Wt% VOCC Results from Paint 1403-0100 by Laboratory 35
Figure 5.3. Mean Wt% VOCC Results from Paint 4206-0100 by Laboratory 35
Figure 5.4. Mean Wt% VOCc Results from Paint MS1-6659A by Laboratory 36
IV
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LIST OF FIGURES
(Continued)
Page
Figure 5.5. h - Laboratories within Paints 38
Figure 5.6. h - Paints within Laboratories 38
Figure 5.7. k - Laboratories within Paints 39
Figure 5.8. k - Paints within Laboratories 39
Figure 5.9. Standard Deviations of Repeatability and Reproducibility
Versus Mean Wt% VOCC 41
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Section 1
Introduction
To reduce the formation of ozone, the Environmental Protection Agency (EPA) regulates
volatile organic compounds (VOC) from a number of facilities and materials. One category of
materials is coatings and inks. The current EPA regulations require the use of EPA Method 24 to
determine the VOC content of coatings and inks.
Method 24 indirectly determines the VOC content of a coating by measuring the coatings
volatile content using the American Society for Testing and Materials (ASTM) method D 2369,
water content by ASTM methods D 3792 or D 4017 and exempt compounds content by ASTM
D 4457. The VOC content is calculated as the difference of the volatile content minus the water
content and exempt content. The precision of Method 24 is poor if the water content is much
larger than the VOC content.
Under a previous contract with Entropy (EPA contract 68D20163, work assignment
Numbers 3-05 and 4-02), EPA developed a method for measuring the VOC content of water-
based coatings directly rather than indirectly as in EPA Method 24. In this method, a Perkin-
Elmer Model ATD-400 automated rube desorber is used to thermally desorb the volatiles from a
weighed sample of coating, and a flame ionization detector on a gas chromatograph (GC) is used
to estimate the total amount of VOCs in the volatilized material.
The purpose of this project was to conduct an interlaboratory study to evaluate the draft
water-based coating method. A total of six laboratories participated in the interlaboratory study.
Each of the laboratories was required to analyze four different water-based coatings following
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the procedure described in the draft method. The results from the participating laboratories were
analyzed using the statistical procedures described in ASTM E 691, Standard Practice for
Conducting an Interlaboratory Study to Determine the Precision of a Test Method.
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Section 2
Summary and Conclusions
The four paints chosen as samples for the interlaboratory study included the following
types of water-based coating: one automotive paint, one wall and trim enamel, one
interior/exterior architectural paint, and one interior/exterior primer. The water contents of these
paints ranged from 30% to 54% and the weight percent VOC levels ranged from 2.9% to 15.4%.
The weight percent VOC content of the test paints was stable during the course of the study.
A total of six laboratories participated in the interlaboratory study of the draft water-
based coating method. In the search for these laboratories, no laboratories were found that had
the Perkin-Elmer ATD-400 which is the required instrument for the draft method. The many
laboratories that plan to perform this method in the future will need to lease or buy the ATD-400.
Presently, Perkin-Elmer is the only firm that leases ATD-400 instruments.
Mechanically, the single Perkin-Elmer ATD-400 system used for the interlaboratory
study proved to be very reliable. The automated tube loading system mis-loaded only one tube
during the entire study. After the ATD-400 focusing trap was packed with Tenax GR and
Carbopak B sorbent as required by the draft method, it was found to be very difficult to install
into the instrument. At one of the laboratories, the sorbent bed migrated so that it was no longer
inside the cooled region of the trap; however, this migration did not have any significant affect
on the test results. The laboratory personnel were able to learn how to operate the ATD-400 with
only one or two hours of training.
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In general, all six of the laboratories were able to follow the analytical portion of the draft
method with a minimum amount of additional instruction from Battelle. All of the laboratories
were able to prepare the standards and samples and to perform the paint analyses without any
major difficulties. Blank levels were not found to be a problem during the course of the
interlaboratory study. All of the laboratories achieved valid calibrations on the first try. The
%RSD limits in the draft method were found to be reasonable.
The data analysis and calculations section was found to be the area of the method where
errors were made by the laboratories. In particular, the various calculations necessary to
compute the corrected weight percent VOC (Wt% VOCC) led to the most errors by the
laboratories. Laboratory personnel who did not have chemistry backgrounds, such as quality
assurance personnel, had a difficult time with these calculations and required additional guidance
from Battelle. Laboratory 1 did find an error with equation 13.2 in the draft method. The weight
percent conversion in this equation is not correct.
The mean Wt% VOCC measured by the six laboratories were very consistent for each of
the four test paints. There was also good agreement between the laboratory Wt% VOCC values
and those measured by Battelle. Since the Battelle measurements were made on a separate ATD-
400 instrument from the one used by the laboratories, these results indicated there was no
evidence of any instrument bias with the draft method. The consistency of the Wt% VOCC
results suggest that the use of different gas chromatographs and chromatographic data systems in
the study did not have a significant affect on the results.
The Wt% VOCC results were analyzed using the statistical procedures described in
ASTM E 691. None of the laboratories were found to have h statistic (a measure of between-
laboratory consistency) above the critical values; therefore, there was not any evidence to show
that any one of the laboratories produced biased data relative to the other laboratories in the
study. For the k statistic (a measure of within-laboratory consistency), only one paint at
laboratory 5 was found to be above the critical value. No calculation errors or physical evidence
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of any instrument or procedures problems were found for this paint, so it was retained in the
precision analysis of the method.
From the ASTM E 691 analysis of the study data, precision statistics were determined for
the draft method. The 95% repeatability limit for the method ranged from 0.15 - 1.32, while the
95% reproducibility limit ranged 0.49 - 3.57. These limits represent the difference between any
two measurements at the same laboratory (repeatability) and the difference between any two
measurements taken at different laboratories (reproducablity) with a 95% confidence. A
precision statement was drafted for the water-based coating method.
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Section 3
Recommendations
The largest source of errors and questions in the draft method were the portions involving
the calculation of the correction factor (RSavg) for the corrected weight percent VOC (Wt%
VOCC). These calculations require some knowledge of chemistry, because functional groups in
the chemical structure of the VOC paint components have to be identified and counted. In the
interlaboratory study, it was found that laboratory personnel, who did not have a chemistry
background, had a difficult time with these calculations. Considering the errors found with this
portion of the draft method, all laboratories should be required to submit these calculations along
with their data. Only by checking these calculations will it be possible to assure the draft method
is being applied consistently. With the number of calculations performed in the draft method,
more guidance needs to be included on the number of significant figures that should be reported.
One way to simplify the calculations would be to tabulate the relative sensitivity (RS;) for
the most common VOC components in water-based coatings and put them in a database. From
this database, the laboratories performing the draft method could select the RSj values that they
need and calculate the final RSavg value for the water-based coating. The calculation of the RSavg
is a calculation that every laboratory should be able to perform. Constructing the RSS database
would free the laboratories from having to make the chemical calculations and eliminate a source
of error in the method.
The draft method does not give any guidance on how to apply the approximately 25 uL
of coating to the PTFE (polvtetrafiuorethylene - type of Teflon®) liners. For this study, a
procedure involving a disposable 1 mL syringe with a luer tip and a 22 gauge luer hub needle
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was used by the laboratories to load the paints onto the PTFE liners. This method of loading the
PTFE liners worked well enough that it should be added to the method.
In the kick-off meetings, it was found that pass levels for the standard calibration and
quality control check standard were scattered over several pages of the draft method. The draft
method would be easier to follow if all of this information were combined into the same section
of the method. Also, a table showing the pass levels of the standards would make the method
much easier to follow.
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Section 4
Procedures
In this section, the key procedures that were used to conduct the interlaboratory study are
discussed. These include the procedures used to select the laboratories and the test paints. The
training and instructions given to the participating laboratories in the kickoff meeting are
described. A brief overview of the ASTM standard practice (E691) that was used to evaluate the
results of the interlaboratory study is given.
Selection of Laboratories
A search was conducted to identify six laboratories that would participate in the
interlaboratory study. Three different sources were used to identify laboratories. The first was a
list of laboratories that had participated in a previous round robin study (1995 U.S. EPA Report)
of coating samples for U.S. EPA. The second source was the yellow page listings of paint
laboratories, testing laboratories, and paint manufacturers in the Columbus, Cleveland,
Cincinnati, and Dayton, Ohio metropolitan areas. The third source was an Internet search of
paint laboratories and paint manufacturers. Battelle attempted to identify laboratories to
participate in the interlaboratory study based on an evaluation of the following factors, in
decreasing order of importance:
• Experience in analyzing paint samples - Laboratories with more demonstrated
experience were preferred
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• Cost to participate - Laboratories willing to participate at their own expense were
preferable to laboratories requiring reimbursement for participation
Access to ATD-400 - Laboratories with an ATD-400 system would be preferable
to laboratories without
• Proximity to Battelle - To save travel/equipment shipment expenses
Initially eight laboratories were identified that would be willing to participate. None of
these laboratories nor any of the other laboratories that were contacted had the Perkin-Elmer
ATD-400 system that is necessary to perform the draft method. To resolve this problem, a
search was done to determine if an ATD-400 could be leased for use in the interlaboratory study.
The only lease source found for the ATD-400 was Perkin-Elmer itself. Arrangements were made
to lease an single ATD-400 system from Perkin-Elmer that could be used by the laboratories to
perform the draft method.
The list of laboratories was reduced to six as a result of scheduling conflicts and a desire
to minimize shipping costs for the ATD-400 system. The final list of participating laboratories is
shown in Table 4.1. Each laboratory was sent a letter describing the interlaboratory study in
more detail. In this letter, the laboratories were told that their anonymity would be protected. In
reporting the results to U.S. EPA, each laboratory would be assigned a number (1 - 6). The
participation of the laboratories would be recognized in the report, but the results would only
reference the number assigned to the laboratories. Also included with the letter was a
Memorandum of Agreement that the laboratories had to sign and return.
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Table 4.1. Six Participating Laboratories
Participating Laboratory
Laboratory
Type
South Coast Air Quality Management District
21865 East Copley Drive
Diamond Bar, California 91765-4182
Contact: Rudy Edden
Phone: 909-396-2391
Joan Niertit
Phone: 909-396-2174
District Air
Quality
Laboratory
Dexter Coating Systems
1 East Water Street
Waukegan, Illinois 60085
Contact: Roger Brown
Phone:847-625-3320
Coating and
Adhesive
Manufacturer
Yenkin-Majestic Paint Corporation
1920 East Leonard Ave
Columbus, Ohio 43236
Contact: Phillip Boadt
RonDucker-ext323
Phone:614-253-8511
Paint
Manufacturer
CTL Engineering
2860 Fisher Rd.
Columbus, Ohio 43204
Contact: Richard Herrold
Phone: 614-276-8123
Engineering and
Product Testing
Laboratory
PPG Industries, Inc.
4325 Rosanna Dr.
Allison Park, PA 15101
Contact: Joseph Benga
Phone:412-492-5511
Paint
Manufacturer
Wilson Environmental Laboratories, Inc.
410 Venture Drive
Columbus, Ohio 43081
Contact: Eric Layman
Phone: 614-431-0010
Environmental
Service
Laboratory
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Selection of Test Paints
Battelle was required by U.S. EPA to obtain at least six water-based coatings with
varying water concentrations that could be used as test coatings for the interlaboratory study.
The EPA work assignment manager (WAM) supplied Battelle with a list of coatings that had
been used in a previous round robin study (1995 U.S. EPA Report) and a draft report on the
development of the draft water-based coating method that also listed several coatings. A number
of these coatings were not found to be available anymore. Several of the manufacturers were
reluctant to provide information to Battelle on the ingredients of the coatings when they found
out the study was being sponsored by U.S. EPA. The search for the paint samples then turned to
local paint suppliers in Columbus, Ohio. These paint suppliers were much more willing to share
information about their products. Material safety data sheets (MSDS) were obtained on a
number of different types of water-based paints such as automotive paints, architectural paints,
primers, and wall paints. A total of six water-based paints were chosen to represent a wide
variety of paint types as well as varying water concentrations. These paints were purchased in
one gallon cans from two suppliers in Columbus, Ohio. Table 4.2 lists the six paints that were
purchased as well as a description of the paints and the paint manufacturers. An MSDS sheet
was obtained for each paint. These MSDS sheets can be found in Appendix A. Also shown in
Appendix A are the calculations for the average relative sensitivities (RSavg) used in the draft
method to calculate the corrected weight percent VOC of the coatings. For these calculations, if
the weight percent of a particular VOC was given as a range on the MSDS sheet, the middle
value of the range was used for the average relative sensitivity calculations.
Of the six candidate paints, U. S. EPA had instructed that four were to be chosen for
actual use in the interlaboratory study. As part of the decision making process in selecting the
study paints, all six of the water-based paints were analyzed at Battelle following the procedures
described in the draft method. The Perkin-Elmer ATD-400 thermal tube desorber leased for the
study was used for these analyses. Table 4.3 lists the uncorrected weight percent VOC ( Wt%
VOCJ, the corrected weight percent VOC (Wt% VOCC) measured for each paint, and the RSavg
from Appendix A used to calculate the Wt% VOCC. Battelle and the WAM chose four paints
that would be represent the range of Wt% VOCC found in the paint analyses. The coatings that
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were selected for use in the interlaboratory study were: MS1-6659A, 1403-0100, 4206-0100, and
4020-1000.
Table 4.2. Coatings Purchased For Interlaboratory Study
Coating ID
(% water)
MS 1-6659 A
(54.0%)
MS 1-6660 A
(43.9%)
1403-0100
(30-40%)
4206-0100
(30-40%)
4020-1000
(30-40%)
25524
(39.1%)
Identity
Silver Waterbome
Industrial Enamel
Gray Waterbome
Industrial Enamel
Ultra Eggshell White
Acrylic
White Devflex
Waterbome Semi-
gloss Enamel
White DIM
Waterbome Primer
White Water-
Reducible Acrylic
Product Use
Automotive Paint
Automotive Paint
Wall and Trim
Enamel
Interior/exterior
Architectural Paint
Flat Interior/Exterior
Primer
Traffic Paint
Manufacture
Martin Senour Paints
Martin Senour Paints
ICI Dulux Paints
Devoe Coatings
Devoe Coatings
ICI Performance
Coatings
Table 4.3. Wt% VOC Results for Paint Samples
Coating ID
MS1-6659A
MS16660A
1403-0100
4206-0100
4020-1000
25524
Sample
Number
4
4
14
4
4
4
wt% vocu
13.7
17.1
3.28
10.4
3.28
2.43
RSavg
1.019
1.022
0.837
1.239
1.359
0.649
Wt% VOCC
13.4
16.7
3.91
8.43
2.41
3.74
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For the interlaboratory study, the four test paints were transferred from the one gallon
cans into smaller vials that would be provided to the participating laboratories. This transfer
procedure involved first shaking the gallon of each paint on a commercial paint shaker. Next 60
cc polypropylene disposable syringes were used to transfer each paint from the one gallon cans to
4 dram glass vials. These syringes had a large opening (8 mm) in the syringe tip and were used
without a needle to minimize the chances of causing separation between the solid and liquid
portions of the paint. Each syringe was filled by immersing the syringe tip approximately four
inches below the surface of the paint before the paint was drawn into the syringe. After the
syringe was removed from the paint, it was wiped off with a paper towel to remove any paint on
the outside surfaces of the syringe. The paint in the syringe was discharged into each 4 dram vial
so that the vial was filled as full as possible to minimize the headspace left in the vial. The vials
were sealed with screw-top caps that had a Teflon liner on the sealing surface of the cap. After
the cap was tightened, it was wrapped with Teflon tap to give added protection from leakage.
Once all of the vials were filled, they were placed in a box and stored in a refrigerator prior to
being sent to the participating laboratories. The laboratories were also asked to refrigerate the
paints samples prior to analyzing them.
Laboratory Kick-off Meetings
Since the six laboratories had to share one Perkin-Elmer ATD-400 thermal tube desorber,
a schedule was established that allowed each laboratory to have possession of the system for two
weeks. In order to perform the analyses described in the draft method, the ATD-400 transfer line
needs to be connected to a gas chromatograph (GC) with a flame ionization detector (FID).
Also, the output of the FID needs to be monitored with an integration system (integrator or PC
based chromatographic system) that allows the total peak area to be measured.. Several of the
participating laboratories also required a GC and integration system to perform the testing either
because they did not have this equipment or because they did not want to take their systems out
of production. In these cases, Battelle provided a Hewlett Packard 5890 GC with a FID and a
Chromperfect data system.
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After the ATD-400 was received at each laboratory, a one day kick-off meeting was held.
In this meeting, Battelle personnel helped the laboratory personnel connect the ATD-400 to the
GC and data system and made sure the system was operating properly. The laboratory personnel
were given training on how to operate the ATD-400. The tube conditioning parameters and tube
analysis parameters required by the draft method were programmed into the ATD-400 as two
separate methods by Battelle personnel prior to shipping it to the laboratories. At the kickoff
meeting, the ATD-operators were shown where these parameters were located in each method
and how to load the methods. The ATD operators used these two programs in sequential fashion
to first clean the PTFE liners and then to analyze the paint samples and standards. The only
information that the ATD-400 operators had to input into the two methods were the start tube
number and the stop tube number. The draft method requires a carrier gas flowrate through the
sample tube of 100 mL/min for tube cleaning and 5 mL/min for tube analysis. The ATD-
operators were left a flowmeter and shown how to adjust the carrier gas flowrate.
Each laboratory was also given all of the materials that would be needed to perform the
draft method. These materials are listed in Table 4.4. The 2-butoxyethanol used for the standard
preparation in the study came from a single one liter bottle of Aldrich 99+% spectrophotometric
grade 2-butoxyethanol (Lot 01139DR). Prior to each kickoff meeting, the one ounce bottle was
emptied and refilled by Battelle personnel with fresh 2-butoxyethanol to avoid any cross
contamination from laboratory to laboratory.
At the kick-off meeting, each participating laboratory was given a packet of information.
This packet of information is shown in Appendix B. Included in the packet was the draft test
method that the laboratories were to follow in performing their work. The details of the draft
method such as sample volumes, loading techniques and standard preparation were reviewed
with each laboratory. Special emphasis was place on the calibration and quality control check
standard accuracy and precision requirements of the draft method.
The laboratories were given information about the paints that they would need to
compute the correction factors for the Wt% VOCC calculations. This information included the
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ingredients of each paint and the chemical structure of specific VOC components. Examples of
the calculations used to determine the correction factor were supplied as well as the Jorgensen, et
al. reference cited in the draft method. Each laboratory was instructed to treat the ingredients
mineral spirits and solvent naphtha as a C10H22 alkane. In cases where the weight percent of the
ingredients were given as a range, the laboratories were instructed to use the middle value of the
range for the average relative sensitivity calculations.
Table 4.4. Materials Supplied to Participating Laboratories
Material
One ounce of 2-butoxyethanol in an amber screw cap bottle
Thirty PTFE liners for sample tubes (Perkin-Elmer Part No. L407-1596)
Sixteen stainless steel tubes, 1/4 inch OD, 5mm ID, 3.5 inches long with end caps
(Perkin-Elmer Part No. L427-0123)
Silanized glass wool for packing PTFE liners (Alltech Pesticide Grade Glass Wool,
Part #: 4034)
Twelve 1 mL polypropylene syringes with a luer tip with 20 gauge luer hub
needles for loading the sample paints into the liners (Beeton-Dickinson 309602
Tuberculin syringe)
One Hamilton #805, 50 ul syringe for loading the standards onto the glass wool
Four sample paints in 4 dram vials labeled with one of the following sample codes
1403-0100
MS 1-6659 A
4206-0100
4020-1000
Logbook to record information while performing the draft method
Data sheets were provided to record the various calibration and QC/QA measurements
required by the draft method and the test results from the four sample paints. Each laboratory
was instructed to analyze the four water-based paints in triplicate for this study. The laboratories
were also asked to submit hard copies of their chromatograms and calculations so Battelle could
determine if they were applying the draft method correctly.
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Overview of ASTM E 691
The statistical methodology used to evaluate the interlaboratory study of the water-based
coating method, as recommended by standard practice ASTM E 691, is detailed below. A copy
of ASTM E 691 can be found in Appendix C.
An interlaboratory study evaluates the precision of laboratory results by measuring within
laboratory and between laboratory variability. These types of variability are referred to as
repeatability and reproducibility, and are defined below:
Repeatability: Precision under the following conditions: independent test results are obtained
with the same method on identical test materials in the same laboratory by the same operator
using the same equipment within short periods of time.
Reproducibility: Precision under the following conditions: test results are obtained with the
same method on identical test items in different laboratories with different operators using
different equipment.
The following statistical model for laboratory results is considered when evaluating these two
types of laboratory precision:
YjL = (i + yL + sjL, L = 1 to p, where p = total number of laboratories in the study.
j=l to nL, where nL is the number of observations made per lab.
(i = true paint sample result
yL = the measurement error associated with different laboratories with different operators using
different equipment. Considered a N(0,a2L) random variable, with a\ being the measurement
error due to different laboratory conditions.
s = error under reproducibility conditions. Considered a N(0,a2r) random variable, with a2r being
the measurement error.
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Note that in this model the four laboratories in which the analysis was done are
considered to be a random sample from the population of all possible combinations of labs,
operators, and equipment. The model has two sources of variability. a2r is the residual error
attributable to measurement error (e.g. sampling and analytical variability) and effects left
unexplained by the model, and a2L is the additional error that results from different laboratory
conditions.
The interlaboratory study takes an Analysis of Variance approach to evaluate
repeatability and reproducibility. Error under repeatability conditions (a2r) is estimated by the
model Mean Squared Error. The estimate of a\ is also estimated by the model, and error under
reproducibility conditions is estimated in the following manner:
a2R (reproducibility error) = a2r + a2L
Two consistency statistics are used to evaluate the performance of laboratories involved
in the study. The first is a between-lab consistency statistic, which is used to determine if a
laboratory is obtaining average sample results that are significantly different from other
laboratories in the study. The statistic is calculated as follows:
y = average result for the laboratory in question.
y* = overall average of all p laboratories considered in the study.
sy = standard deviation of the p average laboratory results
The distribution of h can be equated to a t distribution with p-2 degrees of freedom, and
from this fact critical values for h can be determined. A value for h exceeding the given critical
value means the laboratory in question is producing biased results. In other words, the average
measurement from that laboratory is significantly higher or lower than the measurements
obtained from the other laboratories.
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The second statistic is a within-lab consistency statistic, which is used to determine the
variability of laboratory results as compared to other labs in the study. This statistic is calculated
as follows:
k - s / sr
s = the standard deviation of the n measurements taken in the laboratory in question.
sr = the estimated study-wide measurement error (an estimate of
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Section 5
Results and Discussion
In this section, the results from the various activities conducted as part of the
interlaboratory study are discussed. Comments are made on the performance of the Perkin-
Elmer ATD-400 system and the performance of the laboratories in applying the draft method.
The various quality assurance (QA) activities that occurred before and during the study are
reported. Finally, the results from the laboratories and the ASTM E 691 analysis are reported
and discussed.
Equipment Performance
All six of the participating laboratories were able to complete the testing in the two weeks
that they were scheduled to used the Perkin-Elmer ATD-400 system. Table 5.1 shows the gas
chromatograph (GC) and integrator systems that were used with the ATD-400 system at each
laboratory. None of the laboratories reported any difficulties in operating the ATD-400 system.
The only ATD-400 installation problem that was experienced was at laboratory 3. Problems
were encountered in getting the ATD-400 to trigger the data system. The communication cable
linking the ATD-400 to the data system had to be rewired so that the data system was triggered
properly. During the course of the interlaboratory study, Battelle personnel did all of the
maintenance on the ATD-400 unit leased for this study.
After analyzing the GC chromatograms from laboratories 1, 2, and 3, it was determined
that there was a decrease in the peak resolution of the 50% standard at laboratories 2 and 3. Prior
to shipment to laboratory 4, the ATD-400 system was assembled at Battelle, and the system
performance was evaluated. In this evaluation, the sorbent bed in the focusing trap was found to
19
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Table 5.1. GC and Integrator Systems Used in Interlaboratory Study
Laboratory
1
2
3
4
5
6
GC System
Battelle provided Hewlett-Packard
5890
Battelle provided Hewlett-Packard
5890
Laboratory provided Varian 3400
Battelle provided Hewlett-Packard
5890
Laboratory provided Hewlett-Packard
5890
Laboratory provided Hewlett-Packard
5890
Integrator System
Battelle provided Chromperfect data
system (3.52)
Battelle provided Chromperfect data
system (3.52)
Laboratory Provided Varian Star
Chromatography data system (Version
4.0)
Battelle provided Chromperfect data
system (3.52)
Battelle provided Chromperfect data
system (3.52)
Laboratory provided Chromperfect
data system (Versions. 5)
have migrated so that is was no longer in the region of the trap cooler. This migration had little
affect on the overall performance of the system, since all of the laboratories (1,2, and 3) passed
the calibration and quality control check standard (QCCS) tests required in the draft method.
The only effect was some peak broadening, especially for the 50 % standard. Since the method
requires the total area to be used, these broader peaks would not be expected to cause any
significant errors in the measurements. None the less, a new focusing trap was installed in the
ATD-400 system so that the sorbent bed was located properly within the trap cooler. To guard
against a reoccurrence of this problem, the location of the sorbent was checked during the
installation of the ATD-400 system at laboratories 4, 5, and 6.
The replacement of the focusing trap did not completely improve the peak resolution
problem. After performing several tests, it was found that peak resolution was regained by
20
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replacing the fused silica transfer line between the ATD-400 system and the GC. The old 0.32
mm internal diameter (I.D.) fused silica transfer line was replaced with a 0.53 mm I.D. transfer
line because it was felt that a larger transfer line may prevent this problem in the future. The
draft method does not specifically address what I.D. this transfer line should be. All three
standards (0.5%, 5%, and 50%) as well as a QCCS standard were analyzed on the ATD-400
using the new transfer line. Peak resolution was excellent, and the instrument passed all of the
calibration and QCCS requirements of the draft method.
The leased ATD-400 system proved to be very reliable in this interlaboratory study. The
unit was rugged enough that it could be shipped to all six laboratories and operate normally after
it was reattached to the GC. The automated tube loading system mis-loaded only one tube
during the whole course of the study. The only maintenance difficulty experienced was
installing the focusing trap. This trap consists of a 3 mm I.D. fused silica tube that is sealed in
the system with two graphite ferrules. The middle section of this tube is packed with a 10 mm
long-section of Tenax GR and a 10 mm section of Carbopak B as required by the draft method.
The focusing trap had to be installed twice during the study: once when the unit was originally
received from Perkin-Elmer and once after laboratory 3 had completed their testing. Both times
it was found to be very difficult to seal the graphite ferrules well enough to pass the ATD-400
internal leak test. Likewise, it was very easy to break the fused silica tube while tightening the
ferrules. Eventually, Battelle personnel implemented the use of a helium leak detector to aid in
getting the focusing trap leak free.
From time to time in the interlaboratory study, some of the laboratories obtained split GC
peaks or peaks with a trailing tail. These types of occurrences came and went with no apparent
explanation. Again, since total peak area was being measured, these chromatographic features
did not affect the results.
Laboratory Performance
All of the laboratories were able to prepare the standards and samples and to perform the
paint analyses without any major difficulties. Blank levels were not found to be a problem
21
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during the course of the interlaboratory study. The blank levels ranged from below the detection
limit to 0.2 Wt%. All of the laboratories achieved valid calibrations on the first analysis of the
0.5%, 5%, and 50 % standards. Only one laboratory (laboratory 3) did not pass the percent
accuracy and percent relative standard deviation (%RSD) requirements of the quality control
check standard (QCCS) on the first try. Table 5.2 lists the %RSD of the calibration response
factor, as well as the %RSD and % accuracy of the QCCS. These results show there was some
variability in the %RSD for both the calibration response factor and the %RSD of the QCCS.
The present %RSD limits in the draft method appear to be reasonable. If the limits were
tightened by even 5%, the calibrations and QCCS of some of the laboratories would not have
been acceptable.
Table 5.2. Laboratory QC Check Results
Laboratory
1
2
3
4
5
6
%RSD of Calibration
Response Factor
(Limit: %RSD<30%)
8.36
24.6
25.3
14.1
6.40
22.7
%RSD of Quality
Control Check
(Limit: %RSD<20%)
1.40
15.6
4.01
10.1
3.23
1.17
% Accuracy of Quality
Control Check Standard
(Limits:
90%<%Accuracy
-------
chemistry background performed these calculations required the least assistance from Battelle in
order to make these computations. At laboratory 2, the person performing the draft method,
including the calculations, had a quality assurance background. This laboratory required much
more additional assistance from Battelle to complete the calculations.
One common error involved the calculation of the relative sensitivity (RSj) value for
mineral spirits and solvent naphtha for the paints that contained these components. As mentioned
earlier, all of the laboratories were told to treat mineral spirits and solvent naphtha as a C10H22
alkane. According to Jorgensen, et al., 0.08 should be subtracted from the carbon number of an
hydrocarbon in calculating the effective carbon number (ECN) of the hydrocarbon. This ECN
value is then used to compute the RSj of the hydrocarbon. The ECN for a C10H22 alkane should
be 9.92 (10-.0.08 = 9.92). Laboratories 3, 4 and 5 failed to make this correction and used 10 as
the ECN for mineral spirits and solvent naphtha. Table 5.3 lists the final RSavg values that were
calculated by the laboratories after any gross errors were corrected, as well as the RSavg values
computed by Battelle . With the exception of the values shown in bold print in Table 5.3, any
variation in the values from laboratory to laboratory is due to rounding differences. The bold
print values represent the errrors that resulted from the use of an ECN value of 10 for mineral
spirits or solvent naphtha instead of 9.92.
To investigate the effect that this error in the RSavg for Laboratories 3, 4 and 5 had on the
final Wt% VOCC values, the Wt% VOCcfor paints MS1-6659A, 4206-0100, and 4020-1000 was
also calculated using Battelle's RSavg. The % Difference between the laboratory Wt% VOCC and
the Battelle Wt% VOCC was calculated for each paint. These values are shown in Table 5.4. As
can be seen, the error resulting from using an ECN of 10 instead of 9.92 for mineral spirits and
solvent naphtha resulted in a less than 1% error in the final Wt% VOCC. To assure that the final
database was consistent, the affected Wt% VOCC from laboratories 3, 4 and 5 were corrected
before they were entered into the database.
23
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Table 5.3. Average Paint Relative Sensitivities Used by Laboratories
Laboratory
1
2
3
4
5
6
Battelle
Paint Average Relative Sensitivity (RSavg)
MS1-6659A
1.019
1.019
1.020
1.018
1.021
1.019
1.019
1403-0100
0.837
0.838
0.838
0.838
0.838
0.838
0.837
4206-0100
1.239
1.24
1.245
1.233
1.246
1.241
1.239
4020-1000
1.359
1.362
1.368
1.369
1.368
1.361
1.359
Table 5.4. Comparison of Wt% VOCC Calculated Using Lab and Battelle RS
avg
Paint
MS 1-6659 A
4206-0100
4020-1000
% Difference Between Wt% VOCC Calculated
Using Lab RSavg and Wt% VOCC Calculated Using
Battelle RSavg
Lab 3
-0.098
-0.482
-0.658
Lab 4
0.098
0.487
-0.730
Lab 5
-0.196
-0.562
-0.658
QA Activities
At the beginning of the study, Battelle was required to analyze an audit paint sample
according to the draft method to demonstrate to the Work Assignment Manager (WAM) the
ability of Battelle to conduct the method. The audit paint sample was chosen by the WAM from
one of the six paints purchased for the interlaboratory study (see Table 4.2). The coating chosen
was 1403-0100, utlra eggshell white. Battelle performed the method using a Perkin-Elmer ATD-
400 that was located in Battelle's Hazardous Materials Laboratory (HML). This Perkin-Elmer
24
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ATD-400 was a separate instrument from the leased ATD-400 instrument that was used by the
six participating laboratories. After modifying the ATD-400 to meet the specifications of the
draft method, it was found to meet all of the calibration and QC checks required by the draft
method. Battelle analyzed the audit sample on March 3, 1999 in triplicate and submitted the
results to the WAM on March 6. These results are shown in Table 5.5. After reviewing the audit
results, the WAM was satisfied that Battelle could perform the draft method.
The sample of paint 1403-0100 used for the audit analysis was taken from the original
one gallon can on March 3, 1999. On April 12, the paints samples that would be given to the six
participating laboratories were taken from the one gallon cans of the four test paints, which
included paint 1403-0100, and loaded into the 4 dram sample vials. As each laboratory
performed their portion of the study, the paints were distributed to them. As mentioned in
Section 4, the 4 dram vials were kept refrigerated prior to their distribution to the laboratories.
After laboratory 3 finished their testing on June 30, Battelle collected the four paint samples
supplied to them and archived them in a refrigerator. On August 25, 1999, the paint samples
collected from laboratory 3 were analyzed on the ATD-400 at the HML. A Hewlett-Packard
5890 GC was used for these analyses. The results from the analyses on the 1403-0100 done on
August 25 are also shown on Table 5.5. A comparison of the March 3 and August 25 results on
paint 1403-0100 show that the paint samples in the 4 dram vials remained very stable during the
course of the study.
The leased Perkin-Elmer ATD-400 that was used for the interlaboratory study was
received by Battelle on March 18, 1999. The unit was installed on one of Battelle's Hewlett-
Packard 5890 GCs to meet the specifications of the draft method. The performance of the ATD-
400 system was evaluated by analyzing samples from the six candidate paints. It was at this time
that the results shown in Table 4.3 were obtained. After analyzing a number of samples of the
six candidate paints, the WAM was concerned that the Wt% VOCC values being measured with
the instrument were low; therefore the the WAM submitted four additional audit paint samples
for analysis with the ATD-400 system. These samples were labeled M24-003-A, M24-003-B,
M24-003-C, and M24-003-D and had previously been characterized for Wt% VOC. The purpose
25
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for analyzing these samples was to evaluate the accuracy of the Wt % VOC values measured
with the ATD-400. Samples M24-003-A and M24-003-B were duplicates of one paint, while
samples M24-003-C and M24-003-D were duplicates of another paint. Battelle analyzed
aliquots from samples M24-003-A, M24-003-B, and M24-003-C. The results from these
samples are shown in Table 5.6. All of the VOC content in each of the paints was assumed to be
hexane. When the results were reported to U.S. EPA, the WAM was satisfied that the instrument
was working properly and that it was ready for use in the interlaboratory study.
Table 5.5. Results of Audit Paint 1403-0100, Ultra Eggshell White
Analysis Date
3/03/99
8/25/99
Sample #
1
2
3
1
2
3
Wt% VOCC
4.89
4.34
4.44
4.29
4.57
4.51
Mean Wt%
VOCC
4.55
4.46
% RSD
6.43
3.25
Table 5.6. Results from M24 Audit Samples
Sample
M24-003-A
M24-003-B
M24-003-C
Wt% VOCU
(uncorrected)
46.4
48.6
51.0
Wt% VOCC
(corrected)
26.2
27.4
28.8
To assure the quality of the data reported by the participating laboratories, a thorough
QC/QA audit was made of all of the information submitted by each laboratory. The
chromatograms were checked to determine if the individual laboratory was using the total peak
26
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areas and if they were summing the peak areas from the two desorptions performed for each
analysis. The RSavg calculations were examined to assure that the laboratories had derived this
number correctly. The data from the standard preparation, system calibration, QCCS, and paint
analyses were entered into Excel spreadsheets to check the calculations made by each laboratory.
Any errors found were noted on the data sheets submitted by each laboratory. The data sheets
from each of the laboratories can be found in Appendix D.
Problems Encountered With Draft Method
The draft method states that approximately 25 uL of a coating sample should be applied
to the PTFE liner prior to analysis. The method does not give very detailed instructions on how
to apply this small amount of paint to the liner. When Battelle initially performed the method,
pipets or syringes with needles did not work well for these measurements because the paint
samples were too thick to draw through the small opening of a needle or pipet. The best
procedure that Battelle found to load the 25 uL of paint onto the liners was to use a 1 mL syringe
with a luer tip. First the syringe was filled with paint without attaching a needle. The syringe tip
was immersed approximately 2.5 cm into the 4 dram vial containing the paint, before the paint
was drawn into the syringe with the plunger. The syringe was then removed from the paint and
wiped off with a paper towel. Next a luer hub 22 gauge needle was placed on the tip of the
syringe, and the plunger was depressed until paint was discharged from the tip of the needle.
The liner was loaded by inserting the needle into the glass wool packing. The smallest divisions
on the 1 mL syringe represented 10 uL. By moving the syringe plunger three small divisions,
approximately 30 uL of paint was loaded onto the glass wool. Disposable syringes were used for
this paint loading, because it was so difficult to clean the paint off the syringe and plunger.
All six of the laboratories were given 1 mL disposable syringes and 22 gauge needles as
part of the materials supplied to them. The laboratories were told at the kick-off meeting that
they could use the syringes to load the PTFE liners or a method of their own if they felt it would
work better. All of the laboratories chose to use the syringes supplied to them to load the paint
samples. The mean weight of paint applied to the PTFE liners in the interlaboratory study using
27
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the 1 mL syringes was 31 mg with a %RSD of 28%. Considering the difficulty in accurately
delivering such a small volume of paint (25 uL), these results are very good.
Laboratory 1 found a problem in applying equation 13.2 in the draft method. Equation
13.2 is shown below. This equation fails to show that the weight percent of 2-butoxyethanol in
the standard solution (Wt.%s) needs to be divided by 100 to convert the percentage back into a
fraction. Laboratory 1 followed this equation strictly and results showed a mass value that was
one hundred times too large. Equation 13.2 needs to be revised to include the Wt% conversion.
masss = (Massss) (Wt.%s)
Comments from Laboratories
At the kickoff meeting, the laboratories were asked to give written comments on the draft
method if they desired. The comments received can be found in Table 5.7.
Table 5.7. Laboratory Comments on Draft Method
Laboratory
Comments:
1
The method was very straightforward and no problems were encountered in the
actual preparation and analyses. The instrumentation worked well and required
very little extra attention. The only item that was unclear was the use of the "%"
factor in the calculations. Although it works itself out because it is used at the
front-end and the back-end of the calculations, our numbers in the middle of the
calculations were off by a factor of 100.
Since many material data safety sheets (MSDS) are prepared with limited
individual component and concentration data, determination of accurate average
relative sensitivity values may be difficult.
From the QCCS Data Sheet and the test method, it was a bit unclear how
to calculate the 2-BE Mass (mg). No instructions were included in the
test method explaining the calculation of this step (R^/average RF).
Since there are many calculations in the test method using both very
small numbers and very large numbers, it may be useful to include in the
test method guidelines as far as either significant figures or decimal place
values.
28
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Table 5.7. Laboratory Comments on Draft Method
(Continued)
Laboratory
Comments:
4
(Cont.)
In general, the calculations in the test method were sometimes confusing,
and often a bit too complex and time-consuming.
During the addition of the coatings to the liner, it was a little difficult in
the beginning to obtain consistent weight numbers among the triplicate
preparations. The technique did improve with each sample. However,
base on the data, it appears that achieving consistent sample weights
among the replicates could be a critical factor for achieving acceptable
data.
Since the test method relies on the composition of the coating, it would
appear that the availability of a complete MSDS would be a critical
factor for the calculations. Since not all companies are willing to divulge
certain information, the absence of this information may affect the
results. For example, the MSDS for sample MS1-6659A essentially
listed only 3 solvents. An actual GC compositional analysis of this
sample detected the presence of 10 solvents. Also, most MSDS
information lists only ranges for the concentrations. Depending on
whether each component is at the low or high end of the range, then
using only the middle number could affect the calculations. The MSDS
for sample 4206-0100 listed 3 solvents, each with a range of 1-5%. The
calculations for the EPA method specify using a value of 3 for each. An
actual compositional analysis of this sample detected that one solvent
was in the 3 % range, but that another was in the 1% range, and the third
was near 5%.
This test method relies on the analyst having a good knowledge of
chemistry. The calculations for the effective carbon number involve
knowing the complete structure of the solvent including the molecular
weight, carbon number, and ester, alcohol, and ether linkages. Mistakes
in any of these will result in erroneous calculations.
The general consensus of the personnel in our lab was that this particular
test method uses 2 (three, if you include the computer) rather expensive
pieces of equipment to generate data that must be extensively
manipulated using calculations based on information that may be
inaccurate or incomplete. For the cost of one piece of the equipment, an
analysis can be performed to determine the total VOC content using gas
chromatography, generating accurate data more easily.
29
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Table 5.7. Laboratory Comments on Draft Method
(Continued)
Laboratory
Comments:
The proposed method shows a great deal of promise in measuring the
VOC content of coatings directly rather than indirectly as is currently
done in the gravimetric ASTM, EPA and SCAQMD methods. However,
the proposed method may require modification and tighter QC
requirements in order to make it applicable to the wide range of samples
received for compliance analysis. Comparing the current and proposed
methods might also yield useful results. Potential problems in applying
this method to compliance samples are as follows:
The proposed method requires formulation data to calculate average FID
sensitivity and corrected VOC content. This is a problem for compliance
samples, which almost never have accompanying formulation data.
Even when the data is available, it may be irrelevant because of "field
modification" of the coating, or the data itself may be in dispute.
Because of these issues, the proposed method may need to be modified
to make it applicable to coatings that are completely unknown.
The proposed method calculates VOC as weight percent of material
injected into the instrument. The calculation should be modified to
exclude exempt solvents. Also, since the EPA and SCAQMD require
VOC "of coating", these should be included in the calculations.
The acceptable calibration error (+/- 30% RSD) allows too much error
for compliance purposes. The calibration range of the proposed method
is from 0.5% to 50% VOC (w/w) of material, which translates to about 5
to 500 g/L VOC. SCAQMD method has a repeatability of about 10
grams per liter of VOC over 50-500 g/L. However, the accuracy of the
gravimetric method is unknown. Direct comparison might have revealed
a method bias.
The proposed method may not be suitable for multi-package coating that
require special curing conditions. It would be useful in distinguishing
between water or ammonia emissions and VOC emissions, which the
current gravimetric method can't differentiate.
The lowest standard appears to be too low to yield repeatable results.
30
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ASTM E691 Results
The corrected weight percent VOC (Wt% VOCC) values were the test results analyzed
using the statistical procedures described in ASTM 691. This is the final result that is obtained
from the draft method once all of the measurements and calculations have been completed. The
Wt% VOCC results were arranged in tables by paint. The three Wt% VOCC results reported by
each laboratory were entered into the tables and the following statistics were calculated following
the equations in ASTM 691. The calculations were performed using the PROC GLM procedure
inSAS:
x = individual Wt% VOCC test result
x = the mean of the three test results from each laboratory
x' = the mean of the xs calculated for each laboratory
s = standard deviation of the three test results from each laboratory
d = cell deviation = x-x'
s^ = standard deviation of the laboratory means
sr = repeatability standard deviation
SR = reproducibility standard deviation
k = s/s
Tables 5.8-5.1 1 show the individual Wt% VOCC results measured by each laboratory. As
mentioned earlier, the results from laboratory 3, 4, and 5 were corrected before they were entered
into the tables, so that all of the laboratories were using the same correction factors. Also shown
in these tables are the results of the calculations for x, s, d, h, and k. The results for x', sx, sr, and
SR are shown in Table 5.12.
As mentioned in the QA Activities, Battelle retrieved the paint samples that were used by
laboratory 3 and analyzed them with a separate ATD-400. For comparison of Wt% VOCC
31
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values, the Battelle results have been included in Tables 5.8-5.11. However, the Battelle results
were not used in any of the ASTM E691 precision calculations.
The mean Wt% VOCC values (x) from Tables 5.7-5.10, have been plotted by paint in
Figures 5.1-5.4. The Battelle values have also been included in these figures. The laboratories
show very good agreement on each of the four paints. The mean Wt% VOCC from the Battelle
measurements also compare very well with the laboratory results. In general, the Battelle results
are in the middle of the range of mean Wt% VOCC reported by the six laboratories. Since
Battelle used a different ATD-400 from the laboratories, the good agreement between the
Battelle and six laboratory results indicates there is not any evidence of instrument bias with the
draft method. The consistency of the paint results shows that the draft method was very
insensitive to the GC and chromatographic data system that were used.
Table 5.8. Paint 4020-1000 Wt% VOCC Results
Lab
Number
1
2
3
4 :
5
6
Battelle
Test Results, x
1
3.13
2.64
2.96
2.74
2.97
2.92
2.81
2
3.12
2.62
2.97
2.82
2.89
2.86
2.82
3
3.09
2.60
3.01
2.80
2.74
2.88
2.78
x
3.113
2.620
2.980
2.787
2.867
2.887
2.80
s
0.0208
0.0200
0.0265
0.0416
0.1168
0.0306
0.0241
d
0.2378
-0.2556
0.1044
-0.0889
-0.0089
0.0111
h
1.42
-1.52
0.62
-0.53
-0.05
0.07
k
0.38
0.37
0.49
0.76
2.14
0.56
32
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Table 5.9. Paint 1403-0100 Wt% VOCC Results
Lab
Number
1
2
3
4
5
6
Battelle
Test Results, x
1
5.92
4.94
3.81
4.94
5.03
4.89
4.30
2
5.95
4.84
3.92
4.92
4.99
4.91
4.57
3
6.07
4.87
3.89
5.01
5.10
4.88
4.51
X
5.980
4.883
3.873
4.957
5.040
4.893
4.460
s
0.0794
0.0513
0.0569
0.0473
0.0557
0.0153
0.1450
d
1.0422
-0.0544
-1.0644
0.0189
0.1022
-0.0444
h
1.56
-0.08
-1.59
0.03
0.15
-0.07
k
1.46
0.94
1.05
0.87
1.02
0.28
Table 5.10. Paint 4206-0100 Wt% VOCC Results
Lab
Number
1
2
3
4
5
6
Battelle
Test Results, x
1
9.50
8.87
9.81
10.5
9.87
9.85
9.19
2
9.68
8.69
9.59
10.5
9.72
10.2
9.47
3
9.74
9.14
10.0
10.3
9.94
10.1
8.40
x
9.640
8.900
9.800
10.43
9.843
10.05
9.353
s
0.1249
0.2265
0.2052
0.1155
0.1124
0.1790
0.1421
d
-0.1372
-0.8772
0.0228
0.6561
0.0661
0.2694
h
-0.27
-1.72
0.04
1.29
0.13
0.53
k
0.75
1.36
1.23
0.69
0.67
1.07
33
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Table 5.11. Paint MS1-6659A Wt% VOCC Results
Lab
Number
1
2
3
4
5
6
Battelle
Test Results, x
1
17.3
14.0
15.6
15.5
13.5
16.5
14.3
2
16.1
13.9
15.5
16.7
14.5
16.3
14.4
3
16.0
14.0
15.2
16.4
13.5
16.6
14.5
X
16.47
13.96
15.43
16.20
13.86
16.48
14.39
s
0.7234
0.0700
0.2082
0.6245
0.5860
0.1716
0.1055
d
1.0656
-1.4411
0.0322
0.7989
-1.5378
1.0822
h
0.88
-1.19
0.03
0.66
-1.27
0.89
k
1.53
0.15
0.44
1.32
1.24
0.36
Figure 5.1. Mean Wt% VOCC Results from Paint 4020-1000 by Laboratory
Laboratory
34
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Figure 5.2. Mean Wt% VOCC Results from Paint 1403-0100 by Laboratory
8.000
7.000
6.000
5.000
4.000
3.000
2.000
1.000
0.000
14.000
12.000
2.000
0.000
Laboratory
Figure 5.3. Mean Wt% VOCC Results from Paint 4206-0100 by Laboratory
Laboratory
35
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Figure 5.4. Mean Wt% VOCC Results from Paint MS1-6659A by Laboratory
25.000
0.000
Laboratory
The h and k values reported in Tables 5.8-5.11 are consistency statistics. The h statistic is
a between-laboratory consistency statistic. A large value of this statistic indicates that a
laboratory produces data that yields significantly different Wt% VOCC results from the other
laboratories. The k statistic is a within-laboratory consistency statistic. A large value of this
statistic indicates a laboratory that produces data that is significantly more variable than data
from the other laboratories.
As directed in ASTM E 691, the values of h and k consistency statistics in Tables 5.8-
5.11 were plotted on bar graphs in two ways: paints grouped by laboratory (Figure 5.6 and 5.8)
and laboratories grouped by paint (Figures 5.5 and 5.7). On Figures 5.5-5.8, the paints were
arranged in order of increasing mean Wt% VOCC (x) and the laboratories were arranged in order
of their code number (1-6). For plotting purposes on Figures 5.5-5.8, the paints have been given
the following codes:
36
-------
Paint 4020-1000 = A
Paint 1403-0100 = B
Paint 4206-0100 = C
Paint MS 1-6659A = D
The critical values of the hand k consistency statistics at the 0.5% significance level (a =
0.005) were also plotted as recommended in ASTM E 691. These values are shown as the
horizontal dashed lines in Figures 5.5-5.8. The critical values of h depend on the number of
laboratories participating in the interlaboratory study (six for this study), and the critical values
of k depend both on the number of laboratories and on the number of replicate test results per
laboratory per paint (three for this study). The critical values were obtained from Table 12 in
ASTM E 691. The critical value for h is ±1.92 and for k is 1.98.
An examination of Figures 5.5 and 5.6 show none of the h statistics from the
interlaboratory study exceeded the critical value; therefore, there is not enough evidence to show
that any one of the laboratories produced biased data relative to the other laboratories in the
study. Figure 5.7 and~S>S show that laboratory 5 exceeded the critical k value for paint 4020-
1000 (A). The result means that laboratory^ produced a mean Wt% VOCC whose standard
deviation was significantly higher than that of the other laboratories in the study.
The k statistic for the other three paints analyzed by laboratory 5 were not out of line with
the values from the other laboratories even though these paints had higher mean Wt% VOCC. A
review of the data did not reveal any calculation errors. The %RSD for laboratory 5, paint 4020-
1000 was 4.07%. Since no physical evidence indicated a problem with the laboratory 5 paint
4020-1000 results, the data was retained in the analysis.
37
-------
Figure 5.5. h - Laboratories within Paints
o.u -
2.5 -
2.0 -
o 1.5 -
en
3 '•»-
I "1
jj °-°-
In
'« -0.5 -
o
O -1.0 -
1
•= -1.5-
-2.0 -
-2.5 -
-3.0 -
,l
I
Lab: 123456 123456 123456 123456
Paint: A B C D
Figure 5.6. h - Paints within Laboratories
o
o>
3.0
2.5 -
2.0 -
o 1.5 -
"55
0.5 -
0.0
' -0.5 -
O -1.0-
^ -1.5 -
-2.0 -
Paint: ABCD
Lab: 1
ABCD
2
ABCD
3
ABCD
4
ABCD
5
ABCD
6
38
-------
3.0
2.5 -
in
= 2.0
W
0> 1-3
"w
'in
O 1.0
0.5 -
0.0
3.0
2.5 -
'•a 2-
-------
Table 5.12 summarized the precision statistics for the interlaboratory study of draft water-
based coating method as recommended by ASTM E 691. As defined earlier, x' is the overall
measured mean Wt% VOCC for the eighteen observations reported for each paint (six
laboratories, each making three measurements). The standard deviation of the six different
laboratory means is reported as sx. The repeatability standard deviation (within a laboratory)
and the reproducibility standard deviation (between laboratories) are reported as sr and SR
respectively. Figure 5.9 shows sr and SR plotted at a function of x'.
Table 5.12. Precision Statistics
Paint
4020-1000
1403-0100
4206-0100
MS1-6659A
x'
2.8756
4.9378
9.7772
15.4011
Sx
0.1678
0.6686
0.5092
1.2155
sr
0.0545
0.0544
0.1668
0.4716
SR
0.1736
0.6701
0.5271
1.2751
r
0.15
0.15
0.47
1.32
R
0.49
1.88
1.48
3.57
As stated in ASTM E 691, the 95% repeatability (r) and reproducibility (R) limits were
calculated with the following equations and are reported in Table 5.12.
r = 2.8 sr
R = 2.8sR
40
-------
Figure 5.9. Standard Deviations of Repeatability and Reproducibility Versus Mean Wt% VOCC
3.00
2.50
2.00
1.50
S
-------
with ASTM E 177, Standard Practice for Use of the Terms Precision and Bias in ASTM Test
Methods.
Table 5.13. Precision Statement*
Paint
4020-1000
1403-0100
4206-0100
MS1-6659A
Wt%
Average
2.8756
4.9378
9.7772
15.4011
Repeatability
Standard
Deviation
(Wt %)
0.0545
0.0544
0.1668
0.4716
Reproducibility
Standard
Deviation
(Wt %)
0.1736
0.6701
0.5271
1.2751
Repeatability
Limit
(Wt %)
0.15
0.15
0.47
1.32
Reproducibility
Limit
(Wt %)
0.49
1.88
1.48
3.57
A The table was calculated using the relationship: limit = 2.8 x standard deviation
Interlaboratory Test Program - An interlaboratory study of weight percent volatile organic
chemicals in water-based coatings was conducted in accordance with Practice ASTM E 691 in
six laboratories with four paints, with each laboratory obtaining three test results for each
material
42
-------
References
1. ASTM E-177, Standard for Use of the Terms Precision and Bias in ASTM Test Methods,
1990, 79-90.
2. ASTM E 691, Standard Practice for Conducting a Interlaboratory Study to Determine the
Precision of a Test Method, 1992, 425-443.
3. Jorgensen, A.D., Picel, K.C., Stamoudis, V.C., Prediction of Gas Chromatography Flame
lonization Detector Response Factors from Molecular Structures, Analytical Chemistry,
1990, 62: 683-689.
4. Peterson, M.R., Howe, G.B., Jayanty, R.K.M. Development and Evaluation of a
Procedure to Measure Total VOC in Paints and Coatings Using an Automated Thermal
Desorption Device and a Gas Chromatorgaphy Detector, Draft Report to U.S.
Environmental Protection Agency, Contract No. 68D20163, Research Triangle Institute,
Research Triangle Institute, Research Triangle Park, North Carolina, September 1996.
5. Evaluation of the Water-based Coating Method, U.S. Environmental Protection Agency
Report, August 30, 1995.
43
-------
APPENDIX A
MSDS SHEETS FOR STUDY PAINTS AND AVERAGE RELATIVE
SENSITIVITY CALCULATIONS
-------
MSDS for Paints MS1-6659A and MS1-6660A
-------
MATERIAL SAFETY DATA SHEET
SI-6660A
4 00
ANUFACTURER'S NAME
MARTIN SENOUR PAINTS
101 Prospect Avenue
Cleveland, OH 44115
ATE OF PREPARATION
07-SEP-99
EMERGENCY TELEPHONE NO.
(216) 566-2917
INFORMATION TELEPHONE NO.
(216) 566-2902
Section I — PRODUCT IDENTIFICATION
RODUCT NUMBER
MSI-6660A
HMIS CODES
Health
Flammability
Reactivity
3*
0
0
RODUCT NAME
MSI* Waterborne Industrial Enamel, Gray (Ford)
RODUCT CLASS
Water-reducible Acrylic Coating
Section II — HAZARDOUS INGREDIENTS
NGREDIENT ACGIH OSHA
CAS No. % by WT TLV PEL UNITS V.P.
-Propoxyethanol
2807-30-9
-Butoxyethanol
111-76-2
Cobalt 2-Ethylhexanoate.
_ 136-52-7
(riethylamine.
121-44-8
Titanium Dioxide.
13463-67-7
Carbon Black.
1333-86-4
pH - 8.7
4 Not Established 1.30
7 25 25 PPM (Skin) 0.60
0.2 Not Established 0.00
2 1 25 PPM (Skin) 54.00
STEI, 3 100 PPM (Skin)
14 10 10(5) MG/M3 as Dust ***
•*** Total Dust (Respirable Fraction)
0.4 3.5 3.5 MG/M3 0.00
Section III — PHYSICAL DATA
PRODUCT WEIGHT — 9.37 Ib./gal. EVAPORATION RATE — Slower than Ether
SPECIFIC GRAVITY — 1.13 VAPOR DENSITY — Heavier than Air
BOILING POINT — 185-343 F MELTING POINT — N.A.
VOLATILE VOLUME — 68 % SOLUBILITY IN WATER — N.A.
OC (Theoretical) — 2.77 Ib. 332 gm. (less Federally Exempt Solvents)
Section IV — FIRE AND EXPLOSION HAZARD DATA
FLASH POINT
Not Applicable
FLAMMABILITY CLASSIFICATION
Not Applicable
LEL
N.A.
UEL
N.A.
Continued on page 2
-------
C3/ / / ao %j . i^-j .
MSI-6660A page 2
XTINGUISHING MEDIA
Carbon Dioxide, Dry Chemical, Alcohol Foam
NUSUAL FIRE AND EXPLOSION HAZARDS
Closed containers may explode (due to the build-up of pressure) when
xposed to extreme heat.
PECIAL FIRE FIGHTING PROCEDURES
Full protective equipment including self-contained breathing apparatus
hould be used. Water spray may be ineffective. If water is used, fog
ozzles are preferable. Water may be used to cool closed containers to
revent pressure build-up and possible autoignition or explosion when
xposed to extreme heat.
Section V — HEALTH HAZARD DATA
OUTES OF EXPOSURE
Exposure may be by INHALATION and/or SKIN or EYE contact, depending on
onditions of use. Alcohols and acetates can be absorbed through the skin.
'ollow recommendations for proper use, ventilation, and personal protective
quipment to minimize exposure.
CUTE Health Hazards
FFECTS OF OVEREXPOSURE
Irritation of eyes, skin and upper respiratory system. In a confined
rea vapors in high concentration may cause headache, nausea or dizziness.
IGNS AND SYMPTOMS OF OVEREXPOSURE
Redness and itching or burning sensation may indicate eye or excessive
kin exposure.
EDICAL CONDITIONS AGGRAVATED BY EXPOSURE
None generally recognized.
MERGENCY AND FIRST AID PROCEDURES
If INHALED: If affected, remove from exposure. Restore breathing.
Keep warm and quiet.
If on SKIN: Wash affected area thoroughly with soap and water.
Remove contaminated clothing and launder before re-use.
If in EYES: Flush eyes with large amounts of water for 15 minutes.
Get medical attention.
If SWALLOWED: Get medical attention.
HRONIC Health Hazards
Carbon Black is classified by IARC as possibly carcinogenic to humans
group 2B) based on experimental animal data, however, there is
nsufficient evidence in humans for its carcinogenicity.
Cobalt and cobalt compounds are classified by IARC as possibly
arcinogenic to humans (group 2B) based on experimental animal data,
owever, there is inadequate evidence in humans for its carcinogenicity.
Prolonged overexposure to solvent ingredients in Section II may cause
dverse effects to the liver, urinary and blood forming systems.
Rats exposed to titanium dioxide dust at 250 mg./m3 developed lung
ancer, however, such exposure levels are not attainable in the workplace.
Section VI — REACTIVITY DATA
TABILITY — Stable
ONDITIONS TO AVOID
None known.
NCOMPATIBILITY
None known.
Continued on page 3
-------
MSI-6660A page 3
AZARDOUS DECOMPOSITION PRODUCTS
By fire: Carbon Dioxide, Carbon Monoxide
AZARDOUS POLYMERIZATION
Will not occur
Section VII — SPILL OR LEAK PROCEDURES
TEPS TO BE TAKEN IN CASE MATERIAL IS RELEASED OR SPILLED
Remove all sources of ignition. Ventilate and remove with inert
bsorbent.
ASTE DISPOSAL METHOD
Waste from this product is not hazardous as defined under the Resource
onservation and Recovery Act (RCRA) 40 CFR 261.
Incinerate in approved facility. Do not incinerate closed container.
ispose of in accordance with Federal, State, and Local regulations
egarding pollution.
Section VIII — PROTECTION INFORMATION
RECAUTIONS TO BE TAKEN IN USE
Use only with adequate ventilation. Avoid breathing vapor and spray
1st. Avoid contact with skin and eyes. Wash hands after using.
This coating may contain materials classified as nuisance particulates
listed "as Dust" in Section II) which may be present at hazardous levels
nly during sanding or abrading of the dried film. If no specific dusts
re listed in Section II, the applicable limits for nuisance dusts are
CGIH TLV 10 mg./m3 (total dust), 3 mg./m3 (respirable traction), OSHA PEL
5 mg./m3 (total dust), 5 mg./m3 (respirable fraction).
ENTILATION
Local exhaust preferable. General exhaust acceptable if the exposure to
aterials in Section II is maintained below applicable exposure limits.
efer to OSHA Standards 1910.94, 1910.107, 1910.108.
ESPIRATORY PROTECTION
If personal exposure cannot be controlled below applicable limits by
entilation, wear a properly fitted organic vapor/particulate respirator
pproved by NIOSH/MSHA for protection against materials in Section II.
When sanding or abrading the dried film, wear a dust/mist respirator
pproved by NIOSH/MSHA for dust which may be generated from this product,
nderlying paint, or the abrasive.
ROTECTIVE GLOVES
Wear gloves which are recommended by glove supplier for protection
gainst materials in Section II.
YE PROTECTION
Wear safety spectacles with unperforated sideshields.
Section IX — PRECAUTIONS
OL STORAGE CATEGORY
Not Applicable
RECAUTIONS TO BE TAKEN IN HANDLING AND STORING
Keep container closed when not in use. Transfer only to approved
ontainers with complete and appropriate labeling. Do not take internally.
eep out of the reach of children.
Continued on page 4
-------
MSI-6660A page 4
Section X — OTHER REGULATORY INFORMATION
— _ — — — — _ — ^._«_____ — — __ — __-__—,— _ — __—.___ — — — — _— — — — — — — — — — — — — — — — — — — — — — — —— — —— — —— — —— —
ARA 313 (40 CFR 372.65C) SUPPLIER NOTIFICATION
CAS No. CHEMICAL/COMPOUND % by WT % Element
— __- — — ____„»„__________.„,_____„__.„__„___- — — — _— — — — — —_ — — — — — — — —— — —— — — — — — — — —— — —— — —— —
121-44-8 Triethylamlne. 2
Cobalt Compound. 0.2 0.0
Glycol Ethers 12
ALIFORNIA PROPOSITION 65
WARNING: This product contains a chemical known to the State of
alifornia to cause cancer.
SCA CERTIFICATION
All chemicals in this product are listed, or are exempt from listing,
n the TSCA Inventory.
The above information pertains to this product as currently formulated,
nd is based on the information available at this time. Addition of
educers or other additives to this product may substantially alter the
omposition and hazards of the product. Since conditions of use are
utside our control, we make no warranties, express or implied, and assume
o liability in connection with any use of this information.
-------
-------
1Z:37HPAGE 001/9HRightFAX
MATERIAL SAFETY DATA SHEET
SI-6659A
3 00
ANUFACTURER'S NAME
MARTIN SENOUR PAINTS
101 Prospect Avenue
Cleveland, OH 44115
EMERGENCY TELEPHONE NO
(216) 566-2917
ATE OF PREPARATION
25-AUG-99
INFORMATION TELEPHONE NO.
(216) 566-2902
Section I — PRODUCT IDENTIFICATION
RODUCT NUMBER HMIS CODES
Health 2*
MSI-6659A Flamroability 0
Reactivity 1
RODUCT NAME
MSI* Waterborne Industrial Enamel, Silver
RODUCT CLASS
Water-reducible Acrylic Coating
Section II — HAZARDOUS INGREDIENTS
NGREDIENT ACGIH OSHA
CAS No. % by WT TLV PEL UNITS V. P.
/Mineral Spirits. 1 100 100 PPM 2.00
64742-88-7
-Propoxyethanol 5 Not Established 1.30
2807-30-9
-Butoxyethanol 6 25 25 PPM (Skin) 0.60
111-76-2
obalt 2-Ethylhexanoate. 0.2 Not Established 0.00
136-52-7
pH - 8.7
Section III — PHYSICAL DATA
•
PRODUCT WEIGHT — 8.50 Ib./gal. EVAPORATION RATE — Slower than Ether
SPECIFIC GRAVITY — 1.02 VAPOR DENSITY — Heavier than Air
BOILING POINT — 212-395 F MELTING POINT — N.A.
VOLATILE VOLUME — 69 % SOLUBILITY IN WATER — N.A.
DC (Theoretical) — 2.76 Ib. 330 gnu (less Federally Exempt Solvents)
Section IV — FIRE AND EXPLOSION HAZARD DATA
'LASH POINT LEL UEL
Not Applicable N.A. N.A.
LAMMABILITY CLASSIFICATION
Not Applicable
XTINGUISHING MEDIA
Carbon Dioxide, Dry Chemical, Alcohol Foam
NUSUAL FIRE AND EXPLOSION HAZARDS
Closed containers may explode (due to the build-up of pressure) when
xposed to extreme heat.
-------
PECIAL FIRE FIGHTING PROCEDURES
Full protective equipment including self-contained breathing apparatus
hould be used. Water spray may be ineffective. If water is used, fog
ozzles are preferable. Water may be used to cool closed containers to
revent pressure build-up and possible autoignition or explosion when
xposed to extreme heat.
Section V — HEALTH HAZARD DATA
OUTES OF EXPOSURE
Exposure may be by INHALATION and/or SKIN or EYE contact, depending on
onditions of use. Alcohols and acetates can be absorbed through the skin.
ollow recommendations for proper use, ventilation, and personal protective
quipment to minimize exposure.
CUTE Health Hazards
FFECTS OF OVEREXPOSURE
Irritation of eyes, skin and upper respiratory system. In a confined
rea vapors in high concentration may cause headache, nausea or dizziness.
IGNS AND SYMPTOMS OF OVEREXPOSURE
Redness and itching or burning sensation may indicate eye or excessive
kin exposure.
"EDICAL CONDITIONS AGGRAVATED BY EXPOSURE
None generally recognized.
MERGENCY AND FIRST AID PROCEDURES
If INHALED:
Restore breathing.
If affected, remove from exposure.
Keep warm and quiet.
If on SKIN: Wash affected area thoroughly with soap and water.
Remove contaminated clothing and launder before re-use.
If in EYES: Flush eyes with large amounts of water for 15 minutes.
Get medical attention.
If SWALLOWED: Get medical attention.
HRONIC Health Hazards
Cobalt and cobalt compounds are classified by IARC as possibly
arcinogenic to humans (group 2B) based on experimental animal data,
owever, there is inadequate evidence in humans for its carcinogenicity.
Prolonged overexposure to solvent ingredients in Section II may cause
dverse effects to the liver, urinary and blood forming systems.
Section VI — REACTIVITY DATA
TABILITY — Stable
ONDITIONS TO AVOID
None known.
NCOMPATIBILITY
None known.
AZARDOUS DECOMPOSITION PRODUCTS
By fire: Carbon Dioxide, Carbon Monoxide
AZARDOUS POLYMERIZATION
Will not occur
Section VII — SPILL OR LEAK PROCEDURES
TEPS TO BE TAKEN IN CASE MATERIAL IS RELEASED OR SPILLED
Remove all sources of ignition. Ventilate and remove with
bsorbent.
-------
18/25/99
(PAGE 003/91
|RightFAX|
page 3
ASTE DISPOSAL METHOD
Waste from this product is not hazardous as defined under the Resource)
onservation and Recovery Act (RCRA) 40 CFR 261.
Incinerate in approved facility. Do not incinerate closed container.
ispoae of in accordance with Federal, State, and Local regulations
egarding pollution.
Section VIII — PROTECTION INFORMATION
RECAUTIONS TO BE TAKEN IN USE
Use only with adequate ventilation. Avoid breathing vapor and spray
1st. Avoid contact with akin and eyes. Wash hands"after using. .--.-..-..-
This coating may contain materials classified as nuisance particulates
listed "as Dust" in Section II) which may be present at hazardous levels
nly during sanding or abrading of the dried film. If no specific dusts
re listed in Section II, the applicable limits for nuisance dusts are
CGIH TLV 10 mg./m3 (total dust), 3 mg./m3 (reapirable fraction), OSHA PEL
5 mg./m3 (total dust), 5 mg./m3 (respirable fraction).
•ENTILATION
Local exhaust preferable. General exhaust acceptable if the exposure to
aterials in Section II is maintained below applicable exposure limits.
efer to OSHA Standards 1910.94, 1910.107, 1910.108.
ESPIRATORY PROTECTION
If personal exposure cannot be controlled below applicable limits by
entilation, wear a properly fitted organic vapor/particulate respirator
pproved by NIOSH/MSHA for protection against materials in Section II.
When sanding or abrading the dried film, wear a dust/mist respirator
pproved by NIOSH/MSHA for dust which may be generated from this product,
nderlying paint, or the abrasive.
ROTECTTVE GLOVES 'c
Wear gloves which are recommended by glove supplier for protection
gainst materials in Section II.
YE PROTECTION
Wear safety spectacles with unperforated sideshields.
Section IX — PRECAUTIONS
OL STORAGE CATEGORY
Not Applicable
RECAUTIONS TO BE TAKEN IN HANDLING AND STORING
Keep container closed when not in use. Transfer only to approved
ontainers with complete and appropriate labeling. Do not take internally.
eep out of the reach of children.
Section X — OTHER REGULATORY INFORMATION
ARA 313 (40 CFR 372.65C) SUPPLIER NOTIFICATION
•••••••I
|CAS No. CHEMICAL/COMPOUND
% by WT % Element
Cobalt Compound.
Glycol Ethers
SCA CERTIFICATION
chemicals
Inventory
Continued
-------
RightFAX
page 4
The above information pertains to this product as currently formulated,
nd is based on the information available at this time. Addition of
educers or other additives to this product may substantially alter the
omposition and hazards of the product. Since conditions of use are
utside our control, we make no warranties, express or implied, and assume
o liability in connection with any use of this information.
-------
™ MATERIAL SAFETY DATA SHEET
THE MARTIN-SENOUR CO.
101 PROSPECT AVB. N.W.
CLEVELAND, OH 441 IS
EMERGENCY TELEPHONE NO. (211) «t«-2U7
INFORMATION TELEPHONE NO. (11*) Sf*-2t01
DATE OF PREPARATION 1 -NOT - 91
OlSfC. Tbr Uartm-Scnour C«.
Waterborne Industrial Enamel
SECTION II -
. HAZABOOUS HOBEMEMT
UkwtflSprto
r-PmpoxyKNinot
MSI/N2
:rvji.«»ert «<*--.. i- i«<**x] requtrarntno <* Hie Sioirfund
AJ (SAPAl '«».•»•• 3 13. WOP 377 65 c
Irv/ Page Follows
11-27
its
-------
\MSI™ Waterborne Industrial Enamel
I Section III — PHYSICAL DATA I
PMXVCT wiorr - s«e tau
c aurrrr - l.oi 1.11
KULIXC mat - itj-itt -r |
OUHL* vOLua- - »«oj \
pa - t -i
tv*iauni - H.A.
Section IV — FRE AND EXPLOSION HAZARD DATA
•ee TABU
LEI. H Ap
H.Ap.
nJUHUIUTY i
»>t Appilcab)e
•imxnsurK mot*
Carbon Dioxide. Dry Chemical. Alcohol roam
ima. nti u*> txnosiem moults
Closed rentalnera may explode (due to Che build-up of pressure) whsn exposed to eortrem
SPEL-IU. nu riamoK ncctnjnis
rull protective equipment including eel f-contained breathing ApparAtus should be used.
water spray smy be ineffective. It water le meed, fog monies are preferable. Water may be
lueed to coo: closed eoatainera to prevent pressure build-up and possible Autoignition ox-
explosion ufcen exposed to extreme heat.
I Section V — HEALTH HAZARD DATA
ts of tzKSUft
xposure s»y be b* inHALATlON end/or SKIM or BT1 contect, depending on conditions of use.
Alcoaols sac! ACetAtes CSA be Absorbed through the. skin. To xdnimive exposure, follow
receae>endAtiona (or proper uscr vest 11 At 1 on, And personAt protective equipment.
ACUTE Mean Hazard*
ALI* ter for IS stioutes. Get nedicAl Attention.|
If SWU-U»*D: Get Bedlcsl Attention.
CXHONICHsefelHAiAJas
CATboe •} sck II clssiified by 1AHC AS possibly CArcinogenic to hueens (group 31} besed on
eotperieentAl snietAl dsts. however. f-h*re is insufficient evidence in butftns Cor its CArcinoge-
nielty.
Ccbelt An4 cubslt conpoundx Are classified by 1ARC AS possibly CArcirvooenic to huxtAns (group |
»l bued on experiAuntsl sniKAl d>t>. however, there is insdeguete evidence in bUBsms for its
CATcanogeniclty.
rrolonged e-erexposurs to solvent Ingredients in Section II swry reuse Adverse effects to t*e |
liver, urintxy. end blood Ccreiing systesui.
Kets exposed to tltexiue dioxide oust At 3»0 ng 1*3 developed lung csncer. howerver. sucb
exposure levels Are not sttAie«ble in tiie workplece.
I Swtton VI — REACTIVITY DATA]
ST.UH.ITv - StAbltl
CtxeDrTJOxCS TO AVOID
•one
afHTitiun
Hone knowr.
joaaos DfcattrosiTiai mooucrs
•y fire: Csrbon Dioxids. CArbon honoxid* I
luuuioous roLnaniiATiai • fill not occur
Section VII — $P)LL OR LEAK PROCEDURES
I STTK TO u TAJUH nr out mruuAL is mMsto on SHLLXD
ova all sources of ignition. Ventilate and remove with Inert absorbent.
IWSTC DISPOSAL K1THOO
Mute from theaa products is not hazardous as defined under the Resource Conservation end I
[Recovery Act OCR*I 40 CI* 261.
cinerate in spprpved fAcility. Do not incinerate cloned container. Dispose of in
with Federal. State, and Local regulations regarding pollution.
ordsnce *
I Section Vlfl — PROTECTION INFORMATI
rJUCAOTlpjrl TO U TUB J» US1
Use only with adequate ventilation Avoid breathing vapor and spray mist Avoid ronttct
with (kin and eyas Huh hands after utina
These coatings may contain materials classifiexi AS nuisance particularea (listed 'as Dust- in
Section 11) which eey be preeent at baxardous levels only during sanding or abradimj of Ue
dried flip. If no apeclfic Aiats are listed in Section IX, th« applicable lieitt for nuisaoce
dusts are ACCIH TLV 10 mg./e.l (total dust), 1 eg. /wj (reepirable f ractioal . OSH* PM_ U eg /ml
(total dust), 5 •g./mj (renpirable fraction).
vnrriuiTiui
Local exhaust preferable. General exhsuvt acceptable if the exposure to staterisls in
Section II is maintained below applicable exposure lisUte. Refer to O5HA Standards 1910 M
Itlu.lO-f. 1910.IDi
JtC£*rMTOM1T PJhTfKTruH
If psrsonsl exposure CAnnot be controlled below spplicAble limits by ventilation wear
A properly fitted organic vapor/particulate respirator approved by MIOSH/MSHA for piot«*-lion
against materials in Section II.
Whan sanding or abrading the dried file, wear A dust/miet respirator approved by HIOSR/1SH*
for dust which ear be generated from this product, underlying paint, or the Abrasive
HtOTSCTlVt CUWSS
Hear gloves which are reccewjeoded by glove eupplier fcr protection against watatial* in
Section II.
eye rttmniai
WMSr ssfaty spectacles with unparforsted sideshields.
ISextton DX — PRECAl/nONS |
OOi sratACI CaTaOOnr . Hot Applicable
TAvrioMS TO w TAJrBr t* numuie JUD STOHXK
keep container closed wben not in use. Transfer only to Approved containers with coeplete
And appropriAle labeling. Do not take intemAlly. Keep out of the reach of children.
SacKon X — OTHER REGULATORY ^FORMATION
HAjnrlK: KSI-K22A. HS1-C710 and HSI17J1 contain a chsmicallsl known to the State of Cali-
fornia tn cause cancer. KSI-tCstC and HSI't>}4> contain chemicals known to the State of Cali-
fornia to cause caacer and birth defects or other reproductive hark.
ik comFiamcej
All chemicals In these products are listed, or are <
Inventory.
froet listing, on the TSCA
The above Inforawitloe. pertains to these products u currently formulated, and is based os
I the information available at this tin». addition of reducers or other additive* to these
•products evy substantially alter the composition and haiArds of the products. Since conditional
•of use are outside our control, we suJte no vBrraatiee. express or iattlied and assums i
[liability in connection with any use of this intonation.
{covers MSDS pages MSI/Ni to MSI
-------
MSDS for Paint 1403-0100
-------
Physical
Data
; p.-ddiici
Code
1 MIM-Olim
I40'-OI1I}
i4(u.di:(i
140.1- O.KXI
140.MUOO
14U3-UMJU
I40.«-H>M'
DescriDlion JLt&StZ J^t^i^^L £tf~P
dulux ullra inlcnor acrUu ccr-.heii. wtmr \S ~"
while tin! baic
pure brilliant white
intermediate lint tact
deen tint base
accent base
antiaue while
cielo bianco
WtJGil.
11.12
11.12
11.12
10.41
9.69
9.73
11.13
11.12
voc
trjtlr.
111.51
111.55
111.55
65.19
62.88
58.38
111.33
111.52
» Volatile
bi Volume
59.12
59 It
59.12
65.71
67.96
66.38
59.12
59.12
Flub
Point
none
none
none
none
none
none
none
none
Hulling
Rm«
212-477
212-477
212-477
212-477
212-477
212-477
212-477
212-477
HMIS
•mi
•no
•no
•no
•no
•110
•no
•MO
DOT. proper
shippinc lumr
MJnt *• DTTXeCI IIUIH iTCeZmtf *"
p«im ** inutcvf rimii iTCciUiu **
paim ** pnxeci mim freezing "
oami *" nroiect tu«n ireezin* '•
iwiiu *• ww«x( limn nreziuic "-
punt *" protect num nccztne "
Ingredients
Product Codes with % by Weight
jelhanol. 2.2'-o>vbiv
; limestone
• nepheline svenite
• kieseleuhr
: Quaru
; propanoic acid. 2-methyl-. monoester with
2.2.4-mmethvl- 1 .3-Dcnianediol
I titanium oxide
; vinvl acrvltc cooolvmer
| watei
2-propenoic acid. 2-methyl-. methyl ester, polymer with
: butvl 2-nroDenoate and elhenvlbenzene
1403-0100
1-5
5-10
1-5
1-5
If' W>
tuOfi
30-40
1-5
1403-0110
1-5
5-10
1-5
1-5
20-30
ic-Ifi
?!>-4()
1-5
1403-0120
1-5
5- in
i-5
1-5
2fi. ?f.
1I1--II
?!>--! 1
1-5
140.Vd.WO
10-20
1-5
10-20
10-20
40-50
1-5
1403-0400
10-20
1-5
1-5
10-20
50-60
1-5
1403-0500
5-10
10-20
1-5
20-30
50-60
1403-1000
1-5
5-10
1-5
1-5
20-30
10-20
30-40
1-5
1403-1020
1-5
5-10
1-5
1-5
20-30
10-20
30-40
1-5
1403-IOSt
1-5
5-10
1-5
1-5
20-30
10-20
30-40
1-5
ACGIH-TLV
CHEMICAL NAME
eUunot. 2,2"-oxvbii-
limesione
ncDhcline svcnilc
kieseleuhr
auan?
propanoic acid. 2-methyK monoeitcr with
2.2.4-mmethvl-I3-Denunedinl
litanium oxkte
«invl scrvliccoDolvmcr
witer
2-propenoic acid. 2-meihyl-. methyl ciicr. polymer with butyl
2-propenoate and ethenvl benzene
COMMON NAME
dicl^vlene clvcot
natural calcium carttonaic
same
silica1 diaiomiceous earth
quaru
lexanol
titanium dioxidr
vinvl acrvlic copolvmer
water
butyl acrylate-methyl
methacTvlate-stvrene cop
CAS. NO.
111-46-6
1317^5-3
37244-9(i-5
6l79(K^3-2
|4808-«0-7
25265-77-4
13463-67-7
sun. conf.
7732-18-5
27136-15-8
8-HOUR TWA
ne
10 me/rn1
lOmeAn^
IOmeAnJ
0.) m£/m'
ne
10 mE/m'
ne
ne
ne
STEL
ne
ne
ne
nc
ne
ne
ne
ne
ne
ne
OS*
S-HOURTWA
ne
5mc/nV
ne
6 mpAn'1
0.1 me/m
ne
5mc/m'
ne
ne
nc
IA-PEL
STEL
ne
ne
ne
ne
nr
nc
ne
ne
ne
ne
c
ne
nc
ne
ne
ne
ne
ne
ne
ne
nc
S
ne
ne
nc
ne
nc
nc
ne
ne
ne
ne
S.R.
STD.
ne
nc
ne
ne
ne
nc
nf
[H"
nc
ne
S
2
n
n
n
n
q
n
n
n
n
n
S
3
n
n
p
p
fl
n
n
n
n
n
C
(:
n
n
r)
n
p
n
n
n
n
n
N
n
n
p
n
V
n
n
n
n
n
1 o
n n
n n
D. n
n rP
\
n .1
n ru
L H
n n
Footnotes:
C » Oitaf • Cooatiimwn A
JLSTD • Suppler Recommend
S - Slun • Addrutfttl
pHU fa mJIInn
• milhfn
S2 - 3m S«okm XQ EHS
CERO- Wntc
N - NT?. I . IARC
y * yet. • • »o
Br
• OSH
Form: 1403 . Pa«c 2, prepared 07AH/97
-------
IFIRE AND EXPLOSION HAZARD DATA
I Extinguishing media : Dry chemical or foam water fog. Carbon dioxide.
I Unusual fire and explosion hazards: Closed containers may bunt if exposed to extreme heal or fire.|
In closed tanks, water or foam may cause frothing or eruption.
I Special fire fighting procedures : Water may be used to cool and protect exposed containers.
Firefighters should use full protective clothing, eye protection, and self-contained breathing
apparatus.
[HEAUliIiAZARD DATA
I Primary routed) of exposure : Inhalation, skin contact, eye contact, ingestion.
I Effects of overexposure :
Inhalation : Irritation of respiratory tract, lungs. Prolonged inhalation may lead to dizziness and/or
lighiheadedness. headache, nausea, vomiting, coughing, sneezing, central nervous system
depression, anesthetic effect or narcosis, difficulty of breathing, pneumoconiosis.
Skin contact: Irritation of skin. Prolonged or repeated contact can cause dermatitis, defauing.
Eye contact: Irritation of eyes. Prolonged or repealed contact can cause conjunctivitis.
I Ingestion : Ingestion may cause fatigue, drowsiness, dizziness and/or lightheadedness, nausea,
vomiting, diarrhea, gastro-iniesrinal disturbances, severe abdominal pain, central nervous
system depression, central nervous system damage, liver damage, kidney damage, bladder
damage, pulmonary edema, loss of consciousness, cyanosis, death.
| Supplemental health information : Contains a chemical that is moderately toxic by ingestion. Other |
effects of overexposure may include toxkity to liver, kidney. May be absorbed through skin
Contains crystalline silica which is considered a hazard by inhalation. IARC has classified
crystalline silica as probably carcinogenic for humans (2a). This classification is based on the
findings of laboratory animal studies that were considered sufficient and data from epidemiological I
studies that were considered limited for carcinogenicity. Crystalline silica is also a known cause of f
silicosis, a noncancerous lung disease. NTP has classified crystalline silica a reasonably anticipated I
human carcinogen. A study conducted by NTP. using a continuous breeding protocol,
demonstrated that diethylene glycol hi drinking water at a concentration of 3.5% (6.1 g^cg/day)
resulted in decreased fertility and reproductive performance in mice. These effects were not seen in I
the lower dose levels evaluated. Since the exposure resulting from incidental contact is likely to be [
lower by several degrees of magnitude and the route of exposure used in this study does not reflect
a likely route from occupational or consumer use the significance of these findings to humans is
uncertain.
| Medical conditions aggravated by exposure : Eye. skin, respiratory disorders kidney disorders liver
disorders nervous system disorders
iFmSTAroPROCEDURES
\ Inhalation : Remove to fresh air. Restore and support continued breathing. Gel emergency medical
attention. Have trained person give oxygen if necessary. Get medical help for any breathing
difficulty. Remove to fresh air if inhalation causes eye watering, headaches. HiT»inf«. or other I
discomfort.
| Skin contact: Flush from skin with water. Then wash thoroughly with soap and water. Remove
contaminated clothing. Wash contaminated clothing before re-use.
| Eve coo tact: Flush immediately with large amounts of water, especially under lids for at leas) 15 |
minutes. If irritation or other effects persist, obtain medical treatment.
I Ingestion : If swallowed, obtain medical treatment immediately.
IREACTIVITYDATA
I Stability: Stable
I Incompatibility : Oxidizen. acids, bases, aluminum, zinc, magnesium, sodium, potassium.
I Conditions to avoid : Elevated temperatures, contact with oxidizing agent, contact with aluminum or I
zinc, high concentration of dust, freezing, sparks, open flame.
I Hazardous decomposition products: Carbon monoxide, carbon dioxide, oxygen.
1 Hazardous polymerization : Will not occur
| Steps to be taken In case material Is released or spilled : Comply with all applicable health anil
environmental regulations. Eliminate all sources of ignition. Ventilate area. Spills may be collected |
with absorbent materials. Evacuate all unnecessary personnel. Place collected material in proper
container. Vacuum clean spillage. Large spills - shut off leak if safe to do so. Dike and contain
spill. Pump to storage or salvage vessels. Use absorbent to pick up excess residue. Keep
salvageable material and rinse water out of sewers and water courses. Small spills - use absorbent
to pkk up residue and dispose of properly.
| Waste disposal: Dispose in accordance with all applicable regulations. Avoid discharge to natural
waters.
[SPECIAL PROTECTIONlNFORMATION
| Respiratory protection : Control environmental concentrations below applicable standards. Where
respiratory protection is required, use only NIOSH/MSHA approved respirators in accordance with I
OSHA standard 29 CFR 1910.134.
I Ventilation : Provide dilution ventilation or local exhaust to prevent build-up of vapors.
I Personal protective equipment: Eye wash, safely shower, safety glasses or goggles. Impervious
gloves, impervious clothing, face shield.
| Handling and storage : Store below I00f(38c) Keep away from heal, sparks and open flame. Keep
from freezing.
| Other precautions : Use only with adequate ventilation. Do not take internally. Keep out of reach of
children. Avoid contact with skin and eyes, and breathing of vapors. Wash hands thoroughly after
handling, especially before eating or smoking. Keep containers tightly closed and upright when not |
in me. Avoid conditions which result in formation of inhalaWe particles such as spraying or
abrading (sanding) painted surfaces. If such conditions cannot be avoided, use appropriate
respiratory protection as directed under special protection information.
m
The information contained herein is based on data available at the time of preparation of this data shea which Id Paints believes lobe reliable. However, no warranty it expressed or Implied regarding I
the accuracy of mis data. Id Paints shall not be responsible for the me of this information, or of any product, method or apparatus mentinurd and you mutt make your own determination of to |
suitability and completeness for your own use, for the protection of the environment/ and the heahh and safety of your employees and the users of mis material.
Complies with OSHA hazard communication standard 29CFR1910.1200.
925 Euclid Avenue
Cleveland, Ohio 44115
EMERGENCY TELEPHONE NO. (800)545-2643
-------
MSDS for Paint 4020-1000
-------
Physical Data
Product
Code
4020-1000
4020-7100
Description
white .y
red
WL/Gal.
11.72
11.29
voc
er^tr.
77.48
81.58
% Volatile
by Volume
55.57
58.13
Flash
Point
none
none
Boiling
Ranee
212-453
212-453
HMIS
*310
•310
DOT, proper
shipping name
paint '* protect from freezing ** *
paint ** protect from freezing **
Ingredients
Product Codes with % by Weight
carbonic acid calcium salt
quartz
solvent naphtha (petroleum), medium aliphatic
ethanol, 2-(2-butoxvethoxv)-
titanium oxide
lead
quartz
silica
iron oxide
2-bropenoic acid, polvmer with butyl 2-propenoate and ethenvlbenzene
>*ater
4020-1000
20-30
5-10
1-5
1-5
5-10
.1-1.0
1-5
10-20
30-40
4020-7100
20-30
5-10
1-5
1-5
.OKI
.1-1.0
5-10
10-20
30-40
( CHEMICAL V4MR
* jrhnnic acid calcium sail
!;'i.irl7
•••(vent naphtha i petroleum >. medium aliphatic
-.•ihanol. 2-i2-hu!ox\e!hoxvi-
-. namum oxide
i-Md
;uartx
>iii:a
:r-!nnxide
1 ' •I'ri'penoic acid, polymer with buiU Z-propenoaie and
•'henvihi-ii/ene
' aicr
COMMON NAME
calcium carbonate
quartz
ivdrotrcaied lisht distillate (petroleum)
dieih\lene elvcol monobul\l ether
titanium dioxide
lead
quartz
amorphous silica
feme oxide
s) trenc/acr) late CiipnK mcr
water
CAS. NO.
471-34-1
14808-60-7
64742-88-7
112-34-5
13463-67-7
74VJ-92-I
14808-60-7
7631-86-9
I.-IN-.VM
255rtfi-2H..i
77.;:-j;m
ne
ne
STK1,
ne
ne
ne
ne
ne
ne
ne
ne
tie
ne
ne
OSHA-PtL
8-HOIR TWA
5 me/m'
O.I mi'nr
KXIppm
ne
10ms;m'
0.05 m«'m'
D.I m^m
6 me 'm
10 ms;rii
ne
IK
STK1.
ne
ne
ne
IIS
!K
ne
ne
ne
ne
ne
ne
C
ne
ne
ne
le
ne
ne
K
ne
ne
ne
r.i
S
ne
ne
ne
ne
le
nc
ne
ne
ne
ne
ne
S.R.
STI).
ne
ne
I1C
ne
ne
ne
ne
ne
nc
ne
r,s
S
i
n
n
n
n
n
n
n
n
n
n
n
S
3
n
n
n
..
n
\
n
n
n
n
n
n
n
n
n
n
\
n
n
n
n
n
N
n
n
n
n
n
\
n
n
n
n
1 0
n n:
V n;
n n !
n n !
n ni
v n
v n
n n
n n
n n
n n
•"itnutes:
"r.'ii-i r .n,-.T.trj!;<>n!tlJl sfci-uld
•r I-.! -u-ri i.ist.intjnc
-------
I Paints
MATERIAL SAFETY DATA SHEET
prepared 07/01/97
FIRE AND EXPLOSION HAZARD DATA
Extinguishing media : Dry chemical or foam water fog. Carton dioxide.
Unusual tire and explosion hazards : Vapon are heavier than air and may travel long distances to a
ujurce of ignition and flash back. Closed container! may bunt if exposed 10 extreme heat or fire.
May decompose under fire conditions emitting irritant and/or toxic gases.
Speriftf fire fighting procedarts : Water may be used to cool and protect exposed containers.
Firefighters should use full protective clothing, eye protection, and self-contained breathing
apparatus. Self-contained breathing apparatus recommended.
HEALTH HAZARD DATA
Primary rontefs) of exposure : Inhalation, skin contact, eye contact, ingest ion
Effects of overexDosiire:
Inhalation : Irritation of respiratory tract. Prolonged inhalation may lead to mucous membrane
irritation, draw-lines*, dizziness and/or lightheadcdness, headache, nausea, coughing, difficulty
with speech, central nervous system depression, anesthetic effect or narcosis, difficulty of
breathing, bronchitis, pneumoconiosis.
Skin contact: Irritation of skin. Prolonged or repeated contact can cause dermatitis, defining
Eve contact: Irritation of eyes. Prolonged or repeated contact can cause conjunctivitis, blurred
vision, tearing of eyes, redness of eyes, tevere eye irritation or bums.
Ingestlon : Digestion may cause lung inflammation and damage due to aspiration ot material into
lungs, drowsiness, dizziness and/or lighlhcadedncss. headache, uncoordination, nausea.
gastrointestinal disturbances, apathy, intoxication.
Supplemental health Information : Other effects of overexposure may include toxiciry to liver.
kidney, blood. May be absorbed through skin. Excessive exposure to lead, including ingestion. can
result in lead poisoning. Early symptoms are fatigue, disturbance of sleep, constipation, with more
severe exposure followed by colic, anemia, and neuritis (nerve inflammation). Prolonged
overexposurc can severely damage red blood cell formation, kidneys, nervous and reproductive
systems. Other symptoms include loss of appetite, metallic taste in mouth, anxiety, nausea, pallor.
headache, irritability, muscle and joint pain, tremors, numbness, dizziness and hypertension.
Excessive inhalation of fumes may lead to metal fume fever characterized by a metal Ik taste in
mouth, excessive thirst, coughing, weakness, fatigue, muscular pain, nausea, chills and fever.
Notice - reports have associated repeated and prolonged occupational overexposurc 10 solvents
with permanent brain and nervous system damage. Intentional misuse by deliberately
concentrating and inhaling the content! may be harmful or fatal. Contains crystalline silica which
is considered a hazard by inhalation. IARC has classified crystalline silica as probably
carcinogenic for humans (2a). This classification is based on the findings of laboratory animal
studies that were considered sufficient and data from epidemiologica] studies that were considered
limited for carcinogenkiry. Crystalline silica u also a known cause of silicosis. a noncancerous
lung disease. NTP has classified crystalline silica a reasonably anticipated human carcinogen.
Medkal conditions aggravated by exposure : Eye. skin, respiratory disorders lung disorders
FIRST AID PROCEDURES
Inhalation : Remove to fresh air. Restore and support continued breathing. Get emergency medical
attention. Have trained person give oxygen if necessary. Get medical help for any breathing
difficulty.
Skin contact: Flush from skin with water. Then wash thoroughly with soap and water. Remove
contaminated ckxhing. Wash contaminated clothing before re-use.
Eye contact: Flush immediately with Urge amounts of water, especially under lids for at least 15
minutes. If irritation or other effects persist, obtain medical treatment.
Ingestion : If swallowed, obtain medical treatment immediately
REACTIVITY DATA
Stability: Stable
Incompatibility : Oxidizers, acids, bases. Alkalis aluminum, metals, peroxides, nitric acid.
magnesium.
Conditions to avoid : Elevated temperatures, contact with oxidizing agent, high concentration of
dust, freezing, sparks, open flame. Ignition sources
Hazardous decomposition products : Carbon monoxide, carbon dioxide, lead oxide, toxic gases
Hazardous polymerization : Will not occur
SPILL OR LEAK PROCEDURES
Steps to be taken In case material b released or spilled : Comply with all applicable health and
environmental regulations. Eliminate all sources of ignition. Ventilate area. Place collected
material in proper container. Complete personal protective equipment must be used during
cleanup. Large spills - shut off leak if safe to do so. Dike and contain spill. Pump to storage or
salvage vessels. Use absorbent to pick up excess residue. Keep salvageable material and rinse
water out of sewen and water courses. Small spills - use absorbent to pick up residue and dispose
of properly.
Waste disposal: Dispose in accordance with all applicable regulations. Avoid discharge in natural
waters.
SPECIAL PROTECTION INFORMATION
Respiratory protection : Control environmental concentrations below apptkable standards. Where
respiratory protection is required, use only NIQSrfMSHA approved respirators in accordance with
OSHA standard 29 CTR 1910.134.
Ventilation : Provide dilution ventilation or local exhaust to prevent build-up of vapors. Use
explosion-proof equipment
Personal protective equipment: Eye wash, safety shower, safety glasses or goggles. Impervious
gloves, impervious clothing, apron.
SPECIAL PRECAUTIONS
Handling and storage : Store below lOOf. Keep away from heat, sparks and open flame. Keep from
freezing. Do not store in aluminum containers. Keep container tightly closed in a well-ventilated.
area.
Other precautions : Use only with adequate ventilation. Do not take internally. Keep out of reach ot
children. Avoid contact with skin and eyes, and breathing of vapors. Wash hands thoroughly after
handling, especially before eating or smoking. Keep containers tightly closed and upright when not
in use. Contains lead Dried film of this product may be riarmful if eaten or chewed. Do not tue on
toys, furniture, or surfaces of other ankles which might be chewed by children. Do not apply on
exterior surfaces of dwelling units, such as windowstlls. porches, stairs, or railings to which
children may be commonly exposed. Avoid conditions which result in formation of inhalable
panicles such as spraying or abrading (sanding) painted surfaces. If such conditions cannot be
avoided, use appropriate respiratory protection as directed under special protection information.
Empty containers may contain hazardous residues. Ground equipment when transferring to prevent
accumulation of static charge. *<
The information contained herein ii based on dau available at the time of preparation of this data iheet which ICI Paint! believes to be reliable. However, no warranty u expressed or implied retarding
the accuracy at this data. ICI Palnn shall not be responsible for the use of mil information, or of any product, method or apparatus mentioned and you must make your own determination of its
tuiubiUty and completeness for your own use, for rat protection of the environment, and the health and safety of your employee] and me users of mis material.
Cc^ietwimCerUhazaidccnin»inkarknsiandard29CFKI9IO.I200. 975 Euclid Avenue
Cleveland. Ohio 44115
EMERGENCY TELEPHONE NO. (800)545-2643
O
3
ro
o
O
m
2
O
5
m
3
o
3D
1
m
3D
09
o
30
m
TJ
3
3
m
30
(A
O
ro
o
-------
MSDS for Paint 25524
-------
IP. 01
61-*-B64-O74B
Feb-18-99 OZrZSP ICI GTidden 315
I-IM • .L . 3^ i o • ->J .«*TI -icrtuci- cio art
MATERIAL SAFETY DATA SHEET
or Costings. R«*irs» and Re"!atso
-«r-: AEXCEl
Information
•»3"3 PRODUCTION DRIVE
VENDOR. OH
C'--E>1TREC
( 2 1 ?O 974-38CC
(30C) 424-9300
,'SOO) 424-9300
44.C6'*
5"0duct Class:
Code : 72W-A
XA.5. Number: NONE
! Hazard R»ffrio«:
1 rone -> sxtrerre
i 0 — -> i
i
p-tre - i
Seactw-ity - 0
SECTION II - HAZARDOUS INGREDIENTS
CAS »
25235-77-4
> Th«»sw -ftwrns are "1sted on ^he S«SA TITLE III Saefcr! 3'3 -!r
-------
|Feb-18-99 O2 :28P ICI GUdden 315 ••6T4-B64-O74B^^^^^gP . O2
MPY 27 '92 13:44 FPOM flEXCEL £16 374 3
A£XCEL COLORATION -^
oafaty Data Sheet -"or : 22683-22526 J( 7 2H-A036]
SECTION IV - *IRE AND EXPLOSION HAZARD DA^A
-UNUSUAL FIRE & EXPLOSION HAZARDS: (cent.)
POINT] T£STS ARE NOT A REPRESENTATIVE INDrCA'ION OF TH?
FIRE HAZA9D Or WATER-BCSNE COATINGS".
SECTION V - HEALTH HAZARD DATA
-PERMISSIBLE EXPOSURE LEVEL.
SEE SECTION II =03 INFORMATION ABOUT INDIVIOL'Aw INGREDIENTS.)
-EFFECTS OF OVEREXPOSURE:
SEVERE EYE IRRITATION. EXCESSIVE INHALATION HAY CAUSE
HEADACHES, DIZZINESS A\'C/OR NAUSEA. 3K1N CONTACT MAY CAUSE
IRRITATION OR RASH.
"HE SPECIFIC CHEMICAL IDENTITY OF THE PROPRIETARY PIQMENTCS )|TN|
ISECTION 11 is WITHHELD AS A TRADE SECRET.
JNTRIBUTE TO THE OVERALL
lEXPOSURB TO METHANOL. APPROPRIATE MEASURES SHOULD 9E TAKEN]
ITO PREVENT ABSORPTION SO THAT TUE TLV IS ALWAYS MET.
JNIOSH RECOMMENDS A LIMIT OF 20C ppm . 8 HOUR TWA; SCO pair>. 151
IMINUTE CEILING FOR MSTHANOL.
IOVEREXPOSURE TO METHANCL < OR ITS COMPONENTS ) HAS
ISU9GESTEO AS A CAUSE OF EYE OAMA3E IN HUMANS.
-FIRST AID:
IN ALL SUCH CASES, CONTACT A PHYSIC JAN FOR PROPER
MEDICAL ATTENTION, AND TAKE THIS INFORMATION TO THE
"HYSICIAN.
SECTION VI - REACTIVITY OATA
iTABLITY: ' ] Unstable i*': Stab"1*
HAZARDOUS POLYMgRIZATTON: * 3 May occur -x] W1VI not OCC'jr
INCOMPATIBILITY
N/A
-CONDITIONS TO AVOID:
N/A
HAZARDOUS DECOMPOSITION PRODUCTS:
CO.C02
SECTION VII - SPILL OR LEAK PROCEDURES
•STEPS TO BE TAKEN IN CASE MATERIAL IS RELEASED OR SPILLED
COLLECT IN A RETAINING AREA OR CONTAINER. THEN TRANSFER TO
A CLOSED CONTAINER. AVOID EXPOSURE TO H=AT. 5'ASKS. CIRS
OR OPEN FLAME. AVCIO HOT METAL SURFACES.
-------
MSDS for Paint 4206-0100
-------
Physical
Product
Code
4206-0100
4206-0110
4206-0300
4206-0400
4206-1000
4206-9990
paia * -ri i/ ft __i
J) CO f /€£ IM^
Description
white A
white tint base
intermediate tint base
deep lint base
white-dish hiding
black
- c&
WL/Gal.
10.54
10.23
9.29
9.03
10.39
8.78
T&Uff
voe
er^Itr.
189.53
195.70
215.22
217.81
191.29
222.15
~ fan
% Volatile
bv Volume
57.83
59.32
64.06
64.76
58.64
65.69
l^ £-<
Flash
Point
none
none
none
none
none
none
f>h. Q^-
Boiling"
Ranee
212453
212453
212453
212453
212453
212453
i9Z-l_
HMIS
310
310
310
310
310
*310
C^t^-^^^U-ca^/ \
DOT, proper '
shippine "••"•:
paint ** protect from freezine *
paint ** protect from freezine *
paint <* protect from freezine *
paint ** protect from freezine *
paint ** protect from freezini •
paint •• protect from freezine *
Ingredients
Product Codes with % by Weight
titanium oxide
solvent naphtha (petroleum), medium aliphatic
ethanol, 2-buloxv-
ethanol, 2-(2-buloxvethoxv)-
titaniiim oxirlr
silica
'•vbon black
u-atei
^-propenoic acid, polvmer with ethenvlbenzene and ( 1 -methvlethenvDbenzene. ammonium salt
aluminum hvdroxide
2-propenoic acid. 2-methvl-, methvl ester, polvmer with ethenvlbcnzene and 2-elhvlhexvl 2-propenoaie
4206-0100
1-5
1-5
1-5
10-20
1-5
3040
5-10
5-10
5-10
2-ethvlhexvl ester, acrvlic acid polvmer with stvrene \ 5-10
4206-0110
1-5
1-5
1-5
10-20
1-5
3040
5-10
5-10
5-10
5-10
4206-0300
1-5
1-5
1-5
1-5
5-10
40-50
5-10
5-10
10-20
10-20
4206-040014206-1000
1-5
1-5
1-5
1-5
1-5
40-50
5-10
1-5
10-20
10-20
1-5
1-5
1-5
10-20
1-5
3040
5-10
5-10
5-10
5-10
4206-9990
1-5
1-5
1-5
1-5
50-60
5-10
5-10
10-20
10-20
b 1
rs!
carbon black
' '"ale.
'-propenoie acid, polymer with ethenylbeiucne and
1 metlr-lctlienvDbenzene. ammonium
mi'
3.5 m«/m'
ne
ne
lOmuAn3
ne
ne
STEL
ne
ne
ne
ne
ne
ne
ne
ne
ne
ne
ne
ne
OS1
8-HOUR TWA
10me/m]
100 ppm
25ppm
ne
IOme/mJ
6me/m!
3.5 mg/mj
ne
ne
5mi!/mJ
DC
ne
A-PEL
STEL
ne
ne
ne
ne
ne
ne
ne
ne
ne
ne
ne
ne
C
ne
ne
ne
ne
ne
ne
ne
ne
ne
ne
ne
ne
S
ne
ne
skin
ne
ne
ne
ne
ne
ne
ne
ne
ne
S.R.
STD.
ne
ne
ne
ne
ne
ne
ne
ne
ne
ne
ne
ne
S
2
n
n
n
n
n
n
n
n
n
n
n
n
S
3
n
n
y
Y
n
n
n
n
n
n
n
n
n
n
n
n
n
n
n
n
n
n
N
n_
n
n
n
n
n
n
n
n
n
n
n
n nl
n n'
n n
n n
n nj
n n
n n
Footnotes:
(' • Ccitinf - Cfincomaiion (h* ihnitd not be
exceeded, evea inuinune«ul]r.
S.R.m>. • Sufflier Recommended Suodard
S»SUa-AddiiioiuJeipoiuR.ora»d
itovt liibone eipowie. nuy itnk Ann itin
pea • p«u per million
ni/ta1 • milli|nm> per cuoic meter
S2«S« Seen* 301EHS
Sl-SnSectralUOieninl
CC-CERCLACIxncjl
Ocino|auciiy Lund BY
N.OTT.I.IARC.O-OSHA
1 = ytt. n » no
-------
I MATERIAL SAFETY DATA SHEET
I prepared 07701/971
FIRE AND EXPLOSION HAZARD DATA
EiUn[utshin| media : Dry chemicil or loan water fog. Carbon dioxide.
| Unusual fire and explosion hazards : Vapors are heavier than air and nuy travel long distances lo a|
source of ignition and flash back. Cloied containers nuy burst if exposed lo extreme heal or fur.
May decompose under fire conditions emitting irritant and/or toxk gases.
I Special flre figtiling procedures : Water may be used to cool and protect exposed containers.
Firefighters should use full protective clothing, eye protection, and self-contained breathing
apparatus. Self-contained breathing apparatus recommended.
| HEALTH HAZARD DATA
Primary routed) of exposure : Inhalation, skin contact, eye contact, ingestion.
I Effects of ovemponire :
Inhalation : Irritation of respiratory tract. Prolonged inhalation may lead to mucous membrane
irritation, drowsiness, dizziness and/or lighlheadedncss. headache, nausea, vomiting, chest
pain, coughing, difficulty with speech, central nervous system depression, anesthetic effect or I
narcosis.
Skin contact: Irritation of skin. Prolonged or repealed contact can cause dermatitis, defaning. Skin
contact may result in dermal absorption of component(s) of this product which may cause
headache, nausea, vomiting.
Eye contact: Irritation of eyes. Prolonged or repeated contact can cause conjunctivitis, blurred
vision, tearing of eyes, redness of eyes, severe eye irritation, severe eye irritation or bums.
comeal injury.
Iniesllon : Ingeslion may cause lung inflammation and damage due to aspiration of material into
lungs, fatigue, drowsiness, dizziness and/or lighlheadedness. headache, uncoordinalion.
nausea, vomiting, diarrhea, apathy, intoxication, loss of consciousness.
| Supplemental health Information : Contains a chemical that is moderately toxic by ingestion. Other|
effects of overexposure may include toxicity to liver, kidney, lungs, blood. May be absorbed
through skin. Notice - reports have associated repeated and prolonged occupational overexposure
to solvents with permanent brain and nervous system damage. Intentional misuse by deliberately
concentrating and inhaling the contents may be harmful or fatal. The international agency for
research on cancer (IARC) has classified carbon black as possibly carcinogenic to humans (group
2b) based on sufficient evidence in animals and inadequate evidence in humans.
| Medical conditions aggravated by exposure : Eye. skin, respiratory disorders lung disorder!
asthma-like conditions kidney disorders
| FIRST AID PROCEDURES
1 Inhalation : Remove to fresh air. Restore and support continued breathing. Get emergency medical
attention. Have trained person give oxygen if necessary. Gel medical help for any breathing
difficulty. Remove lo fresh air if inhalation causes eye watering, headaches, dizziness, or other |
discomfort.
| Skin contact: Rush from skin with water. Then wash thoroughly with soap and water. Remove
contaminated clothing. Wash contaminated clothing before re-use. Dispose of contaminated
leather items, such as shoes and belts.
| Eye contact: Rush immediately wiib Urge amounts of water, especially under lids for at least 15
minutes. If irritation or other effects persist, obtain medical treatment.
I Ingestion: If swallowed, obtain medical treatment immediately.
REACTIVITY DATA
Stability: Stable
1 Incompatibility : Oxidize 13. acids, bases. Alkalis aluminum, zinc, magnesium. Nitrates
I Conditions to avoid : Elevated temperatures, contact with oxidizing agent, freezing, sparks, open
Hame. Ignition sources
I Hazardous decomposition products : Carbon monoxide, carbon dioxide, toxic gases, unidentified I
organic compounds.
[ Hazardous polymerization : Will not occur
[SPllLORLEAKPROCEDURES
I Steps to be taken In case material b released or spilled : Comply with all applicable health and
environmental regulations. Eliminate all sources of ignition. Ventilate area. Spills may be collected]
with absorbent materials. Use non-sparking tools. Evacuate all unnecessary personnel. Place
collected material in proper container. Complete personal protective equipment must be used
during cleanup. Large spills - shut oft leak if safe to do so. Dike and contain spill. Pump to storage I
or salvage vessels. Use absorbent to pick up excess residue. Keep salvageable material and rinse
water out of sewers and water courses. Small spills - use absorbent to pick up residue and dispose
of properly.
I Waste disposal: Dispose in accordance with all applicable regulations. Avoid discharge to natural
waters. _
I SPECIAL PROTECTION INFORMATION
I Respiratory protection : Control environmental concentrations below applicable standards. Where
respiratory protection is required, use only NIOSH/MSHA approved respirators in accordance withl
OSHA standard 29 CFR 1910.134.
Ventilation : Provide dilution ventilation or local exhaust to prevent build-up of vapors. Use
explosion-proof equipment.
I Personal protective equipment: Eye wash, safety shower, safety glasses or goggles. Impervious
gloves, impervious clothing, apron.
aa*MaaiHBaaaa«Baa*HaBaaa^BavBaaavB«BaaiHBi
[SPECIAL PRECAUTIONS
| Handling and storage : Store below lOOfUSc). Keep away from heal, sparks and open flame Keep
from freezing. Do not store in aluminum containers. Keep container tightly closed in a
well-ventilated area.
I Other precautions : Use only with adequate ventilation. Do not take internally. Keep out of reach of
children. Avoid contact with skin and eyes, and breadline, of vapors. Wash hands thoroughly after I
handling, especially before eating or smoking. Keep containers lightly closed and upright when not |
in use. Avoid conditions which result in formation of inhalable panicles such as spraying or
abrading (sanding) painted surfaces. If such conditions cannot be avoided, use appropriate
respiratory protection as directed under special protection information. Empty containers may
contain hazardous residues. Ground equipment when transferring to prevent accumulation of static |
The information contained herein b bued on data available at the time of preparation of mis data sheet which ICI Paints believe* lo be reliable. However, no warranty b expressed or implied retarding!
the accuracy of this data. ICI Paints shall not be responsible for the use of ibis information, or of any product, method or apparatus mentioned and you aunt make your own determination of iu|
suitability and completeness for your own use. for the protection of me environment, and the health and safely of your employees and the users of this material.
Cc«n^ieiwimOSHAriaiardammMmicalionnandird»CFR19l0.121X). 923 Eudid Avenue EMERGENCY TELEPHONE NO. (800)545-2643
Cleveland. Oroo 44115
-------
Average Relative Sensitivity Calculations
-------
Compound
2-butoxyethanol
2-propoxyethanol
Mineral Spirits and Solvent
Naphtha
Hexane
triethylamine
ethanol, 2,2'-oxybis
propanoic acid, 2-methyl-,
monesterwith2,2,4-trimethyl-1,3-
pentanediol
methanol
ethanol, 2-(2-butoxyethoxy)-
Ester Alcohol Ether Amine
Linkage Linkage Linkage Linkage
Other names CAS No. Carbon (-1.27 (-0.64 (-0.78 (-0.58
Number each) each) each) each)
111-76-2 6 -0.64 -0.78
ethylene glycol 2807-30-9 5 -0.64 -0.78
monopropyl ether
64742-88-7 10
110-54-3 6
121-44-8 6 -0.58
diethylene glycol 111-46-6 4 -1.28 -0.78
Texanol 25265-77-4 12 -1.27 -0.64
67-56-1 1 -0.64
diethylene glycol 112-34-5 8 -0.64 -1.56
Effective
Carbon
Number
4.58
3.58
9.92
5.92
5.42
1.94
10.09
0.36
5.80
MW
118
104
142.29
86.18
101.19
106
216.32
32.04
162
Relative
Sensitivity
1.000
0.887
1.796
1.770
1.380
0.472
1.202
0.289
0.922
monobutyl ether
-------
MS1-6659A Silver Waterborne Industrial Enamel (Automotive Paint)
Ingred.
No.
1
2
3
4
5
Cas
No.
64742-88-7
2807-30-9
111-76-2
136-52-7
7732-18-5
wt/wt%
1
5
6
0.1
54.0
Ingredient
Mineral Spirits
2-Propoxyethanol
2-Butoxyethanol
Cobalt 2-Ethylhexanoate
Water
Actual
VOC
1.00
5.00
6.00
Fraction
of Total
VOC
0.083
0.417
0.500
Rel.
Sens
1.796
0.887
1.000
Contribution
0.150
0.370
0.500
12.00
1.00
Avg RS=
1.019
MS1-6660A Gray Waterborne Industrial Enamel (Automotive Paint)
Ingred.
No.
1
2
3
4
5
6
7
Cas
No.
121-44-8
2807-30-9
111-76-2
136-52-7
13463-67-7
1333-86-4
7732-18-5
wt/wt%
2
4
8
0.2
14
0.4
43.9
Ingredient
Triethylamine
2-Propoxyethanol
2-Butoxyethanol
Cobalt 2-Ethylhexanoate
Titanium Dioxide
Carbon Black
Water
Fraction
Actual of Total
VOC VOC
2.00 0.143
4.00 0.286
8.00 0.571
Rel.
Sens
1.380
0.887
1.000
Contribution
0.197
0.253
0.571
14.00
1.00
Avg RS= 1.022
-------
1403-0100 Dulux Ultra Interior Acrylic Eggshell White (Interior Wall Paint)
Ingred.
No.
1
2
3
4
5
6
7
8
Cas
No.
111-46-6
37244-96-5
61790-53-2
25265-77-4
13463-67-7
27136-15-8
7732-18-5
wt/wt%
1-5
5-10
1-5
1-5
20-30
10-20
1-5
30-40
Ingredient
Ethanol, 2,2'-oxybis
Nepheline syenite
Silica, diatomaceous earth
Propanoic acid, 2-methyl-,
monester
with 2,2,4-trimethyl-1 ,3-pentanediol
(Texanol)
Titanium oxide
Vinyl acrylic copolymer
2-Propenoic acid, 2-methyl-, methyl
ester,
polymer with butyl 2-propenoate
ethenylbenzene
Water
Middle
Est.
VOC
3.00
3.00
and
6.00
Fraction
of Total Rel.
VOC Sens Contribution
0.500 0.472 0.236
0.500 1.202 0.601
1 .00 Avg RS= 0.837
-------
4206-0100 Acrylic Semi-Gloss Architectural Paint
Ingred.
No.
1
2
3
4
5
6
7
8
9
10
Cas
No.
64742-88-7
111-76-2
112-34-5
13463-67-7
7631-86-9
89678-90-0
21645-51-2
27136-15-8
25153-46-2
7732-18-5
wt/wt%
1-5
1-5
1-5
10-20
1-5
5-10
5-10
5-10
5-10
30-40
Ingredient
Solvent naphtha (petroleum),
medium aliphatic
2-Butoxyethanol
Ethanol, 2-(2-butoxyethoxy)-
Titanium oxide
Silica
2-Propenoic acid, polymer with
ethenylbenzene
and (l-methylethenyl)benzene,
ammonium salt
aluminum hydroxide
Middle Fraction
Est. of Total
VOC VOC
3.00 0.333
3.00 0.333
3.00 0.333
Rel.
Sens Contribution
1.796 0.599
1.000 0.333
0.922 0.307
2-Propenoic acid, 2-methyl-, methyl
ester,
polymer with ethenylbenzene and
propenoate
2-Ethylhexyl ester, acrylic acid
styrene
Water
2-ethylhexyl 2-
polymer with
9.00 1.00
Avg RS= 1 .239
-------
4020-1000 Waterbase Primer (White)
Ing red
No.
1
2
3
4
5
6
7
8
Cas
No.
64742-88-7
112-34-5
14808-60-7
471-34-1
25586-20-3
13463-67-7
7631-86-9
7732-18-5
wt/wt%
1-5
1-5
5-10
20-30
10-20
5-10
1-5
30-40
Middle Fraction
Est. of Total
Ingredient VOC VOC
Solvent naphtha (petroleum), 3.00 0.500
medium aliphatic
Ethanol, 2-(2-butoxyethoxy)- 3.00 0.500
Quartz
calcium carbonate
2-Propenoic acid, polymer with
butyl
2-propenoate and ethenylbenzene
Titanium oxide
Silica
Water
Rel.
Sens Contribution
1.796 0.898
0.922 0.461
6.00
1.00
Avg RS= 1.359
-------
25524 Latex Traffic Paint
Ingred.
No.
1
2
3
4
5
6
7
Cas
No.
13463-67-7
471-34-1
unknown
25265-77-4
67-56-1
7732-18-5
wt/wt%
8.52
19.2
13.683
1.108
1.704
14.90
39.1
Actual
Ingredient VOC
Titanium dioxide
Calcium Carbonate
Acrylic Resin
Propanoic acid, 2-methyl-, 1.11
monester
with 2,2,4-trimethyl-1 ,3-pentanediol
(Texanol)
Methanol 1 .70
Proprietary Pigment
Water
Fraction
of Total Rel.
VOC Sens Contribution
0.394 1.202 0.474
0.606 0.289 0.175
2.81
1.000 Avg RS= 0.649
-------
APPENDIX B
LABORATORY KICK-OFF MEETING HANDOUT
-------
Inter-laboratory Study of Draft Water-Based Coating Method (ATD-FID)
Battelle would like to thank Laboratory Name. Inc. for participating in an
interlaboratory study of a draft method developed by U.S. Environmental Protection Agency
(EPA) to measure the VOC content of water-based coatings. As a participant, you will be
required to analyze four water-based coating samples in triplicate following the draft test
method. A copy of the draft test method can be found in Attachment 1. Battelle is providing you
with the four water-based paint samples. As part of the draft test method, you will be required to
perform several calculations in order to compute the corrected Wt% VOC for each coating.
Attachment 2 contains information on the coatings that you will need to compute the correction
factors for the Wt% VOC calculations. This information includes the ingredients of each paint
and the chemical structure of specific VOC components. Attachment 3 shows examples of the
calculations used to determine the correction factors. Attachment 4 contains the reference cited
in the draft test method on which the correction factor calculations are based.
The deliverables for this work will be the various calibration and QC/QA measurements
required by the draft test method, as well as the test results from the four paint samples. Data
sheets can be found in Attachment 5 to record all of the required information. Battelle is also
providing a logbook to record information while performing the draft test method. Please record
any special events that arise during any phase of the testing. All of the data should be reported to
Battelle within two weeks after completion of the testing (Date). This report should include the
data sheets as well as the raw data (chromatograms and calculations) generated in performing the
test method. Also please provide a short narrative on specific aspects of the apparatus, reagents,
calibration, or procedure that you feel were a problem and any ways you feel the method could
be improved.
Battelle is providing you with various materials needed to perform the test method.
Attachment 6 contains a list of the supplied materials. These materials include the Perkin-Elmer
ATD-400 thermal tube desorber. Since this unit must be shared with other participating
laboratories, Battelle would like you to complete the testing within two weeks.
Finally if there are any problems or concerns that arise in performing the testing, please contact
Battelle at the following numbers:
Pat Callahan
Phone: 614-424-4206
Fax: 614-424-3638
E-mail: callahap@battelle.org
Bill Keialev
Phone: 614-424-5286
Fax: 614-424-3638
E-mail: keigley@battelle.org
-------
Attachment 1.
Draft Test Method
-------
Measurement of Total VOC in Paints and Coatings Using an
Automated Thermal Desorber and a Flame Ionization Detector
1. Scope and.Application
1.1 Applicability. This method is applicable for
determination of the total volatile organic compound (VOC)
content of paints and coatings. The term "coating" used in this
method shall be understood to mean paints and coatings.
1.2 Principle. The method is based on the response of a
flame ionization detector (FID) to VOCs that are released from a
coating that is heated at 110° C. Since the response of an FID
per unit mass of VOC is compound dependent, a correction of the
apparent VOC weight percent of a coating must be made based on a
predicted average relative sensitivity of the coating. (Relative
to the calibration standard FID response per unit mass) .
2g • wuum-ru im. *•• • A. £ %if j, -J- Vt.-» <3
• ^y^mPUi^LIi' ^^ ^ ^»!B.^»^1^? d
A sample of a whole coating is weighed into a PTFE liner
containing a plug of silanized' glass wool and then inserted into
a stainless steel tube. The tube is placed in an automated
thermal desorber where it is heated at 110° C while purging with
helium for 30 minutes. During tube heating, volatile components
are collected on a solid sorbent trap which is cooled to -30° C.
After tube desorption, the trap is heated to 325° C and the
desorbed compounds are transferred directly to a flame ionization
detector. Tube desorption is repeated for another 30 minute
period and the analysis results are summed with those from the
first desorption.
3. nafini^tma [Reserved]
4.
4.1 Any residual VOC from the glass wool, PTFE liners, or
sample tubes constitutes a positive bias for a coating analysis.
In addition, residual VOC in the sorbent trap of the Automated
Thermal Desorption unit will cause a positive bias.
4.2 Cross -contamination may occur if the devices used to
transfer coating during the sample preparation process are not
adequately cleaned between uses. All such devices should be
cleaned with acetone or other suitable solvent and checked for
plugs or cracks before and after each use.
5. fl
5.1 Many solvents used in coatings are hazardous.
Precautions should be taken to avoid unnecessary inhalation and
skin or eye contact. This method may involve hazardous
materials, operations, and equipment. This test method does not
purport to address all of the safety problems associated with its
use. It is the responsibility of the user of this test method to
establish appropriate safety and health practices and to
determine the applicability of regulatory limitations in regards
to the performance of this test method.
-------
5.2 2-butoxyethanol is harmful if inhaled or absorbed
through the skin. The user should obtain relevant health and
safety information from the manufacturer. 2-butoxyethanol should
be used only with adequate ventilation. Avoid contact with skin,
eyes, and clothing. In case of contact, immediately flush skin
or eyes with plenty of water for at least 15 minutes. If eyes
are affected, consult a physician. Remove and wash contaminated
clothing before reuse.
5.3 User's manuals for the gas chromatograph, thermal
desorber, and other related equipment should be consulted for
specific precautions to be taken related to their use.
6. Eguipa»xit_ancL Supplies
6.1 Sample Collection.
6.1.1 Sampling Containers. Dual-seal sampling containers,
four to eight fluid ounce capacity, should be used to collect the
samples. Glass sample bottles or plastic containers with
volatile organic compound (VOC) impermeable walls must be used
for corrosive substances (e.g., etch primers and certain coating
catalysts such as methyl ethyl ketone (MEK) peroxide). Sample
containers, caps, and inner seal liners must be inert to the
compounds in the sample and must be selected on a case-by-case
basis.
6.1.2 Other routine sampling supplies needed include
waterproof marking pens, tubing, scrappers/spatulas, clean rags,
paper towels, cooler/ice, long handle tongs, and mixing/stirring
paddles..
6.1.3 Personal safety equipment" needed includes-eye
protection, respiratory protection, hard hat, gloves, steel toe
shoes, etc.
6.1.4 Shipping supplies needed include shipping boxes,
packing material, shipping labels, strapping tape, etc.
6.1.5 Data recording forms and labels needed include
coating data sheets and sample can labels.
NOTE: The actual requirements will depend upon the conditions
existing at the source sampled.
6.2 Laboratory Equipment and Supplies.
6.2.1 Gas Chromatograph (GC) . Any instrument equipped with
a flame ionization detector may be used.
6.2.2 Recorder. If available, an electronic data station
or integrator may be used to record the detector response and
associated data. If a strip chart recorder is used, it must meet
the following criteria: A 1 to 10 millivolt (mV) linear response
with a full scale response time of 2 seconds or less and a
maximum noise level of +0.03 percent of full scale.
6.2.3 Automated Thermal Desorber. A Perkin Elmer Model
ATD-400, or equivalent, fitted with a 3 mm ID sorbent trap
-------
01/ii/aa io:ui -(i-CH
containing a 10 mm l^ong section of Tenax GR and a 10 mm long
section of Carbopack B.
6.2.4 Sample analysis tubes. Stainless steel tubes, 1/4
inch OD, 5 mm ID, 3,5 inches long, with end caps. (PE Part No.
L427-0123)
6.2.5 Tube liners. PTFE liners for sample tubes, 2 inches
long with bevelled end. (PE Part No. L407-1596) . NOTE: Liners
should fit snugly to prevent slipping out of tube during
processing.
6.2.6 Silanized glass wool. For packing into bevelled end
of PTFE insert.
6.2.7 Disposable pipet or syringe. For transferring
coating or calibration standard to tube liner.
6.2.8 Capillary restrictor. SO cm long and 0.1 mm ID fused
silica tubing for attaching thermal desorber transfer tube to
FID. The restrictor is attached to the 2nd of the transfer tube
inside the GC oven with a zero volume union.
6.2.9 Tube and Tube Fittings. Supplies to connect the
thermal desorber and GC to gas cylinders.
6.2.10 Pressure Regulators. Devices used to regulate the
pressure between gas cylinders and the thermal desorber and GC.
6.2.11 Plow Meter. A device used to determine the carrier
gas flow rate through the thermal deserter and GC. Either a
digital flow meter or a soap film flow neter may be used to
measure gas flow rates.
6.2.12 Balance. Used to determine the weights of standards
and samples. An analytical balance capable of accurately
weighing to 0,0001 g is required.
7 . Raqgp«fe,p flP^ SfnRT"^*"^^
7.1- Purity of Reagents. Reagent grade chemicals shall be
used in all tests. Unless otherwise specified, all reagents
shall conform to the specifications of t:he Committee on
Analytical Reagents of the American Cheriical Society, where such
specifications are available. Other grades may be used provided
it is first ascertained that the reagent: is of sufficient purity
to permit its use without lessening the accuracy of
det ermination.
7.2 Support Gases. Helium carrie:: gas shall have a purity
of 99.995 percent or higher. Ultra-high purity grade hydrogen
(99.999 percent) and zero-grade air shall ,be used for the flame
ionization detector. Dry grade nitrogen or air shall be used for
the ATD-400 Peltier cooler purge gas anJ for valve actuation.
7.3 2-Butoxyethanol. Compound us sd to calibrate the FID
response.
7.4 Reagent grade water. Solvent; for 2-butoxyethanol in
calibration standards.
7.5 Calibration Standards. Calibration standards are used
to determine the response of the detector to known amounts of 2-
-------
butoxyethanol. Calibration standards must be prepared at a
minimum of three concentration levels in water. The lowest
concentration standard should contain nominally 0.51 by weight of
2-butoxyethanol in water. The mid-level standard should contain
nominally 5%, and the high level standard should contain
nominally 50%. Calibration standards should be stored for 1 week
or less in sealed vials with minimal headspace. Calibration
standards are prepared by weighing an appropriate amount of 2--
butQxyethanol into a vial containing a weighed amount of water.
8. Saa^B.jC^lJ..ection>_Er.eseryAtion,_JCran0port,__and .Storage
8.1 Copies of material safety data sheets (MSDS) Cor each
sample should be obtained prior to sampling. The MSDS contains
information on the ingredients, and physical and chemical
properties data. The MSDS also contains recommendations for
proper handling or required safety precaution.
8.2 A copy of the blender's worksheet can be requested to
obtain data on the exact coating being sampled. The
manufacturer's formulation information from the product data
sheet should also be obtained.
8.3 Prior to sample collection, thoroughly mix the coating
to ensure that a representative, homogeneous sample is obtained.
It is preferred that this be accomplished using a coating can
shaker or similar device; however, when necessary, this may be
accomplished using mechanical agitation or circulation systems.
8.3.X Water-thinned coatings tend to incorporate or entrain
air bubbles if stirred too vigorously,- mix these types of
coatings slowly and only as long as necessary to homogenize.
8.3.2 Each component of multicomponent coatings that harden
when mixed must be sampled separately. The component mix ratios
must be obtained at the facility at the time of sampling and
submitted to the analytical laboratory.
8.4 Sample Collection. Samples must be collected in a
manner that prevents or minimizes loss of volatile components and
that does not contaminate the coating reservoir. A suggested
procedure is as follows. Select a sample collection container
which has a capacity at least 25 percent greater than the
container in which the sample is to be transported. Make sure
both sample containers are clean and dry. Using clean, long-
handled tongs, turn the sample collection container upside down
and lower it into the coating reservoir. The mouth of the sample
collection container should be at approximately the midpoint of
the reservoir (do not take the sample from the top surface) .
Turn the sample collection container over and slowly bring it to
the top of the coating reservoir. Rapidly pour the collected
coating into the sample container, filling it completely. It is
important to fill the sample container completely to avoid any
loss of volatiles due to volatilization into the headspace.
-------
Return any unused coating to the reservoir or dispose as
appropriate .
NOTE: If a company requests a set of samples for its own
analysis, a separate set of samples, using new sample containers,
should be taken at the same time.
8.5 Once the sample is collected, place the sample
container on a firm surface and insert the inner seal in the
container by placing the seal inside the rim of the container,
inverting a screw cap, and pressing down on the screw cap which
will evenly force the inner seal into the container for a tight
fit. Using clean towels or rags, remove all residual coating
material from the outside of the sample container after inserting
the inner seal. Screw the cap onto the container.
8.5.1 Affix a sample label clearly identifying the sample,
date collected, and person collecting the sample.
8.5.2 Prepare the sample for transportation to the
laboratory. The sample should be maintained at the coating's
recommended storage temperature specified on the Material Safety
Data Sheet, or, if no temperature is specified, the sample should
be maintained within the range of 5° C to 38° C.
8.6 The shipping container should adhere to U.S. Department
of Transportation specification DOT 12-B. Coating samples are
considered hazardous materials; appropriate shipping procedures
should be followed.
9 .
9.1 Laboratories using this method should operate a formal
quality control program. The minimum requirements of the program
should consist of an initial demonstration of laboratory
capability and an on-going analysis of blanks and quality control
samples to evaluate and document data quality. The laboratory
must maintain records to document the quality of the data
generated. When results indicate atypical method performance, a
quality control check standard (see section 9.4) must be analyzed
to confirm that the measurements were performed in an in-control
mode of operation.
9.2 Before processing any samples, the analyst must
demonstrate, through analysis of a reagent blank (water) , that
there are no interferences from the analytical system, glassware,
and reagents that would bias the sample analysis results. Each
time a set of analytical samples are processed or there is a
change in reagents, a reagent blank should be processed as a
safeguard against chronic laboratory contamination. The blank
samples should be carried through all stages of the sample
preparation and measurement steps.
9.3 Required instrument quality control parameters are
found in the following sections:
-------
9.3.1 Baseline noise must be demonstrated to be <5 percent
of full scale using the procedures given in Section 11.1.
9.3.2 The GC system must be calibrated as specified in
section 11.2.
9.3.3 A one-point daily calibration check must be performed
as specified in section 11.3.
9.4 To establish the ability to generate results having
acceptable accuracy and precision, the analyst must perform the
following operations,
9.4.1 Prepare or purchase a quality control check standard
(QCCS) containing nominally 5% 2-butoxyethanol in water. If
prepared in the laboratory, the QCCS must be prepared
independently from the calibration standards.
9.4.2 Analyze three aliquots of the QCCS according to the
method beginning in section 12.6 and calculate the weight percent
of 2-butoxyethanol. . _
9.4.3 Calculate the mean weight percent (X) from the three
results obtained in section 9.4.2.
9.4,4 Calculate the percent accuracy using the known
concentration (T) in the QCCS using Equation 1, section 13.
9.4.S Calculate the percent relative standard deviation
(percent ESD) using equation 4, Section 13, substituting x for
RF.
9.4.6 If the percent accuracy (section 9.4.4) is within the
range 90 percent to 110 percent and the percent RSD (section
9.4.5) is <20 percent, system performance is acceptable and
sample analysis may begin. If these criteria are not met, then
system performance is not acceptable and the test must be
repeated. Repeated failures indicate a general problem with the
measurement system that must be located and corrected. In this
case, the entire test, beginning at Section 9.4.1, must be
repeated after the problem is corrected.
9.5 Great care must be exercised to maintain the integrity
of all standards. It is recommended that all standards be stored
at .-10°C to 0°C in screw-cap amber glass bottles with Teflon
liners.
9.6 Unless otherwise specified, all weights are to be
recorded within 0.1 mg.
10. Tnhe Condi tie^ng
Before beginning tube conditioning, load an appropriate
number of liners with approximately 2 cm long plugs of silanized
glass wool. (Insert the plug into the large opening and push down
to bevelled end.) Insert liners into sample tubes (bevelled end
first) and install tube caps. Load sample tubes into the thermal
desorber and establish the following conditions:
Tube desorption temperature.- 200° C
Tube desorption time; 10 min.
-------
01/11/39
Carrier gas flowrate through tube: 100 cc/min. minimum
Switching valve temperature: 175° C
Condition sample tubes using a tube conditioning mode (Mode
1 on ATD-400) in which no tube flow passes through the cold trap.
11. Calibration
11.1 Detector Baseline Drift. Operate the GC at initial
(i.e., before sample injection) conditions on the lowest
attenuation to be used during sample analysis. Adjust the
recorder pen to zero on the chart and obtain a baseline for at
least one minute. Initiate the GC operating cycle that would be
used for sample analysis. On the recorder chart, mark the pen
position at the end of the simulated sample analysis cycle.
Baseline drift is defined as the absolute difference in the pen
positions at the beginning and end of the cycle in the direction
perpendicular to the chart movement. Calculate the percent
baseline drift by dividing the baseline drift by the chart width
representing full-scale deflection and multiply the result by
100. ^
11.2 Calibration of GC. Bring all calibration standards to
room temperature while establishing the GC and thermal desorber
operating conditions.
The GC must be calibrated using a minimum of three
concentration levels of 2-butoxyethanol. (See section 7.5 for
instructions on preparation of the calibration standards.)
Prepare calibration standard tubes following the procedure in
Section 12.6. Analyze loaded tubes using the established method.
11.2.1 Tabulate the area responses and the 2-butoxyethanol
masses (Equation 2, Section 13) for the calibration standards.
Calculate the response factor for each mass using Equation 3,
Section 13.
11.2.2 Using the RF's from the calibration, calculate the
percent relative1 standard deviation (percent RSD) using Equation
4, Section 13. The percent RSD must be less than 30 percent.
This criterion must be met-in order for the calibration to be
valid. If the criterion is met, the mean RF is to be used until
the next calibration.
11.3 Daily Calibration Check. The response factor
(section 11.2.2) must be checked and verified at least once each
day that samples are analyzed. This is accomplished by analyzing
the mid-level calibration standard.
Calculate the percent change in the RF since the last
calibration using Equation 5, Section 13. If the percent change
is less than 10 percent, the last calibration curve is assumed to
be valid. If the percent difference is greater than 5 percent,
the analyst should consider this a warning limit. If the percent
difference exceeds 10 percent, corrective action must be taken.
If no source of the problem can be determined after corrective
-------
action has been taken, a new three-point (minimum) calibration
must be generated. This criterion must be met before coating
analysis begins,
12. Coating_Analysis Procedure
12.1 All samples and standards must be allowed to warm to
room temperature before analysis.
12.2 Set the GC to the operating conditions listed below:
Column oven temperature: 150° C
FID temperatures 250° C
FID air flowrate: Per manufacturer instructions.
FID hydrogen flowrate: Per manufacturer instructions.
FID range; Set high enough to prevent exceeding data system
input range.
12.3 Set the thermal desorber to the operating conditions
listed below:
Tube desorption temperature: 110° C
Tube desorption time: 30 win.
Number of desorptions and injections per tube: 2
Switching valve temperature: 175* C
Transfer line temperature: 175° C
Trap low temperature: -30° C
Trap high temperature: 325° C
Trap hold time: 5 min.
Trap heating rate: 5° C/sec
Tube desorption flowrate: 5 cc/min.
Trap inlet split flowrate: 100 ee/min.
Trap outlet split flowrate: 50 cc/min.
Carrier flowrate to FID: 1 cc/min.
Helium pressure: 20 psig
12.4 Perform the. daily calibration check as described in
section 11,3. Samples are not to be analyzed until the criteria
in section 11.3 are met.
12.5 Place the as-received coating sample on a paint
shaker, or similar device, and shake the sample for a minimum of
5 minutes to achieve hotnogenization.
12.6 NOTE: The steps in this section must be performed
rapidly and without interruption to avoid loss of volatile
organics. These steps must be performed in a laboratory hood
free from solvent vapors. All weights must be recorded to the
nearest 0.1 mg.
12.6.1 Add approximately 25 (J.L of coating to a tared PTFE
liner. Weigh the liner and record weight. Insert the liner into
a stainless steel sample tube.
12,S.2 Cap the tube with standard storage caps.
a
-------
. 12.7 Load tubes into the automated thermal desorber and
analyze.
12.8 Measure total area of FID response during the period
from 0 min. to 5.5 min. run time.
12.9 Perform two consecutive desorptions and analyses for
each sample tube. Record the total area for both desorptions.
13. Data_ Analysis. and .Calculations
13.1 Calculate the percent accuracy for the QCCS (see
Section 9.4) as follows:
f *\
%Accuracy = 100 —
V 1)
where
%Accuracy = accuracy as a percent of the true value
x = mean measured value
T = true value
13.2 Calculate the mass of 2-butoxyethanol loaded in the
calibration standard tube (see Section 11.2.1) as follows:
massa = (massM) (Wt.%B)
where
mass( = mass of 2-butoxyethanol in standard solution (mg)
mass|v = mass of standard solution loaded into tube (mg}
Wt.% = weight percent of 2-butoxyethanol in standard solution
13.3 Calculate the response factor for each calibration
level (see Section 11.2.1) as follows:
where
RF = response factor for 2-butoxyethanol
RFID = area response of FID between 0 and 5.5 min run time
massg = mass of 2-butoxyethanol in standard solution (mg)
-------
13.4 Calculate the relative standard deviation for the
multilevel calibration {see Section 11.2.2) as follows:
n
L
(RFt - RF)2
(n - 1)
RF
%RSD = 100
where
%RSD = relative standard deviation
RFt = response factor for calibration level i
RF = mean response factor for all calibration levels
n = number of calibration levels
13.5 Calculate the percent difference between the daily
calibration check standard response factor and the mean response
factor (see Section 11.3) as follows:
JR? - RF ,
cc' uoo
RF
where
RF = mean response factor for all calibration levels
RF = response factor for calibration check standard
13.6 Calculate the uncorrected mass of voc in the coating
sample from the total area response of both tube desorptions (see
Section 12.9} as follows:
VOC massu =
where
FID
•MHIBBHIM
RF
(6)
VOC massu = uncorrected mass of VOC in sample (mg)
RrlD = area response of FID between 0 and 5.5 min run time
RF = mean response factor for all calibration levels
10
-------
Oi/ll/99
13.7 Calculate the uncorrected weight percent VOC in the
coating sample as follows:
(VOC mass \
- ii_ 100
sample wt . )
where
Wt.% VOCu = uncorrected weight percent VOC
VOC massu = uncorrected mass of VOC in sample (mg)
sample wt. = weight of coating loaded into tube (mg)
13.8 Calculate effective carbon numbers for each compound
using Jorgensen's technique (Reference 1). Use effective carbon
numbers and molecular weights to calculate a relative sensitivity
for each compound as follows:
(8)
where
R^ = relative sensitivity of VOC component
HH( = molecular weight of calibration standard compound
ECNa = effective carbon number of calibration standard compound
HWi = molecular weight of component i in coating
CCKi = effective carbon number of component i in coating
13.9 Using the estimated weight percent of each VOC in the
coating (from the MSDS or other source), calculate the estimated
weight fraction of the total VOC for each individual VOC as
follows:
11
-------
Wt.%. (9)
n
where
FVOCA = estimated VOC component i weight fraction of total VOC
Wt.tt = estimated VOC component i weight percentage of coating
n = number of VOC components in coating
13.10 Calculate the average relative sensitivity of the
coating as follows:
n (10)
i=l
where
RS = average relative sensitivity of coating components
that are VOC's
= estimated VOC component i weight fraction of total VOC
= relative sensitivity of VOC component i
13.11 Calculate the corrected weight percent VOC in the
coating as follows:
Wt.% VOC (11)
wt.% vocc =
where
It.% VOCe = corrected weight percent VOC
Ft.% VOC^ = uncorrected weight percent VOC
RS = average relative sensitivity of coating components
that are voc's
14. MeUao.dJEsr^ormance [Eeserved]
15 • Pollution p*rQyj5»Tifci1Qp [Reserved]
12
-------
16. Waste Management
16.1 The coating samples and laboratory standards and
reagents may contain compounds which require management as
hazardous waste. It is Che laboratory's responsibility to ensure
all wastes are managed in accordance with all applicable laws and
regulations.
16.2 To avoid excessive laboratory waste, obtain only
enough sample for laboratory analysis.
16.3 It is recommended that discarded waste coating solids,
used rags, used paper towels, and other non-glass or non-sharp
waste materials be placed in a plastic bag before disposal. A
separate container, designated "For Sharp Objects Only," is
recommended for collection of discarded glassware and other
sharp-edge items used in the laboratory. It is recommended that
unused or excess samples and reagents be placed in a solvent-
resistant plastic or metal container with a lid or cover designed
for flammable liquids. This container should not be stored in
the area where analytical work is performed. It is recommended
that a record be kept of all compounds placed in the container
for identification of the contents upon disposal.
17. Rafareneea
1. Jorgensen, et al. Anal. Chera. 1990, 62 683-689.
13
-------
Attachment 2.
Ingredients of the Four Test Paints and Structures of VOC Components
-------
Paint Ingredients
Coating
MS1-6659A
Ingred.
No.
1
2
3
4
5
Cas
No.
64742-88-7
2807-30-9
111-76-2
136-52-7
wt/wt%
1
5
6
0.1
54.0
Ingredient
Mineral Spirits
2-Propoxyethanol
2-Butoxyethanol
Cobalt 2-Ethylhexanoate
Water
Coating
1403-0100
Ingred.
No.
1
2
3
4
Cas
No.
111-46-6
37244-96-5
61790-53-2
25265-77-4
wt/wt%
1-5
5-10
1-5
1-5
Ingredient
Ethanol, 2,2'-oxybis
Nepheline syenite
Silica, diatomaceous earth
Propanoic acid, 2-methyK monester
with 2,2,4-trimethyH,3-pentanediol (Texanol)
5
6
7
8
13463-67-7
27136-15-8
20-30
10-20
1-5
30-40
Titanium oxide
yinyl acrylic copolymer
2-Propenoic acid, 2-methyl-, methyl ester,
polymer with butyl 2-propenoate and
Water
ethenylbenzene
-------
Paint Ingredients
Coating
4206-0100
Ingred.
No.
1
2
3
4
5
6
7
8
9
10
Cas
No.
64742-88-7
111-76-2
112-34-5
13463-67-7
7631-86-9
89678-90-0
21645-51-2
25750-06-5
25153-46-2
Wt/Wt%
1-5
1-5
1-5
10-20
1-5
5-10
5-10
5-10
5-10
30-40
Ingredient
Solvent naphtha (petroleum), medium aliphatic
2-Butoxyethanol
Ethanol, 2-(2-butoxyethoxy)-
Tttanium oxide
Silica
2-Propenoic acid, polymer with ethenylbenzene
and (l-methylethenyl)benzene, ammonium salt
aluminum hydroxide
2-Propenoic acid, 2-methyl-, methyl ester,
polymer with ethenylbenzene and 2-ethylhexyl 2-propenoate
2-Ethylhexyl ester, acrylic acid polymer with
styrene
Water
Coating
4020-1000
Ingred.
No.
1
2
3
4
5
6
7
8
Cas
No.
64742-88-7
112-34-5
14808-60-7
471-34-1
25586-20-3
13463-67-7
7631-86-9
7732-18-5
wt/wt%
1-5
1-5
5-10
20-30
10-20
5-10
1-5
30-40
Ingredient
i
Solvent naphtha (petroleum), medium aliphatic
Ethanol, 2-(2-butoxyethoxy)-
Quartz
calcium carbonate
2-Propenoic acid, polymer with butyl
2-propenoate and ethenylbenzene
Titanium oxide
Silica
Water
-------
Library Reference Spectra
Page
Query:
CAS: 111-76-2
Serial: 3806 CAS Reg No: 111-76-2 MW: 118 Form: C6 H14 O2
Ethanol, 2-butoxy- (CAS)
2-Butoxyethanol
2-N-BUTOXYETHANOL
29 45
25
57
50
87
75
100
125
H 0 C H 2 C H 2 0 (C H j ) 3 X •
150
175
200
225
250
-------
Library Reference Spectra
Page
Query:
CAS: 2807-30-9
Serial: 2127 CAS Reg No: 2807-30-9 MW: 104 Form: C5 H12 O2
Ethanol, 2-propoxy- (CAS)
2-Propoxyethanol
Ethylene glycol monopropyl ether
27
,!8 ,1 M
43
73
86
, ,?. .1 1. 104
25
50
75
100
125
150
175
200
225
250
-------
Library Reference Spectra
Page
Query:
CAS: 112-34-5
Serial: 13208 CAS Reg No: 112-34-5 MW: 162 Form: C8 H18 O3
Ethanol, 2-(2-butoxyethoxy)- (CAS)
2-(2-Butoxyethoxy)ethanol
2-(2-BUTOXY-ETHOXY)ETHANOL
29
J
45
57
25
50
75
75
H*(CK2)
119 132 144
100
125
150
175
200
225
250
-------
Library Reference Spectra
Page
Query:
CAS: 111-46-6
Serial: 2210 CAS Reg No: 111-46-6 MW: 106 Form: C4 H10 O3
Ethanol, 2,2'-oxybis- (CAS)
Diethylene glycol
PEG
45
31
JlL, III
57
25
50
75
75
88 99
100
125
150
175
200
225
250
-------
Propanoic acid, 2-methyl-, monester
with 2,2,4-trimethyI-l,3-pentanedioI (Texanol)
Cas: 25265-77-4
MW: 216.32
O H3
CH3-CH-C-0-CH2-C-CH-CH-CH3
CH3 CH3 CH3
Mineral Spirits and Solvent Naphtha (petroleum), Medium Aliphatic
•
Ci0H22 Alkane
MW: 142.29
Me(CH2)8Me
-------
974
Ch. 27 / Organic Chemirtry
TABLE 27-1
Some Classes
Type of
compound
alkanes
alkenes
alkynes
alcohols
alkyl halides
ethers
aldehydes
ketones
acids
esters
amines
of Organic Compounds
General
structural
formula
R— H
\O
/R
D/C=C\>
R R
R— OsC— R
R— OH
R— X
R— 0— R
O
R— C— H
R— C— R
f
R— C— OH
o
R— C— 0— R
R— NH2
Example
CH3CH2CH2CH2CH3
CH3CH2CH2CH=CH2
CH3CH2O=CCH3
CH3CH2CH2CH2CH2OH
CH3CH2CHCH2CH3
Br
CH3CH2OCH2CH2CH3
O
CH3CH2CH2CH2CH
CHjCHjCCHzCHa
ft
CH3CH2CH2CH2COH
0
CH3CH2CH2CH2COCH3
CH3CH2CH2CH2CH2NH2
Name
pentane
1-pentene
2-pentyne
1-pentanol
3-bromopentane
ethyl propyl ether
pentanal
3-pentanone
pentanoic acid
methyl pentanoate
pentylamine
Some of the functional groups appearing here and discussed later in the chapter have distinctive names:
?
—OH, hydroxyl; C=O, caibonyl; —C—OH, caiboxyl; —NH2, amino.
tinctive functional groups are indicated in blue. You may find it helpful to refer to
this table from time to time.
Example 27-5 illustrates that when we name organic compounds we must desig-
nate the functional groups present, as well as follow the other nomenclature rules
outlined in (27.1).
Example 27-5
Naming functional groups in an organic compound. Use information from
Table 27-1 and from elsewhere in this section to derive an acceptable name for
the compound
Solution. First we should convert the condensed formula into a structural
formula.
H
H H—C—H H H H
I
:-O
-C-C-C-H
H
H H
From the presence of the group C—0—C we see that this is an ether. The group
shown on the left is isopropyl; the one on the right is propyl. We can call the
compound isopropyl propyl ether.
SIMILAR EXAMPLE: Exercise 5.
-------
Attachment 3.
Example of Calculations for Effective Carbon Number (ECN) and VOC FID
Sensitivities Relative to 2-Butoxyethanol
-------
CH3CH2CH2CH2-0-CH2CH2-OH 111-76-2
butyl cellosolve
ethylene glycol monobutyl ether
2-butoxyethanol
CH3CH2CH2CH2-0-CH2CH2-0-CH2CH2-OH 112-34-5
diethylene glycol monobutyl ether
CH3CH2CH2-O-CH2-CH-OH3 1569-01-3
OH
n-propoxypropanol
l-propoxy-2-propanol
O
C-0-CH2CH2CH2CH3
84-74-2
C-O-CH2CH2CH2CH3
6
dibutylphthalate
0 H3COH
CH3-CH-C-O-CH2-C-CH-CH-CH3 25265-77-4
CH3 CH3 CH3
texanol
texanol ester alcohol
2,2,4-trimethylpentane-1,3-diol
monoisobutyrate
HO-CH2CH2-OH 107-21-1
ethylene glycol
1,2-ethanediol
O
CH3-C-O-CH=CH2 108-05-4
vinyl acetate
acetic acid ethenyl ester
FIGURES.
STRUCTURES, SYNONYMS, AND CAS NUMBERS OF VOC's IN TEST COATINGS
-------
concept.9'10 Table 3 demonstrates the approach and Table 4 gives calculated values for all
VOC's listed on the MSDS's for the four test coatings.
TABLE 3. CALCULATION OF EFFECTIVE CARBON NUMBERS1
Compound
2-butoxvethanol
diethylene glycol
monobutvl ether
1 -propoxy-2-propanol
(mixture of isomers)
dibutvbhthalate
2,2,4-trimethylpentane-
1 ,3-diolmonoisoburyrate
ethvlene elvcol
vinvl acetate
Carbon
Number
6
8
6
16
12
2
4
Carbon Number Corrections for:
Ester Alcohol Ether
Linkage(s) Linkage(s) Linkage(s)
(- 1.27 each) (-0.64 each) (-0.78 each)
-0.64
-0.64
-0.64
-0.78
-1.56
-0.78
-2.54
-1.27
-0.64
-1.28
-1.27
Effective
Carbon
Number
4.58
5.80
4.58
13.46
10.09
0.72
2.73
'Calculations based on Jorgensen, etal.,Anal. Chem., 1990, 62,683-689
TABLE 4. VOC FID SENSITIVITIES RELATIVE
Compound CAS No. MW
2-butoxyethanol
diethylene glycol monobutyl
ether
1 -propoxy-2-propanol (mixture
ofisomers)
dibutylphthalate
2,2,4- trimethylpentane- 1 ,3-diol
monoisobutyrate
ethylene glycol
vinvl acetate
111-76-2
112-34-5
1569-01-3
84-74-2
25265-77-4
107-21-1
108-05-4
118.18
162.23
118.18
278.35
216.32
62.07
86.09
TO 2-BUTOXYETHANOL
Effective Calculated FID
Carbon Sensitivity Relative
Number to 2-Butoxyethanol1
4.58
5.80
4.58
13.46
10.09
0.72
2.73
1.000
0.923
1.000
1.248
1204
0.299
0.818-
'On a mass basis
9 Andrew D. Jorgensen, Kurt C. Picel, and Vassilis C. Stamoudis, Prediction of gas
chromatography flame ionization detector response factors from molecular structures, Anal.
Chem., 1990, 62, 683-689.
10Magdolna Morvai, Ildiko Palyka, and Ibolya Molnar-Perl, Flame ionization detector
response factors using the effective carbon number concept in the quantitative analysis of esters,
J. Chromatog. Sci., 1992, 30, 448-452.
-------
VARIABIL.XLS: Middle
Coating ID
IS-91-
IS-91-
IS-91-
IS-91-
IS-91-
IS-91-
IS-91-
CAS No.
7429-90-5
none
none
none
112-25-4
111-76-2
7732-18-5
Wt/Wt % Ingredient
3% aluminum
acrylic polymer
melamine resin
polyurethane polymer
2-hexyloxyethanol
4% ethylene glycol-mono butyl ether
water
IS-91-
CT05
CT05
CT05
CT05
CT05
CT05
111-76-2
112-34-5
1569-01-3
84-74-2
7631-86-9
21645-51-2
<5% 2-bufoxyethanol
<5% diethylene glycol monobutyl ether
<5% n-propoxypropanol
<5% dibutylphthalate
<5% silica - amorphous
<5% aluminum hydroxide
CT05
CP05
CP05
CP05
CP05
111-76-2
7779-90-0
25265-77-4
84-74-2
<5% 2-butoxyethanol
<5% zinc phosphate
<5% 2,2,4-trimethyl-l-l,3-penta/iediol monois
<5% dibutylphthalate
CP05
Y4118
Y4118
Y4118
Y4118
Y4118
Y4118
Y4118
Y4118
107-21-1
14808-60-7
25265-77-4
13463-67-7
108-05-4
Trade Secret
25035-69-2
»
7732-18-5
1-5% 1,2-ethanediol
10-20% quartz
1-5% propanoic acid, 2 -methyl-, monoester with
2,2,4-trimethyl-l ,3-pentanediol
10-20% titanium dioxide
<1 .0% acetic acid ethenyl ester
10-20% vinyl acrylic copolymer
1 -5% 2-propenoic acid, 2-methyl-, polymer with
butyl 2-propenoate and methyl 2-methyl-2-
propenoate
30-40% water
Y4118
Middle
VOC
4.0
4.0
2.5
2.5
2.5
2.5
10.0
2.5
2.5
2.5
7.5
3.0
3.0
0.5
6.5
ATD-FID Calculations
Fraction
ofTotal
VOC
1.00
1.00
0.25
0.25
0.25
0.25
1.00
0.33
0.33
0.33
1.00
0.46
0.46
0.08
1.00
Rel. Sens.
1.000
RS.,.-=
1.000
0.923
1.000
1.248
RS.yt=
1.000
1.204
1.248
RS.rt~
0.299
1.204
0.818
RS.,.=
Contri-
bution
1.000
1.000
0.250
0.231
0.250
0.312
1.043
0.333
0.401
0.416
1.150
0.138
0.555
0.063
0.757
Page 1 of 2
Calculations Using Middle Values of Ranges for All VOC's
Appendix C
-------
Attachment 4.
Reference for Test Method
-------
Anal. Cheat 1MO. 82. 683-989
with a vapor cell in an oven and comparing the LJF intensity
If in the same system.
Figure 5 shows the PMT output voltage Vr as a function
of the Na density n for three vapor cells with different buffer
gas pressures. The Fairbank formula was used for the con-
version from temperature to Na number density (1). Vr was
proportional to n over a number density range from 10T to 1011
cm"3. The detection limit 107 cm"8 is relatively high, because
it is determined by stray light and no attempt to decrease it
has been made. The VT value for the vapor cell with a He
gas pressure of 1 atm is 50% smaller than that of the evac-
uated cell because of collisional quenching by He. From Figure
5, the output PMT voltage of 1 mV corresponds to the atomic
density n of 1.68 X 107 atoms/cm1 at 1 atm.
We calculated the total number of dissociated atoms N
passed through the observing region in the atomizer by the
following formula:
N = nsvS (7)
where s is the cross section of the discharge tube, v is the He
velocity, and S is the integrated pulse form of the LJF signal
in mV; consider the absolute density and the atomization
efficiency for the LIF signal shown in Figure 2A obtained for
a concentration of 10 ng/cm3. The nmTimnm number density
is 1.18 X 10" atoms/ cm3, because the peak voltage in Figure
2A is 700 mV and a 10% ND filter is used. Integration of the
envelope of the LJF signal in Figure 2A provides S » 280 mV
s; s = 0.043 cm2, o = 108 cm/s and n - 1.68 X 107 atoms/(cm3
mV). Therefore, N = 2.62 X 1011 atoms. We define the
atomizing efficiency 0. as
o - number of dissociated atoms N
1 number of atoms (ions) in sample water
Since the number of atoms in a 10 nL sample of water of 10
ng/cm3 is 2.7 X 10", 0, is calculated to be 9.7%. However,
shown in Figure 2A, since the plasma was turned on and off,
the integration should not be done along the envelope but the
pulse shape. In that case, the efficiency is given by /9. • 1.6%.
The feature of this type of atomizer is that the instanta-
neous number density obtained in the observation region is
large, because rapid injection of the sample is attained by flash
heating. According to the results mentioned above, a peak
density of 1.18 X 107 atoms/cm3 is obtained for the sample
of 1 pg/cm3. Therefore, we can expect atomic detection of
less than 1 pg/cm3 by decreasing the noise sources.
ACKNOWLEDGMENT
The authors thank Shin'ichi Ichitsubo and Tatsuya Izuha
for their assistance.
LITERATURE CITED
(1) Fairbank, W. M., Jr.: Hansch, T. W.; Schawtow, A. L. J. Opt. Soe.
Ant. 1975, 65. 199-204.
(2) GettJwachs. J. A.; KWn, C. F.; Wessel, J. E. IEEEJ. Quantum. Bac-
tron. 1978, 06-14. 121-125.
(3) Barykki, V. I.; Latokhov. V. S.; MIsNn, V. I.; Semchishen, V. A. JETP
Lett. 1977. 28. 357-360.
(4) She. S. Y.; Fairbank. W. M.. Jr. Opt. Lett. 1978, 2. 30-32.
(5) Fraser, L. M.; Wtofordner. J. 0. Anal. Cham. 1971. 43, 1693-1697.
(6) Fraser, L. M.; WkMfordnar, J. 0. Anal. Cham. 1972, 44, 1444-1451.
(7) Weeks, S. J.; Haraguchl, H.; Wlnefontrwr, J. 0. Anal. Cham. 1978,
50. 360-368.
(8) Hohkner, J. P.; Hargts, P. J.. Jr. Appl. Ptiys. Latt 1977. 30, 344-346.
(9) Hohkner, J. P.; Hargfe, P. J., Jr. Anal. Chlm. Act* 1971, 97, 43-49.
(10) Kawaguchi, H.; vatee, B. L Anal. Cham. 1975, 47, 1029-1034.
(11) Beenakker. C. I. M. SpaetrocHm. Aeta 1976. 31B. 483-486.
RECEIVED for review September 22,1989. Accepted December
21,1989.
Prediction of Gas Chromatography-Flame lonization Detector
Response Factors from Molecular Structures
Andrew D. Jorgensen*
Department of Chemistry, University of Toledo, Toledo, Ohio 43606
Kurt C. Picel1 and Vassilis C. Stamoudis1
Argonne National Laboratory, Argonne, Illinois 60439
The prediction of flame lonization detector response factors
as a function of molecular structure components to evaluated
with modem capillary column gas chromatography equipment
that Included an on-column Injector. The effect on the
standard carbon content based response by electronegative
atoms Is analyzed for various functional groups. This study
updates much earlier work that characterized the decrease
In signal response by using average correction factors for
each functional group. The effective carbon number concept
based on naphthalene as the Internal standard was used. For
56 compounds containing a single functional group, predictions
based on these average responses reproduced the actual
response to within 1.7% on average. This model was then
extended to btfunctlonal groups wKh similar success for sev-
eral molecules. The effects of changes In temperature pro-
gramming and concentration were found to be minimal within
the range studied.
1 Environmental Research Division.
2 Environment, Safety and Health, Support Services Division.
INTRODUCTION
High sensitivity, uniform response to hydrocarbons, and
a broad linear range have made the flame ionization detector
(FID) perhaps the most widely used detector in gas chro-
matography. The FID response of hydrocarbons is generally
proportional to the mass of carbon present in the sample, but
the degree of signal reduction due to partially oxidized carbon
atoms in heteroatomic compounds varies markedly with
heteroatom and bond types. Compounds that contain, for
example, oxygen, nitrogen, or halogens give varied responses
but can be quantified by the FID if corrections are made for
the usual loss of sensitivity caused by the presence of these
atoms in various functional groups. Correction factors can
be determined either through the analysis of authentic
standards or from accurate predictions of loss of response
based on measurements made for compounds of related mo-
lecular structure.
Predictive methods would be quite useful if they could
accurately indicate the change in response caused by the
presence of one or more heteroatomic functional groups.
Correction factors have long been used for various function-
0003-2700/90/0362-0683S02.50/0 © 1990 American Chemical Society
-------
684 • ANALYTICAL CHEMISTRY, VOL. 62, NO. 7, APRIL 1, 1990
alities. However, a comprehensive approach is needed for
determining FID response precisely so that a broadly appli-
cable system for predicting response can be developed.
Modem analytical instrumentation allows highly precise re-
sponse measurements to be made for the wide variety of
substances that are needed for the development of such a
system. Furthermore, systematic response predictions could
be easily automated on computerized data systems to greatly
facilitate analysis of complex organic mixtures and reduce the
requirement for analyzing large numbers of authentic stand-
ards. To this end the present work has determined the re-
sponse of a large number of compounds from many different
chemical classes in order to critically reevaluate the conclusions
of earlier reports and to begin to develop a systematic ap-
proach for predicting FID response in general on the basis
of molecular structure. A system to accurately predict the
response for a large number of compounds, many of them
related to coal liquids, will be presented.
Although many questions about the specifies of flame
chemistry in the FID remain unanswered, there is general
agreement that the primary source of ions in the flame is the
chemical ionization caused by the reaction of an oxygen atom
with a radical containing a single carbon (7-5). The most
commonly proposed reaction is
CH + 0 — CHO+ -1- e-
(1)
Schaefer (6) has presented data suggesting that reactions other
than eq 1 are also significant contributors to ion production.
He based his conclusion on the temperature dependence of
the ion current.
Some work has been able to distinguish the relative con-
tribution of the ground state of CH compared to that of some
excited states of the radical (7,8). Although the latter are
much more effective at producing ions, it was demonstrated
that the reaction of the former is primarily responsible for
the ion current in the FID.
The origin of CH and related radicals has been the cause
for considerable speculation, and divergent views have been
defended. Blades (2, 9) has presented data to support the
theory that in most cases radicals are produced by a series
of hydrogen-stripping and hydrogen-cracking reactions that
occur in the reducing section of the flame. For example
C2H6 -1- 'H ~ 'C2H6 -1- H2
•C2H6 -1- -H -» 2'CH3
(2)
(3)
Sternberg (1) presented a table that summarized data from
a variety of compounds and allowed prediction of the effective
carbon number (ECN) of a compound from its structure. For
example, he found that the presence of a carbonyl group
reduced the effective number of carbons by one, while a
primary alcohol caused a decrease of 0.6 carbon. Other re-
searchers working at about the same time obtained similar
results (10-12).
More recently two groups have reported on the FID re-
sponse of various compounds. Tong and Karasek (13) de-
termined a large number of absolute response factors for
aliphatic and aromatic hydrocarbons and a few substituted
species. They concluded that average response values were
sufficiently accurate for the quantification of hydrocarbon
compounds in many applications. A slight quantitative dis-
tinction between alkanes and aromatics was seen. However,
their study included only a small number of nonhydrocarbons,
and it was not possible to make a firm statement about most
other classes.
Scanlon and Willis (14) used their own data and some
results from the literature to maintain that the ECN concept
is of value in checking the results from samples of known
composition. The evaluation of column performance was
mentioned as an example. Their instrumentation was also
of modern design, and they did employ an internal standard,
but some of their results were achieved by using a split rather
than an on-column injection.
Frequently we need to find the approximate concentration
of a large number of species in a complex mixture, such as
a coal-derived liquid. Typically a gas chromatograph/mass
spectrometry analysis provides the molecular structure for the
components. Because hundreds of compounds may be present
and because a degree of accuracy equal to a few percent is
sufficient, the preparation and analysis of accurately prepared
standards are not practical or required. In many cases it would
also be quite difficult to obtain a substance in sufficient purity
for use as a standard. We therefore concluded that it was time
to expand the review of ECNs to a wider range of compounds
than has been reported in the recent literature and to develop
a systematic approach for predicting FID response. We
wanted to confirm that the presence of a particular functional
group could be characterized by a single adjustment to the
ECN and to determine whether these effects could be de-
scribed in a simple additive fashion for polyfunctional com-
pounds. Our eventual aim was to develop a computer program
that would query the user for structural information about
each peak in a chromatogram, calculate the ECN from in-
formation in a data base, and use the area and concentration
of the internal standard to calculate the concentration of the
component.
EXPERIMENTAL SECTION
Instrumentation. All analyses were performed by using a
Hewlett-Packard 5880A gas chromatograph equipped with an FID
and a J&W Scientific on-column injector. The column was J&W
Scientific's DB-5, 30 m X 0.32 mm i.d., with a 0.25-itm film
thickness, purchased from Alltech Associates. The carrier gas
was helium at a linear flow velocity of 40 cm/a. The detector gas
flows were 35 mL/min for hydrogen, 410 mL/min for air, and
30 mL/min for nitrogen as the make-up gas. The oven was
programmed for an initial hold of 2 min at 30 °C, then 10 °C/min
until all peaks were eluted or a temperature of 300 °C was reached.
All mass measurements were performed on a Mettler AC100
analytical balance.
Chemicals. The solvent for all mixtures was methylene
chloride (HPLC grade from Baker Chemicals and Fisher Scien-
tific). The compounds were of 98% or greater stated purity, except
for two with 97% and two unstated. They were obtained from
Aldrich Chemical Co., Fluka Chemicals, and Chemical Procure-
ment Laboratories (one compound only). Naphthalene was the
internal standard; it had a stated purity of 99+%. The purity
of each compound was checked by performing a separate GC
analysis of the substance at high concentration hi methylene
chloride. The final relative response factors for each compound
was corrected for the total amount of chromatographable im-
purities that were found. The average correction was 0.6%. Only
three corrections were above 2%, and 2.6% was the largest
Procedure. An accurately weighed sample of approximately
60 mg of each compound was dissolved in solvent in a 25-mL
volumetric flask to make stock solutions. A mixture of 5-10
compounds was prepared by adding 0.90 mL of stock solution
for each and a like amount of the internal standard stock, using
a 1.0-mL gas-tight syringe, to a second 25-mL volumetric flask
to give concentrations of about 50 ppm by mass. A few compounds
were also studied at 200 and 10 ppm to look for a concentration
effect At least three sets of all stock solutions, including the
internal standard and mixtures, were prepared, and each mixture
was analyzed 3 or more times. Solutions were usually analyzed
within 24 h of preparation. Injection volumes were between 1
and 2 /tL. •
RESULTS AND DISCUSSION
The precision of the relative response factors (RRF) mea-
surements was uniformly good. For the set of three or more
injections of the same solution, the average variation from the
-------
ANALYTICAL CHEMISTRY. VOL 62. NO. 7, APRIL 1. 1990 • MS
Table I. FIO Response for Nitrogen Heterocycles
ECN
minus % error
no. of in pre-
name formula RRF ECN carbons diction
pyrole
pyridine
2-picoline
3-picoline
2,3-lutidine
3,4-lutidine
3,5-lutidine
3-ethylpyridine
5-ethyl-2-methyl-
pyridine
2-propylpyridine
indole
5-methylindole
quinoline
4-methylquinoline
carbazole
acridine
averages
C4H,N
C5H.N
C,HTN
C,H,N
CrH^
CfHjN
C,H,,N
C,HUN
C,H7N
CjH7N
CjoHfN
CUH»N
CUH,N
0.646
0.691
0.727
0.723
0.752
0.801
0.772
0.747
0.788
0.760
0.811
0.815
0.825
0.854
0.897
0.973
3.38
4.26
5.28
5.25
6.28
6.70
6.45
6.26
7.45
7.18
7.41
8.34
8.32
9.54
11.70
12.21
-0.62
-0.74
-0.72
-0.76
-0.72
-0.30
-0.55
-0.75
-0.56
-0.82
-0.69
-0.66
-0.68
-0.46
-0.30
-0.79
-0.62
-0.2
2.6
1.8
2.4
1.4
-4.8
-1.1
2.1
-1.0
2.7
-0.5
0.4
0.7
-1.7
-2.8
1.4
1.7
Table II. FIO Response for Ketones
name
ECN
minus % error
no. of in pre-
formula RRF ECN carbons diction
3-pentanone
2-hexanone
3-heptanone
3-octanone
3-nonanone
cyclohexanone
1-indanone
3-methylcyclo- '
pentanone
acetophenone
benzylacetone
benzophenone
9-fluorenone
averages
C,H100 0.614 4.12 -0.88
C,H120 0.659 5.15 -0.85
C,HM0 0.686 6.11 -0.89
CgHjeO 0.711 7.11 -0.89
C^gO 0.738 8.19 -0.81
CjHjoO 0.672 5.14 -0.86
C,H,0 0.799 8.24 -0.76
C,H100 0.654 5.00 -1.00
C,H,0 0.761 7.13 -0.87
C10H120 0.790 9.14 -0.86
C,3H,00 0.887 12.60 -0.40
CMH,0 0.887 12.47 -0.53
-0.80
1.8
1.1
1.5
1.3
0.2
1.2
-0.5
3.9
1.0
0.7
-3.2
-2.2
1.6
Table III. FID Response for Hydrocarbons
name
n-octane
n-decane
n-dodecane
n-tetradecane
1,2,4- trimethylbenzene
averages
ECN
minus
no. of
formula RRF ECN carbons
Alkanes
C,H« 0.854 7.61 -0.39
C,oHM 0.891 9.89 -0.11
C,,Ha, 0.928 12.34 +0.34
CMH3o 0.884 13.68 -0.32
Aroma tics
CgHu 0.970 9.09 +0.09
-0.08
% error
in pre-
diction
4.1
0.3
-3.4
1.8
-1.9
2.3
mean for the RRF was usually a few tenths of a percent For
the set of replicate solutions of the same compound, the av-
erage variation from the mean was 1.1% for the entire com-
plement of 71 compounds. This number is quite consistent
with an assumption that the primary sources of uncertainty
are the determination of mass and the delivery of 0.90 mL
of solution. The four normal hydrocarbons did exhibit an
average variation for the replicate set of solutions equal to
2.6%, more than twice the value for the entire set This may
Table IV. FID Response for Ethers and Furans
ECN
minus
no. of % error in
name formula RRF ECN carbons prediction
Ethers
anisole C,H(0 0.728 6.14 -0.86
diphenyl ether C,3H100 0.859 11.41 -0.59
xanthene CI3H100 0.868 12.20 -0.80
Furans
2,3-benzofuran C,H,0 0.761 7.01 -0.99
dibenzofuran C,jH,0 0.866 11.35 -0.66
averages
-0.78
1.4
-1.6
0.2
3.0
-1.1
1.5
Table V. FIO Response for Alcohols and Phenols
ECN
name
no. of % error in
formula RRF ECN carbons prediction
Primary Alcohols
1-pentanol
1-heptanol
CjHuO
C,H,0
0.663
0.728
4.56
6.60
-0.44
-0.40
-4.4
-3.6
Secondary Alcohols
2-hexanol
3-octanol
2-nonanol
1-indanol
2-indanol
C«H140
C.H180
C^HjoO
C.H.oO
C^wO
0.667
0.725
0.743
0.824
0.842
5.32
7.37
8.36
8.62
8.42
-0.68
-0.63
-0.64
-0.38
-0.68
0.8
-0.1
-0.0
-3.1
-0.7
Phenols
phenol
p-cresol
1-naphthol
2-naphthol
averages
(W>
C,H,0
C10H,0
C,«H,0
0.709
0.756
0.806
0.804
5.21
6.38
9.06
9.05
-0.79
-0.62
-0.94
-0.95
-0.64
2.9
-0.3
3.2
3.4
2.0
Table VI. FIO Response for Amines and Esters
name
aniline
4-aminobiphenyl
1-aminonaphthalene
2-aminofluorene
averages
ethyl acetate
propyl acetate
methyl benzoate
averages
formula RRF ECN
Amines
CgH7N 0.748 5.43
CUH,,N 0.868 11.45
C10H»N 0.873 9.75
C,,HUN 0.851 12.03
Esters
C4H,Oj 0.400 2.75
CsH10Oj 0.462 3.68
C»H,0, 0.635 6.75
ECN
minus % error
no. of in pre-
carbons diction
-0.57
-0.55
-0.25
-0.97
-0.58
-1.25
-1.32
-1.25
-1.27
-0.3
-0.3
-3.4
3.2
1.8
-0.8
1.2
-0.3
0.8
have been due to the less than ideal solvent for such nonpolar
compounds. Preliminary additional work with hexane as the
solvent improved precision.
Tables I-VI give the results for a set of 56 compounds.
Except for the hydrocarbons, each compound contained only
one functional group. The fifth column in each table gives
the difference between the ECN and the actual number of
carbons in a given compound, i.e., the change in ECN due to
the presence of the functional group. The average value for
this change is given for each class of compounds. For example,
nitrogen heterocycles with one nitrogen atom (Table I) have
ECN values that are, on average, 0.62 less than their actual
-------
686 • ANALYTICAL CHEMISTRY, VOL. 62, NO. 7. APRIL 1, 1990
Table VII. Summary of ECN Changes and Prediction
Errors
Nitrogen Heterocycles
14-1
class
nitrogen heterocycles
ketones
amines primary
alcohols and phenols
ethers and furans
esters
hydrocarbons
no. of
com-
pounds
16
12
4
11
5
3
5
total 56
av %
error in
predic-
tion
1.7
1.6
1.8
2.0
1.5
0.8
2.3
avl.7
average
ECN
change
-0.62
-0.80
-0.58
-0.64
-0.78
-1.27
-0.08
ref 1
ECN
change
-1.0
-0.6
-0.6 (le)
-0.75 (2°)
-1.0
-1.25
0
carbon count For this set of compounds the range is between
0.30 and 0.82 carbons.
For each class of compounds, the average ECN loss was used
to calculate a predicted ECN value. The last column of each
table gives the difference between this predicted ECN and
the actual ECN is a percentage of the latter. A negative
number indicates that the predicted ECN and therefore the
RRF was lower than the observed RRF. Below this last
column is the average of the absolute value of these percent
errors in prediction. Note that some tables have distinctions
within a group, e.g., primary and secondary alcohols and
phenols. However, the statistics are calculated for the entire
group. A case could be made for treating these subgroups
separately. Sternberg (1) has done this for some classes, and
we are pursuing this line of research in the case of alcohols
and hydrocarbons.
Table VD summarizes the group data from Tables I-VI and
gives the comparable numbers quoted by Sternberg (1). Note
that the average difference between the predicted ECN and
its experimental value was only 1.7%. Of the 56 compounds,
36 (64%) differed by less than 2% and 43 (77%) by less than
3%. These results clearly indicate that one can assume a
single value for the change in ECN due to the presence of one
functional group and achieve a quite reasonable degree of
accuracy, at least under the conditions of these experiments.
Even though the range of values for the shift in ECN seems
at first glance to be rather large (e.g., -0.30 to -0.82 for the
nitrogen heterocycles), one must remember that these are
fractions of a single carbon out of the total number of carbons
in a compound. Therefore, a difference of 0.30 between the
experimental and predicted ECN is only 3% for a compound
with 10 carbons.
Ironically, the poorest prediction record was found for
hydrocarbons, but only a small number of these compounds
were included because there are numerous reports in the
literature for this class. This group's average prediction error
of 2.3% is quite acceptable for the purposes of this work. The
second highest percent error in prediction was found for the
alcohols and phenols. This finding seems to support the need
for discriminating among the three chemically different hy-
droxyl groups (primary, secondary, and phenol). However,
the 2.0% average difference is not high enough to justify any
distinction at this time.
The last column of Table VTJ gives the results of Sternberg
as reported in 1962 (1). Excellent agreement is seen for
primary amines, esters, and hydrocarbons. The average value
for all of the alcohols and phenols is also quite reasonable,
given the earlier data for primary and secondary alcohols. The
observed effects of oxygen for ketones and ethers, including
furans, are less than those obtained by Sternberg to a rather
significant degree. This may very well reflect more efficient
chromatography with modern columns and perhaps the use
of higher purity standards in the present work. In fact, it is
12-
u
I
1
s
I
1
10-
8-
8-
4-
« a 10
Number of Carbons
12
14
Figure 1. ECN versus carbon number of nitrogen heterocycles.
Symbols Indicate experimental points: ( ) ECN equals number of
carbons (no effect); (•••) each heteroatom reduces ECN by 1.0 (fun
effect); ( ) carbon number minus average change In ECN for group.
Ethers and Flirans
14-i
12-
10-
8-
8-
4-
A Ethers
D Furans
46 8 10 12
Number of Carbons
14
Figure 2. ECN versus carbon number for ethers and furans. Symbols
and Ones are as In Figure 1.
quite surprising that only these differences are found, given
the significant changes that have occurred in instrumentation
in the last 26 years.
Figures 1-5 present these results in graph form for five of
the compound classes studied. The plots give ECN versus
the actual number of carbons. Symbols indicate experimental
points, the dashed line is for the case of ECN equaling the
number of carbons (no effect), and the dotted line is for the
case in which each heteroatom causes as reduction of exactly
one carbon in the ECN (full effect). The solid line through
the symbols is not the best line in a least-squares sense but
is determined by subtracting the average change in ECN for
the group from the number of carbons. That is, the intercept
is shifted with the data, but the slope is fixed at one. In all
cases it is apparent that the solid line gives a significantly
better fit to the data than either the dashed line (no effect)
or the dottled line (full effect).
Table VIII includes the results from three additional groups
of compounds. Two of the three sulfides studied showed very
slight increases in response from what would be expected from
-------
Ketones
12-
10-
8-
6-
4-
2 4 6 8 10 12 14
Number of Carbons
Figure 3. ECN versus carbon number for ketones. Symbols and fines
are as In Figure 1.
Alcohols and Phenols
14-1
12-
V
!„
C
o
•e
-------
688 •» ANALYTICAL CHEMISTRY, VOL. 62, NO. 7, APRIL 1, 1990
Table IX. Compound! with Multiple Functionalities
structure name group(s)
1,4-naphthoquinone two ketones
no. of ECN ECN %
carbons reduction predicted experimental difference
10 2 x 0.80 8.40
8.34
+0.8
xanthone
ketone + ether
13 0.80 + 0.78 11.42 11.56
-1.2
4-methozyphenol phenol + ether
7 0.64 + 0.78 5.58
5.50
+1.5
4-ethoxyphenol phenol + ether
8 0.64 + 0.78 6.58
6.37
+3.3
catechol
two phenols
6 2 X 0.64 4.72
4.94
-4.4
4-acetylpyridine N in ring + ketone
7 0.62 + 0.80 5.58
5.52
+1.1
carbonyl carbon, this ether oxygen has an effect only for the
20% of the time when the carbonyl oxygen does not remain.
Therefore that total reduction of carbon will be
carbonyl carbon
second ether carbon
total
0.80 + 0.20(0.78/2)
0.78/2
'0.88
•0.39
<1.27
Interestingly, this is exactly the value found in the small
set of three esters studied in the present work, and it is vir-
tually identical with Stemberg's result of 1.25 (1). One must
be cautious about over-interpreting from this quite small
sample of compounds, but the agreement is quite supportive
of the suggested analysis. These facts lend further weight to
our working model, which does include the additivity of effects.
Additive effects were further studied by using aminc-
pyridines. The results are summarized in Table VIII. Al-
though three of the four compounds have quite consistent
shifts in ECN, one of them gave a value almost twice that of
the other three. Somewhat more disturbing is the fact that
the presence of an amino group and a nitrogen in a ring would
be expected to cause a change in response equal to -0.58 and
-0.62, respectively. This sum of -1.20 is not too far from the
4-aminopyridine result of-1.39, but it is quite far from the
approximately -0.80 found for the other three compounds.
Possible sorptive losses would produce effects in the opposite
direction. We have no other suggestions for these discrep-
ancies.
We have performed some experiments to see if the numbers
reported here are valid for other experimental conditions. A
set of ketone mixtures was analyzed in duplicate at a tem-
perature program rate of 4 °C/min rather than the 10 °C/min
used for all of the other studies. The mean RRF values from
these runs were on average slightly greater than the results
in Table II, with two-thirds higher and one-third lower. The
average of the absolute values of the percent deviations was
2.1%.
The concentration dependence of the results was tested with
additional mixtures of these ketones at nominal concentrations
of 200 and 10 ppm. At the higher concentration, five of the
eight compounds differed by less than 3% from the results
in Table II and seven of eight by less than 4%. At the lower
concentration, the results for 3-pentanone and 1,4-naphtho-
quinone were above the numbers in Table II by about 6%,
the 3-heptanone was low by the same amount, and 2-hexanone
was low by almost 11%. The remaining four compounds
differed by 2.5% or less. The analysis scheme presented in
the present work must be used with caution at low concen-
trations. Some of the variations seen in all three of these tests
of conditions must be ascribed to differences in chromato-
graphic conditions and small data sets.
Variations in flame conditions might be expected to cause
unacceptable deviations. We have begun a comprehensive
study using a wide variety of hydrogen and air flow rates.
Preliminary indications are that although absolute responses
do vary measurably with hydrogen concentration, the relative
responses as obtained by using an internal standard are
sufficiently constant for the type of analysis that we propose.
If one wanted to use the RRF values reported in this work
but did not want to use naphthalene as an internal standard,
a simple determination of the RRF between the desired in-
ternal standard and the naphthalene would give a correction
factor that could be applied to all of the needed numbers. If
the new standard were one of the other compounds in this
study, even that experiment would be unnecessary. Scanlon
and Willis (14) used tridecane and tetradecane as their ECN
standards and found the ECN of naphthalene to be 10.01.
Therefore, our assumed value of 10 would make the present
RRF values be appropriate also for the alkanes that they used.
Future work in this area is needed to more firmly establish
the additivity of effects before the entire process can be ac-
curately modeled. We would envision the automated use of
RRF values from a computerized data base or from a calcu-
lation, either based on the individual contributions of all the
structural groups.
-------
Anal. Chem. 1000. 62, 689-693
68*
One can, therefore, conclude that FID responses for a wide
variety of compounds can be predicted to a good degree of
accuracy, typically 2-3%. This obviates the need to obtain
high-purity standards and to accurately prepare and analyze
solutions of these compounds as long as one confirms that good
chromatographic conditions are present If one needs greater
accuracy than this method provides, standards of actual purity
greater than 98% would have to be obtained, and at least two
sets of standard solutions would have to be prepared, because
one can expect a single solution to differ from the mean of
a set of standards by 1% or more (see text above). Although
the primary use for this technique is expected to be the
quantification of components in a complex organic mixture
if a molecular or at least a general structural identification
can been made, other uses for response prediction would be
in evaluations of sample purity and column performance.
ACKNOWLEDGMENT
Victoria Vlastnik is acknowledged for assistance in data
collection and Doug Hoffman for technical assistance. The
preliminary work cited was performed by Maria Portellos.
LITERATURE CITED
(1) Stemberg. Jamas C.; Gateway. WUBam S.; Jones, David T. L In Qaa
Chromatography; Brenner, N., Calten, J. E., Weiss, M. 0., Eds.; Aca-
demic Press: New York. 1962; pp 231-207.
(2) Blades. Arthur T. J. Cttromatogr. So/. 1973, 11, 251-265.
(3) Blades. Arthur T. Can. J. Cham. 1976, 64, 2919-2924.
(4) Nicholson, Anthony J. C.; Swtngter, 0. L Combo*/. Flame 1960, 38,
43-62.
(5) Nicholson, Anthony J. C. J. Chem. Soc., Faraday Tnnt. 1, 1982.
78, 2183-2194.
(6) Schaeler, B. A. Combust. Flame 1964, 50, 43-49.
(7) Cool. Terr! A.; Tjossem, Paul J. H. Chem. Phyt. Lett. 1964, 111,
82-88.
(8) Cool, Terr* A.; Goldsmith, John E. M. Appt. Opt. 1987. 20,
3542-3561.
(9) Blades. Arthur T. J. Chromatogr. $d 1984. 22, 120-121.
(10) Perkins, Q.. Jr.; Rouayheb, Q. M.; Uvely. L 0.; Hamilton, W. C. In Qes
Chromatography; Brenner, N., Calen, J. E., Weiss, M. D., Ed*.; Aca-
demic Press: New York, 1962; pp 269-285.
(11) Perkins, Gerald, Jr.; Laramy, R. E.; Uvely. L. 0. Anal. Chem. 1963.
35, 360-362.
(12) Ackman, R. Q. J. Gat Chromatogr. 1964, 2, 173-179.
(13) Tong. H. Y.; Karasek, F. W. Anal. Chem. 1984, 50. 2124-2128.
(14) Scanton. James T.; WRRs, Donald E. J. Chromatogr. Sd. 1988. 29,
333-340.
RECEIVED for review September 18,1989. Accepted December
22,1989. A.D.J. gratefully acknowledges the support of the
Argonne National Laboratory Education Division. This work
was supported by the U.S. Department of Energy, Assistant
Secretary for Fossil Energy, under Contract W-31-109-Eng-38.
Surface-Enhanced Raman Analysis of Sulfa Drugs on Colloidal
Silver Dispersion
i W. S. Sutherland, J. J. Laserna,1 M. J. Angebranndt, and J. D. Winefordner*
Department of Cherqistry, University of Florida, Gainesville, Florida 32611
Surface-enhanced Raman spectrometry (SERS) of three suHa
drugs (sulfadlazlne, sulfamerazlne, and sulfamethazlne) Is
reported. Silver colloidal dispersions prepared by simple bo-
rohydrlde reduction of silver nitrate are used as substrates.
The capability of SERS for spectral fingerprinting of analytes
with close structural properties using easily prepared sub-
strates and relatively simple Instrumentation to Illustrated. By
careful attention to the timing In the measurement, quantita-
tive Information can be obtained from sliver colloids. Linearity
was achieved up to 100 ng mL*1. Limits of detection range
In the low nanograms per mllllllter level.
The discoveries of sulfonamides (sulfa drugs) and antibiotics
constitute some of the most significant medical achievements
of this century. They have therapeutic uses both in human
and veterinary medicine and in disease prevention in livestock.
In 1985, over 100 x 106 kg of these drugs were used annually.
Over 5000 sulfa drugs, which have a general structure of the
type H2NC8H4S02NHR, have been synthesized and tested.
Fewer than 30 of these have proven worthy of sustained use
(1). Their biological activity is based on the inhibition of the
biosynthesis of folate cofactors in bacteria by blocking a step
in the formation of dihydrofolic acid from p-aminobenzoic acid
(2). The sulfapyrimidines, where the R group is a pyrimidine
* Author to whom correspondence should be addressed.
1 On leave: Department of Analytical Chemistry, Faculty of Sci-
ences, University of Malaga, 29071 Malaga, Spain.
ring, have been touted as the ultimate stage of development
of sulfa drugs. Important members of this group are sulfa-
diazine, sulfamerazine, and sulfamethazine (3).
During the 1940s, these drugs enjoyed widespread use in
combating bacterial infections in humans and in the treatment
of diseases affecting pet and food-producing animals. Re-
cently, the reduction of sulfa drug use in humans has been
triggered by increased bacterial resistance to the drugs and
the development of more effective antimicrobial agents.
However, the use of sulfa drugs in veterinary medicine has
persisted because the drugs are easily administered in feed
and water, are economical, and have proven to be effective
for the treatment of livestock diseases. The use of combi-
nations of two or more sulfa drugs was also shown to be of
therapeutic value. During treatment with sulfa drugs, the
higher the concentration of drug that can be maintained in
the body, the greater its effect However, increasing the drug
concentration also increases the side effects, the most common
of which is crystalluria, a deposition of crystals in the renal
tubules due to the limited solubility of the sulfa drugs in water.
However, when used in combination, each drug acts inde-
pendently. Since all of the sulfapyrimidines have been shown
to have the same therapeutic effect, combination therapy
allows a higher total drug concentration to be maintained in
the blood while minimizing the effects of crystalluria.
The use of sulfa drugs to promote growth and treat diseases
of livestock animals has been a major cause of sulfa drug tissue
residue in swine marketed for human consumption. In 1973,
the U.S. Food and Drug Administration set a tolerance of 100
ng of sulfonamide per gram of edible tissue. Random assays
-------
Attachment 5.
Data Sheets
-------
Standard Data Sheet
Standard
0.50%
5%
50%
5% QCCS
Date
Vial Wt
*
Vial+H2O Wt
Vial+H2O+
2-BE Wt
H2OWt
(mg)
2-BE Wt
(mg)
Wt % 2-BE
Analyst:
-------
QCCS Data Sheet
Date
Sample
QCCS-1
QCCs-2
QCCS-3
Coating+
Liner
Wt
Liner
Wt
Massss
(mg)
Rfid
2-BE Mass
(mg)
Wt % 2-BE
Mean Measured Conc.(X)=
^m
True Cone. (T)=
Analyst:
-------
Calibration Data Sheet
Date
Nominal
Std %
0.5
Coating+
Liner
Wt
Liner
Wt
(mg)
Standard
Wt % 2-BE
Mass,
(mg)
R
fid
Average RF (RF) =
RF
(area unit/mg)
%RSD
Analyst:
-------
Paint Results Data Sheet
VOC massu (mg)
Wt% VOCU
Sample
Wt(mg)
Wt% VOCC
(corrected)
MS1-6659A
MS1-6659A
MS 1-6659 A
1
2
3
1403-0100
1403-0100
1403-0100
1
2
3
.
4206-0100
4206-0100
4206-0100
1
2
3
4020-1000
4020-1000
4020-1000
1
2
3
Analyst:
-------
Attachment 6.
Materials
-------
Materials Provided for Interlaboratory Study
1. One ounce of 2-Butoxyethanol for preparing standards.
2. Thirty (30) PTFE liners for sample tubes
3. Silanized glass wool for packing the PTFE liners
4. Sixteen (16) 1A inch stainless steel tubes
5. Twelve (12) 1 cc syringes with 20 gauge needles for loading the sample paints into
the PTFE liners
6. One Hamilton #805 50uL syringe
7. Four sample paints labeled with one of the following sample codes:
A. 1403-0100
B. MS1-6659A
C. 4206-0100
D. 4020-1000
6. Logbook
7. Perkin-Elmer Model ATD-400 Thermal Tube Desorber (SN 48996) with Hewlett
Packard 5890 GC (BMI Tag# X-52157)
8. Chrom Perfect data system on Dell model GXL5133 Pentium Computer (SN 5X789)
with Digital DEClaser 1800 printer (SN 2M42400778)
-------
APPENDIX C
ASTM STANDARD PRACTICE E691-92
-------
Designation: E 691 - 92
Standard Practice for
Conducting an Intel-laboratory Study to Determine the
Precision of a Test Method1
This standard is issued under the fixed designation E 691; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (<) indicates an editorial change since the last revision or reapproval.
INTRODUCTION
Tests' performed on presumably identical materials in presumably identical circumstances do
not, in general, yield identical results. This is attributed to unavoidable random errors inherent in
every test procedure; the factors that may influence the outcome of a test cannot all be completely
controlled. In the practical interpretation of test data, this inherent variability has to be taken into
account. For instance, the difference between a test result and some specified value may be within
that which can be expected due to unavoidable random errors, in which case a real deviation from
the specified value has not been demonstrated. Similarly, the difference between test results from
two batches of material will not indicate a fundamental quality difference if the difference is no
more than can be attributed to inherent variability in the test procedure. Many different factors
(apart from random variations between supposedly identical specimens) may contribute to the
variability in application of a test method, including: a the operator, b equipment used, c
calibration of the equipment, and d environment (temperature, humidity, air pollution, etc.). It is
considered that changing laboratories changes each of the above factors. The variability between
test results obtained by different operators or with different equipment will usually be greater than
between test results obtained by a single operator using the same equipment. The variability
between test results taken over a long period of time even by the same operator will usually be
greater than that obtained over a short period of time because of the greater possibility of changes
in each of the above factors, especially the environment.
The general term for expressing the closeness of test results to the "true" value or the accepted
reference value is accuracy. To be of practical value, standard procedures are required for
determining the accuracy of a test method, both in terms of its bias and in terms of its precision.
This practice provides a standard procedure for determining the precision of a test method.
Precision, when evaluating test methods, is expressed in terms of two measurement concepts,
repeatability and reproducibility. Under repeatability conditions the factors listed above are kept or
remain reasonably constant and usually contribute only minimally to the variability. Under
reproducibility conditions the factors are generally different (that is, they change from laboratory to
laboratory) and usually contribute appreciably to the variability of test results. Thus, repeatability
and reproducibility are two practical extremes of precision.
The repeatability measure, by excluding the factors a through d as contributing variables, is not
intended as a mechanism for verifying the ability of a laboratory to maintain "in-control"
conditions for routine operational factors such as operator-to-operator and equipment differences
or any effects of longer time intervals between test results. Such a control study is a separate issue
for each laboratory to consider for itself, and is not a recommended part of an interlaboratory
study. :
The reproducibility measure (including the factors a through d as sources of variability) reflects
what precision might be expected when random portions of a homogeneous sample are sent to
random "in-control" laboratories.
To obtain reasonable estimates of repeatability and reproducibility precision, it is necessary in an
interlaboratory study to guard against excessively sanitized data in the sense that only the uniquely
best operators are involved or that a laboratory takes unusual steps to get "good" results. It is also
important to recognize and consider how to treat "poor" results that may have unacceptable
assignable causes (for example, departures from the prescribed procedure). The inclusion of such
results in the final precision estimates might be questioned.
An essential aspect of collecting useful consistent data is careful planning and conduct of the
1 This practice is under the jurisdiction of ASTM Committee E-11 on Statistical
Methods and is the direct responsibility of Subcommittee El 1.20 on Test Method Currem ^^ ^ Jfln ,5 1992 ^^^ my 1992. Originally
Evaluauon and Quahty Control. published as E 691-79. Last previous edition E 691-87.
425
-------
E691
study. Questions concerning the number of laboratories required for a successful study as well as
the number of test results per laboratory affect the confidence in the precision statements resulting
from the study. Other issues involve the number, range, and types of materials to be selected for the
study, and the need for a well-written test method and careful instructions to the participating
laboratories.
To evaluate the consistency of the data obtained in an interlaboratory study, two statistics may
be used: the "fc-value", used to examine the consistency of the within-laboratory precision from
laboratory to laboratory, and the u/»-value", used to examine the consistency of the test results from
laboratory to laboratory. Graphical as well as tabular diagnostic tools help in these examinations.
1. Scope
1.1 This practice describes the techniques for planning,
conducting, analyzing, and treating the results of an
interlaboratory study (ILS) of a test method. The statistical
techniques described in this practice provide adequate infor-
mation for formulating the precision statement of a test
method.
1.1.1 A computer software package for performing the
calculations and producing the tables and graphs associated
with Practice E691. This software can be run on PC
compatible computers, and hard copy tables and graphs can
be printed on dot-matrix printers.
1.2 This practice does not concern itself with the develop-
ment of test methods but rather with gathering the informa-
tion needed for a test method precision statement after the
development stage has been successfully completed. The data
obtained in the interlaboratory study may indicate, however,
that further effort is needed to improve the test method.
1.3 Since the primary purpose of this practice is the
development of the information needed for a precision
statement, the experimental design in this practice may not
be optimum for evaluating materials, apparatus, or indi-
vidual laboratories.
1.4 Field of Application—This practice is concerned ex-
clusively with test methods which yield a single numerical
figure as the test result, although the single figure may be the
outcome of a calculation from a set of measurements.
1.4.1 This practice does not cover methods in which the
measurement is a categorization, such as a go-no-go alloca-
tion (two categories) or a sorting scheme into two or more
categories. For practical purposes, the discontinuous nature
of measurements of these types may be ignored when a test
result is defined as an average of several individual measure-
ments. Then, this practice may be applicable, but caution is
required and a statistician should be consulted.
1.5 The information in this practice is arranged as follows:
Section
Scope
Referenced Documents
Terminology
Summary of Practice
Significance and Use
Planning the Interlaboratory Study (ILS)
ILS Membership
Basic Design
Test Method
Laboratories
Materials
Number of Test Results per Material .
Protocol
Conducting the Testing Phase.of the ILS
Pilot Run
Full Scale Run
1
2
3
4
5
6
7
8
9
10
11
12
13
14
Calculation and Display of Statistics
Calculation of the Statistics
Tabular and Graphical Display of Statistics
Data Consistency
Flagging Inconsistent Results
Investigation
Task Group Actions
Examples of Interlaboratory Studies
Precision Statement Information
Repeatability and Reproducibility
Annexes
Theoretical Considerations
Index to Selected Terms
References
Tables and Figures
Tables
Section
15
16
17
18
19
20
21
Al
A2
Table
Glucose in Serum Example 1-7
Pentosans in Pulp Example 8-11
Critical Values of Consistency Statistics, h and k 12
Figures Fig.
Glucose in Serum Example 1-5
Pentosans in Pulp Example 6-10
1.6 This standard may involve hazardous materials, oper-
ations, and equipment. This standard does not purport to
address all of the safety problems associated with its use. It is
the responsibility of the user of this standard to establish
appropriate safety and health practices and determine the
applicability of regulatory limitations prior to use.
2. Referenced Documents
2.1 ASTM Standards:
E 177 Practice for Use of the Terms Precision and Bias in
ASTM Test Methods2
E 456 Terminology Related to Quality and Statistics2
E 1169 Guide for Conducting Ruggedness Tests2
2.2 ASTM Adjunct:
E 691 Conducting an Interlaboratory Study to Determine
the Precision of a Test Method3
3. Terminology
3.1 Definitions—For formal definitions of statistical
terms, see Terminology E 456.
3.2 Descriptions of Terms Specific to This Standard:
3.2.1 Test Method and Protocol—In this practice, the
term "test method" is used both for the actual measurement
process and for the written description of the process, while
the term "protocol" is used for the directions given to the
laboratories for conducting the ILS.
2 Annual Book of ASTM Standards, Vol 14.02.
3 An adjunct is available from ASTM Headquarters. Request PCN: 12-
5-6910-34 for S'/i" disk and 12-506911-34 for a 3'A" disk.
426
-------
<§> E691
2.5 t-
2.15
-2
-2.15
-2.5 •-
MAT: ABCDE ABODE ABCDE ABODE ABODE ABCDE ABCDE ABCDE
LAB: 12 3 4 5 6 7 8
FIG. 1 Glucose In Serum: h—Materials within Laboratories
3.2.2 Observations, Test Determinations and Test Results:
3.2.2.1 A test method often has three distinct stages, the
direct observation of dimensions or properties, the arith-
metic combination of the observed values to obtain a test
determination, and the arithmetic combination of a number
of test determinations to obtain the test result of the test
method. In the simplest of test methods a single direct
observation is both the test determination and the test result.
For example, the test method may require the measurement
of the mass of a test specimen prepared in a prescribed way.
Another test method may require the measurement of the
area of the test specimen as well as the mass, and then direct
that the mass be divided by the area to obtain the mass per
unit area of the specimen. The whole process of measuring
the mass and the area and calculating the mass per unit area
is a test determination. If the test method specifies that only
one test determination is to be made, then the test determi-
nation value is the test result of the test method. Some test
methods require that several determinations be made and
the values obtained be averaged or otherwise combined to
obtain the test result of the test method. Averaging of several
determinations is often used to reduce the effect of local
variations of the property within the material.
3.2.2.2 In this practice, the term "test determination" is
used both for the process and for the value obtained by the
process, except when "test determination value" is needed
for clarity.
3.2.2.3 The number of test determinations required for a
test result should be specified in each individual test method.
The number of test results required for an interlaboratory
study of a test method is specified in the protocol of that
study.
3.2.3 Test Specimens and Test Units—In this practice a
test unit is the total quantity of material needed for obtaining
a test result as specified by the test method. The portion of
the test unit needed for obtaining a single test determination
is called a test specimen. Usually a separate test specimen is
required for each test determination.
3.2.4 Precision, Bias, and Accuracy of a Test Method:
3.2.4.1 When a test method is applied to a large number
of portions of a material, that are as nearly alike as possible,
the test results obtained nevertheless will not all have the
same value. A measure of the degree of agreement among
these test results describes the precision of the test method
for that material.
3.2.4.2 Numerical measures of the variability between
such test results provide inverse measures of the precision of
the test method. Greater variability implies smaller (that is,
poorer) precision and larger imprecision.
3.2.4.3 This practice is designed only to estimate the
precision of a test method. However, when accepted refer-
427
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691
TABLE 1 Glucose in Serum ILS Test Result Data
A
1 41.03
41.45
41.37
2 41.17
42.00
41.15
3 41.01
40.68
42.66
4 39.37
42.37
42.63
5 41.88
41.19
41.32
6 43.28
40.50
42.28
7 41.08
41.27
39.02
8 43.36
42.65
41.72
B
78.28
78.18
78.49
77.78
80.38
79.54
79.18
79.72
80.81
84.08
78.60
81.92
78.16
79.58
78.33
78.66
79.27
81.75
79.76
81.45
77.35
80.44
80.80
79.80
Material
C
132.66
133.83
133.10
132.92
136.90
136.40
132.61
135.80
135.36
138.50
148.30
135.69
131.90
134.14
133.76
137.21
135.14
137.50
130.97
131.59
134.92
135.46
135.14
133.63
0
193.71
193.59
193.65
190.88
200.14
194.30
192.71
193.28
190.28
195.85
196.36
199.43
192.59
191.44
195.12
195.34
198.26
198.13
194.66
191.99
187.13
197.56
195.99
200.82
E
292.78
294.09
292.89
292.27
309.40
295.08
295.53
290.14
292.34
295.19
295.44
296.83
293.93
292.48
294.28
297.74
296.80
290.33
287.29
293.76
289.36
298.46
295.28
296.12
TABLE 2* Interlaboratory Study Worksheet for Glucose in Serum
Initial Preparation of Test Result Data for Material A
ence values are available for the property levels, the test
result data obtained according to this practice may be used in
estimating the bias of the test method. For a discussion of
bias estimation and the relationships between precision, bias,
and accuracy, see Practice E 177.
3.2.5 Repeatability and Reproducibility—These terms
deal with the variability of test results obtained under
specified laboratory conditions. Repeatability concerns the
variability between independent test results obtained within
a single laboratory in the shortest practical period of time by
a single operator with a specific set of test apparatus using
test specimens (or test units) taken at random from a single
quantity of homogeneous material obtained or prepared for
the ILS. Reproducibility deals with the variability between
single test results obtained in different laboratories, each of
which has applied the test method to test specimens (or test
units) taken at random from a single quantity of homoge-
neous material obtained or prepared for the ILS.
3.2.5.1 Repeatability Conditions—The within-laboratory
conditions spelled above for repeatability. The single-
operator, single-set-of-apparatus requirement means that for
a particular step in the measurement process the same
combination of operator and apparatus is used for every test
result and on every material. Thus, one operator may
prepare the test specimens, a second measure the dimensions
and a third measure the breaking force. "Shortest practical
period of time" means that the test results, at least for one
material, are obtained in a time not less than in normal
testing and not so long as to permit significant changes in test
material, equipment or environment.
3.3 For further discussion of the terms discussed above,
see Practice E 177, and the formal definitions in Practice
E456.
Laboratory Test Results, x
Number
1
2
3
4
5
6
7
8
1
41.03
41.17
41.01
39.37
41.88
43.28
41.08
43.36
2
41.45
42.00
40.68
42.37
41.19
40.50
41.27
42.65
3
41.37
41.15
42.66
42.63
41.32
42.28
39.02
41J2
T
41.2833
41.4400
41.4500
41.4567
41.4633
42.0200
40.4567
42.5767
5
0.2230
0.4851
1.0608
1.8118
0.3667
1.4081
1.2478
0.8225
d
-0.2350
-0.0783
-0.0683
-0.0616
-0.0550
0.5017
-1.0616
1.0584
h
-0.39
-0.13
-0.11
-0.10
-0.09
0.83
-1.75
1.75
k
0.21
0.46
1.00
1.70
0.34
1.32
1.17
0.77
* Average of cell averages. T •= 41.5183
Standard deviation of cell averages, s* = 0.6061
Repeatability standard deviation, s, - 1.0632
Reproducibility standard deviation, sn = 1.0632
where:
x = individual test result,
n
X = cell average, - £ x/n where n «= number of test results per cet •
3,
£ <= average of ceN averages - Z 7/p where p = number of laboratories - 8,
s = cell standard deviation- V Z (x - xW(n - 1)
d = ceH deviation - JT -
s, = standard deviation of cell averages
sr = repeatability standard deviation =
sa = reproducibility standard deviation
h = d/s,. and
* =s/s,
= larger of s, and
- 1)/n
4. Summary of Practice
4.1 The procedure presented in this practice consists of
three basic steps: planning the interlaboratory study, guiding
the testing phase of the study, and analyzing the test result
data. The analysis utilizes tabular, graphical, and statistical
diagnostic tools for evaluating the consistency of the data so
that unusual values may be detected and investigated, and also
includes the calculation of the numerical measures of preci-
sion of the test method pertaining to both within-laboratory
repeatability and between-laboratory reproducibility.
5. Significance and Use
5.1 ASTM regulations require precision statements in all
test methods in terms of repeatability and reproducibility.
This practice may be used in obtaining the needed informa-
tion as simply as possible. This information may then be
used to prepare a precision statement in accordance with
Practice El 77.
PLANNING THE INTERLABORATORY STUDY (ILS)
6. ILS Membership
6.1 Task Group*—Either the task group that developed
the test method, or a special task group appointed for the
purpose, must have overall responsibility for the ILS, in-
cluding funding where appropriate, staffing, the design of the
ILS, and decision-making with regard to questionable data.
The task group should decide on the number of laboratories,
materials, and test results for each material. In addition, it
4 To facilitate the preparation of the final report on the ILS, the task group can
obtain the Research Report format guide from ASTM Headquarters.
428
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E 691
TABLE 3 Glucose in Serum-h A
TABLE 5* Glucose in Serum-h •
Laboratory
1
2
3
4
5
6
7
8
A
-0.39
-0.13
-0.11
-0.10
-0.09
0.83
-1.75
1.75
B
-1.36
-0.45
0.22
1.85
-0.99
0.21
-0.16
0.67
Material
C
-0.73
0.10
-0.21
2.14
-0.71
0.55
-1.00
-0.15
D
-0.41
0.15
-1.01
0.96
-0.64
0.97
-1.33
1.31
E
-0.46
1.64
-0.68
0.49
-0.34
0.17
-1.62
0.79
* Critical value -2.15.
should specify any special calibration procedures and the
repeatability conditions to be specified in the protocol (see
12.3 and 12.4).
6.2 ILS Coordinator—The task group must appoint one
individual to act as overall coordinator for conducting the
ILS. The coordinator will supervise the distribution of
materials and protocols to the laboratories and receive the
test result reports from the laboratories. Scanning the reports
for gross errors and checking with the laboratories, when
such errors are found, will also be the responsibility of the
coordinator. The coordinator may wish to consult with the
statistician in questionable cases.
6.3 Statistician:
6.3.1 The test method task group should obtain the
assistance of a person familiar with the statistical procedures
in this practice and with the materials being tested in order to
ensure that the requirements outlined in this practice are met
in an efficient and effective manner. This person should also
assist the task group in interpreting the results of the data
analysis.
6.3.2 When a person having adequate knowledge of both
the materials and the proper statistical techniques is not
available, the task group should obtain the services of a
statistician who has experience in practical work with data
from materials testing. The task group should provide the
statistician with an opportunity to become familiar with the
statistical procedures of this practice and with both the
materials and the test method involved. The statistician
should become a member of the task group conducting the
ILS, (task group members need not be members of ASTM).
6.3.3 The calculations of the statistics (see Section 15) for
each material can be readily done by persons not having
statistical knowledge, (see 15.1.3 and 15.4.2.)
6.4 Data Analyst—This individual should be someone
who is careful in making calculations and can follow the
directions in Sections 15 through 17.
6.5 Laboratory ILS Supervisor—Each laboratory must
TABLE 4 Glucose in Serum-ft*
Laboratory
1
2
3
4
5
6
7
8
A
0.21
0.46
1.00
1.70
0.34
1.32
1.17
0.77
B
0.11
0.89
0.56
1.85
0.52
1.09
1.38
0.34
Material
C
0.22
0.79
0.63
2.41
0.44
0.47
0.77
0.36
D
0.02
1.78
0.61
0.74
0.72
0.63
1.45
0.94
E
0.18
2.33
0.69
0.22
0.24
1.03
0.64
0.42
Laboratory
1
2
3
4
5
6
7
8
A
-0.39
-0.13
-0.11
-0.10
-0.09
0.83
-1.75
1.75
B
-1.36
-0.45
0.22
1.85
-0.99
0.21
-0.16
0.67
Material
C
-0.88
0.39
-0.08
1.59
-0.64
1.09
-1.28
0.01
D
-0.41
0.15
-1.01
0.96
-0.64
0.97
-1.33
1.31
E
-0.46
1.64
-0.68
0.49
-0.34
0.17
-1.62
0.79
* Recalculated values after correcting Cell C4, (see 20.1.4 and 20.1.5).
8 Critical value-2.15.
have an ILS supervisor to oversee the conduct of the ILS
within the laboratory and to communicate with the ILS
Coordinator. The name of the supervisor should be obtained
on the response form to the "invitation to participate" (see
9.4).
7. Basic Design
7.1 Keep the design as simple as possible in order to
obtain estimates of within- and between-laboratory vari-
ability that are free of secondary effects. The basic design is
represented by a two-way classification table in which the
rows represent the laboratories, the columns represent the
materials, and each cell (that is, the intersection of a row with
a column) contains the test results made by a particular
laboratory on a particular material (see Table 1).
8. Test Method
8.1 Of prime importance is the existence of a valid,
well-written test method that has been developed in one or
more competent laboratories, and has been subjected to a
ruggedness test prior to the ILS.
8.2 A ruggedness test is a screening procedure for investi-
gating the effects of variations in environmental or other
conditions in order to determine how control of such test
conditions should be specified in the written description of
the method. For example, the temperature of the laboratory
or of a heating device used in the test may have an effect that
cannot be ignored in some cases but may be much less in
others. In a ruggedness test, deliberate variations in temper-
ature would be introduced to establish the allowable limits
on control of temperature. This subject is discussed more
fully in Refs (1,2 and 3) see also Guide E 1169.
8.3 As a result of carrying out the screening procedure,
and of some experience with the test method in the spon-
soring laboratory and one or two other laboratories, a written
TABLE 6*" Glucose in Serum-*
Laboratory
1
2
3
4
5
6
7
8
A
0.21
0.46
1.00
1.70
0.34
1.32
1.17
. 0.77
B
0.11
0.89
0.56
1.85
0.52
1.09
1.36
0.34
Material
C
0.36
1.40
1.12
1.02
0.78
0.83
1.38
0.63
0
0.02
1.78
0.61
0.74
0.72
0.63
1.45
0.94
E
0.18
2.33
0.69
0.22
0.24
1.03
0.84
0.42
* Critical value - 2.06.
* Recalculated values after correcting cell C4, (See 20.1.4 and 20.1.5).
8 Critical value - 2.06.
429
-------
E691
2.5
1.5
c . _
r-5
u
-1
-1.5
-2
TTTTT
J
1J
-J,
-2.15
-2.5 -f-
LAB: 12345678 12345678 12345678 12345678 12345678
MAT: A B C D E
FIG. 2 Glucose In Serum: ft—Laboratories within Materials
version of the test method must have been developed (but
not necessarily published as a standard method). This draft
should describe the test procedure in terms that can be easily
followed in any properly equipped laboratory by competent
personnel with knowledge of the materials and the property
to be tested. The test conditions that affect the test results
appreciably should have been identified and the proper
degree of control of the test conditions specified in the
description of the test procedure. In addition, the test
method should specify how closely (that is, to how many
digits) each observation in the test method is to be measured.
8.4 The test method should specify the calibration proce-
dure and the frequency of calibration.
9. Laboratories .
9.1 Number of Laboratories:
9.1.1 An ILS should include 30 or more laboratories but
this may not be practical and some ILS have been run with
fewer. It is important, that enough laboratories be included
in the ILS to be a reasonable cross-section of the population
of qualified laboratories; that the loss or poor performance of
a few will not be fatal to the study, and to provide a
reasonably satisfactory estimate of the reproducibility.
9.1.2 Under no circumstances should the final statement
of precision of a test method be based on acceptable test
results for each material from fewer than 6 laboratories. This
would require that the ILS begin with 8 or more laboratories
in order to allow for attrition.
9.1.3 The examples given in this practice include only 8
and 7 laboratories, respectively. These numbers are smaller
than ordinarily considered acceptable, but they are conven-
ient for illustrating the calculations and treatment of the
data.
9.2 Any laboratory considered qualified to run the test
routinely (including laboratories that may not be members of
ASTM) should be encouraged to participate in the ILS, if the
preparatory work is not excessive and enough suitably
homogeneous material is available. In order to obtain an
adequate number of participating laboratories, advertise the
proposed ILS in where appropriate (for example, trade
magazines, meetings, circulars, etc.).
9.3 "Qualified" implies proper laboratory facilities and
testing equipment, competent operators, familiarity with the
test method, a reputation for reliable testing work, and
sufficient time and interest to do a good job. If a laboratory
meets all the other requirements, but has had insufficient
experience with the test method, the operator in that
laboratory should be given an opportunity to familiarize
himself with the test method and practice its application
before the ILS starts. For example, this experience can be
obtained by a pilot run (see Section 13) using one or two trial
430
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• E 691
TABLE 7 Glucose in Serum—Precision Statistics
NOTE—This table (with the column for ST omitted) is a useful format for the
presentation of the precision of a test method as required by Section A21 of the
Form and Style of ASTM Standards.
TABLE 8 Pentosans in Pulp-ILS Test Results
Mate-
rial
A
B
C
D
E
r
41.5183
79.6796
134.7264
194.7170
294.4920
V
0.6061
1.0027
1.7397
2.5950
2.6931
s,
1.0632
1.4949
1.5434
2.6251
3.9350
s«
1.0632
1.5796
2.1482
3.3657
4.1923
r
2.98
4.19
4.33
7.35
11.02
R
2.98
4.42
6.02
9.42
11.74
samples provided by the task group and returning the raw
data and the test results to the task group. The importance of
this familiarization step cannot be overemphasized. Many
interlaboratory studies have turned out to be essentially
worthless due to lack of familiarization.
9.4 Obtain written ensurance from each potential partici-
pating laboratory that it is properly equipped to follow all the
details of the procedure and is willing to assign the work to a
skilled operator in a timely manner. The decision of a
laboratory to participate should be recorded on a response
form to a written invitation. The invitation should include
information covering the required time for calibrating the
apparatus and for testing all of the materials, and other
possible costs. The response form should include the name,
address, and telephone number of the person supervising the
ILS work within the laboratory, the address and other
markings required to ensure the ILS sample material will be
promptly delivered to the ILS supervisor, answers to brief
questions concerning equipment, environment, and per-
sonnel, including previous use of the test method, upon
which the apparent competence of the laboratory may be
judged, and an affirmation that the laboratory understands
what is involved and agrees to carry out its responsibilities
with diligence.
9.5 The ILS should not be restricted to a group of
laboratories judged to be exceptionally qualified and
equipped for the ILS. Precision estimates for inclusion in a
test method should be obtained through the efforts of
qualified laboratories and personnel operating under condi-
tions that will prevail when the test method is used in
practice.
10. Materials
10.1 Material designates anything with a property that can
be measured. Different materials having the same property
may be expected to have different property levels, meaning
higher or lower values of the property. Different dilutions of
the same material or compound to be assayed are considered
"different materials" for the purpose of this practice. The
terminology "different levels of material" may be used, if
appropriate.
10.2 The number and type of materials to be included in
an ILS will depend on the range of the levels in the class of
materials to be tested and likely relation of precision to level
over that range, the number of different types of materials to
which the test method is to be applied, the difficulty and
expense involved in obtaining, processing, and distributing
samples, the difficulty of, length of time required for, and
expense of performing the test, the commercial or legal need
for obtaining a reliable and comprehensive estimate of
Laboratory
1
2
3
4
5
6
A
0.44
0.49
0.44
0.41
0.41
0.41
0.51
0.51
0.51
0.40
0.36
0.37
0.49
0.49
0.49
0.43
0.41
0.40
B
0.96
0.92
0.82
0.83
0.83
0.84
0.92
0.93
0.92
0.96
0.94
0.94
0.82
0.82
0.84
0.88
0.92
0.88
C
1.23
1.88
1.24
1.12
1.12
1.12
1.11
1.13
1.11
1.15
1.13
1.13
0.98
0.98
0.98
1.11
1.12
1.11
D
1.25
1.25
1.42
1.25
1.25
1.26
1.35
1.35
1.35
1.29
1.29
1.29
1.23
1.23
1.23
1.31
1.30
1.31
E
1.98
1.92
1.80
1.99
1.94
1.95
2.05
2.08
2.03
2.05
2.04
2.04
1.94
1.96
1.96
2.01
1.99
1.98
F
4.12
4.16
4.16
4.10
4.11
4.10
4.11
4.16
4.16
4.20
4.20
4.22
4.61
4.63
4.53
3.93
3.92
3.84
G
5.94
5.37
5.37
5.26
5.26
5.26
5.16
5.16
5.21
5.20
5.20
5.20
5.00
5.00
4.96
4.85
4.87
4.91
H
10.70
10.74
10.83
10.07
10.05
9.82
10.01
10.17
10.17
10.98
10.67
10.52
10.48
10.27
10.38
9.57
9.57
9.62
I
17.13
16.56
16.56
16.08
16.04
16.13
16.01
15.96
16.06
16.65
16.91
16.75
15.71
15.45
15.66
15.05
14.73
15.04
0.186 0.866 1.05 1.13 1.98 4.21 5.27 11.5 18.8
0.171 0.900 0.962 1.15 1.93 4.18 5.32 10.8 18.2
0.153 0.831 0.927 1.15 1.98 4.16 5.10 11.5 18.1
precision, and the uncertainty of prior information on any of
these points.
10.2.1 For example, if it is already known that the
precision is either relatively constant or proportional to the
average level over the range of values of interest, a smaller
number of materials will be needed than if it is merely
known that the precision is different at different levels. The
ruggedness test (see 8.2) and the preliminary pilot program
(see Section 13) help to settle some of these questions, and
may often result in the saving of considerable time and
expense in the full ILS.
10.2.2 An ILS of a test method should include at least
three materials representing different test levels, and for
development of broadly applicable precision statements, six
or more materials should be included in the study.
10.2.3 The materials involved in any one ILS should
differ primarily only in the level of the property measured by
the test method. When it is known, or suspected, that
different classes of materials will exhibit different levels of
precision when tested by the test method, consideration
should be given to conducting separate interlaboratory
studies for each class of material.
10.3 Each material in an ILS should be made to be or
selected to be as homogeneous as possible prior to its
subdivision into test units or test specimens (see 3.2.3). If the
randomization and distribution of individual test specimens
(rather than test units) does not conflict with the procedure
for preparing the sample for test, as specified in the test
method, greater homogeneity between test units can be
achieved by randomizing test specimens. Then each test unit
would be composed of the required number of randomized
test specimens. (See Section 11 and 14.1 for the quantity of
each material needed, its preparation and distribution.)
NOTE—It may be convenient to use established reference materials,
since their homogeneity has been demonstrated.
431
-------
E691
3 4~
2.5
g 1.5
v
B
o
u
1
0 -
LJiLLl
2.06
1
MAT: ABCDE ABODE ABCDE ABCDE ABCDE ABCDE ABCDE ABCDE
LAB: i '2; 3 4.5 67 8
FIG. 3 Glucose In Serum: k—Materials within Laboratories
11. Number of Test Results per Material
11.1 In the design of an ILS a sufficient total number of
test results on each material must be specified to obtain a
good estimate of the measure of repeatability, generally the
repeatability standard deviation. In many cases, the standard
deviation in question will be a function of the property level
being measured. When this occurs, the standard deviation
should be determined separately for each level. It is generally
sound to limit the number of test results on each material in
each laboratory to a small number, such as three or four. The
minimum number of test results per laboratory will normally
be three for a chemical test and three or four for a physical or
optical test. The number may be as small as two when there
is little danger that a test unit will be lost or questionable test
results obtained, or as many as ten when test results are apt
to vary considerably. Generally, the time and effort invested
in an ILS is better spent on examining more materials across
more laboratories than on recording a large number of test
results per material within a few laboratories.
12. Protocol
12.1 In the protocol, cite the name, address, and tele-
phone number of the person who has been designated ILS
coordinator (see 6.2). Urge the laboratories to call the
coordinator when any questions arise as to the conduct of
the ILS.
12.2 Clearly identify the specific version of the test
method being studied. If the test method allows several
options in apparatus or procedure, the protocol should
specify which option or options have been selected for the
TABLE 9 Pentosans In Pulp-h *
Laboratory
Material
1 0.46
2 0.05
3 0.93
4 -0.19
5 0.75
6 0.08
7 -2.08
0.35
-1.14
0.88
1.40
-1.28
0.21
-0.41
2.05
-0.05
-0.07
0.05
-0.94
-0.09
-0.94
0.56
-0.23
1.21
0.32
-0.57
0.56
-1.85
-1.51
-0.39
1.35
1.16
-0.51
0.23
-0.33
-0.17
-0.38
-0.18
0.12
1.97
-1.37
0.01
1.73
0.35
-0.04
0.07
-0.91
-1.42
0.21
0.63
-0.75
-0.50
0.57
-0.04
-1.45
1.54
0.36
-0.25
-0.32
0.38
-0.69
-1.30
1.84
* Critical value » 2.05.
432
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-
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2.06
LAB: 12345678 12345678 12345678 12345678 12345678
MAT: A B C D K
FIG. 4 Glucose In Serum: k—Laboratories within Materials
ILS. Test units and test data sheets must be provided for each
option.
12.3 When special calibration procedures are 'required
before every determination or every test result, they should
be described specifically in the test method. If the test
method specifies calibration only daily or less frequently, the
ILS task group must decide whether to require recalibration
before obtaining each test result. While doing so will
eliminate calibration drift and help ensure relative indepen-
dence of the test results, changes in calibration may increase
the variability between test results.
12.4 Describe any special circumstances that must be
addressed in implementing the repeatability conditions, such
as the period of time between obtaining the test results for
Laboratory
1
2
3
4
5
6
7
A '
1.93
0.00
0.00
1.02
0.00
1.02
1.10
TABLE
B
2.24
0.18
0.18
0.36
0.36
0.72
1.07
10
C
2.61
0.00
0.08
0.08
0.00
0.04
0.44
Pentosans in
0
2.62
0.15
0.00
0.00
0.00
0.15
0.31
Material
• E
2.32
0.67
0.64
0.15
0.29
0.39
0,73
Pulp-fr*
F
'0.71
0.18
0.89
0.36
1.63
1.52
0.77
G
2.47
0.00
0.22
0.00
0.17
0.23
0.87
H
0.34
0.72
0.48
1.21
O.S4
0.15
2.09
I
1.53
0.21
0.23
0.61
0.64
0.84
1.76
* Critical value - 2.03.
the same material; that is, not less than in normal testing and
not so long as to likely permit significant changes in test
material, equipment or environment.
12.5 Specify the required care, handling, and conditioning
of the materials to be tested. Explain the coding system used
in identifying the materials and the distinction between test
units and test specimens, where appropriate.
12.6 Supply data sheets for each material for recording the
raw data as observations are made. Give instructions on the
number of significant digits to be recorded, usually one
more, if possible, than required by the test method. Also,
supply test result sheets on which test results can be
calculated and reported. In many instances this can be
combined with the raw data sheet. Specify the number of
significant digits to be reported, usually two more than
required by the test method. Request the laboratories send
raw data and test result sheets as soon as the testing is
completed, and at least weekly if testing will continue over
several weeks.
12.7 Request that each laboratory keep a record (or log) of
any special events that arise during any phase of the testing.
This record, to be sent to the ILS coordinator, will provide a
valuable source of information both in dealing with unusual
data and in making improvements in the test method in
future revisions.
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4.5 -
3.5 -
5 3
o
I"
1.5 -
1 —
.5 -
0
•
0 50 100 150 200 250 300 350 400
Averages
FIG. S Glucose in Serum: Standard Deviations of Reproducibillty (O) and Repeatability (•) Versus Average
12.7.1 Instruct the laboratories to notify the ILS coordi-
nator promptly whenever an error in test procedure arises, so
that a decision can be made as to whether a new set of test
units should be sent to the laboratory for a complete retest of
the material.
12.8 Enclose with the protocol a questionnaire requesting
information on specific aspects of the apparatus, reagents,
calibration, or procedure, as well as any other information
that might assist in dealing with data inconsistencies, or
ensure the task group that the laboratory complied with the
current requirements of the test method. Also obtain any
other information that may be needed in preparing the final
research report on the ILS (see Footnote 3).
CONDUCTING THE TESTING PHASE OF THE ILS
13. Pilot Run
13.1 Before investing laboratory time in the full scale ILS,
it is usually wise to conduct a pilot run with only one, or
TABLE 11 Pentosans in Pulp—Precision Statistics
Material
A
B
C
D
E
F
G
H
1
T
0.4048
0.8841
1.1281
1.2686
1.9809
4.1814
5.1843
10.4010
16.3610
s,
0.1131
0.0447
0.1571
0.0676
0.0538
0.2071
0.2172
0.5630
1.0901
s.
0.0150
0.0322
0.1429
0.0375
0.0396
0.0325
0.1330
0.1936
0.2156
s«
0.1137
0.0519
0.1957
0.0742
0.0628
0.2088
0.2428
0.5848
1.1042
r
0.04
0.09
0.40
0.11
0.11
0.09
0.37
0.54
0.60
fl
0.32
0.14
0.55
0.21
0.18
0.58
0.68
1.64
3.09
perhaps two, material(s) to determine whether the test
method as well as the protocol and all the ILS procedures are
clear, and to serve as a familiarization procedure for those
without sufficient experience with the method (see 9.3). The
results of this pilot run also give the task group an indication
of how well each laboratory will perform in terms of
promptness and following the protocol. Laboratories with
poor performance should be encouraged and helped to take
corrective action.
13.2 All steps of the procedures described in this practice
should be followed in detail to ensure that these directions
are understood, and to disclose any weaknesses in the
protocol or the test method.
14. Full Scale Run
14.1 Material Preparation and Distribution:
14.1.1 Sample Preparation and Labelling—Prepare
enough of each material to supply 50 % more than needed
by the number of laboratories committed to the ILS. Label
each test unit or test specimen with a letter for the material
and a sequential number. Thus, for ten laboratories and two
test results for each laboratory the test units for material B
would be numbered from Bl to B30, or, if five test
specimens per test unit are required, the test specimens may
be numbered B1 to B150.
14.1.2 Randomization—For each material independently,
allocate the specified number of test units or test specimens
to each laboratory, using a random number table, or a
suitable computerized randomization based on random
numbers. See Ref. (4) for a discussion of randomization.
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MAT: ABCDEFGHI ABCDEFGHI ABCDEFGHI ABCDEFGHI ABCDEFGHI ABCDEFGHI ABCDEFGHI
LAB: 1234567
RG. 6 Pentosans in Pulp: h—Materials within Laboratories
14.1.3 Shipping—Ensure that the test units are packaged
properly to arrive in the desired condition. When the
material is sensitive to the conditions to which it is exposed
(light, heat, humidity, etc), place special directions for
opening the package on a label outside the package. Clearly
indicate the name of the person who has been designated as
ILS supervisor at the laboratory on the address of each
package. Follow each laboratory's instructions for ensuring
prompt delivery of the package.
14.1.4 Follow-up—Once the test units have been shipped,
the ILS coordinator should call each laboratory ILS super-
visor within a week to ten days to confirm that all test units
have arrived safely. If the task group has decided to inter-
mingle test units from different materials in the order of
testing, the testing should not start until all the test units
have arrived at the laboratory so they can be tested in the
specified order.
14.1.5 Replacement Sets of Test Units—As the ILS
progresses, a laboratory may discover that the test method
was not used properly on some test units. The laboratory ILS
supervisor should discuss this with the ILS coordinator, who
may send a replacement set of test units, replace the misused
test units, or do nothing, as may seem desirable.
14.2 Checking Progress—From time to time, at intervals
appropriate to the magnitude of the ILS, the coordinator
should call each ILS supervisor to ascertain how the testing is
progressing. By comparing the progress of all laboratories,
the coordinator can determine whether some laboratories are
lagging considerably behind the others and so advise these
laboratories.
14.3 Data Inspection—The completed data sheets should
be examined by the coordinator immediately upon receipt in
order to detect unusual values or other deficiencies that
should be questioned. Replacement sets of test units or of
specific test units may be sent when there is missing or
obviously erroneous data. The task group can decide later
whether or not the additional data should be used in the
estimation of the precision of the test method.
CALCULATION AND DISPLAY OF STATISTICS
15. Calculation of the Statistics
15.1 Overview—The analysis and treatment of the ILS
test results have three purposes, to determine whether the
collected data are adequately consistent to form the basis for
a test method precision statement, to investigate and act on
any data considered to be inconsistent, and to obtain the
precision statistics on which the precision statement can be
based. The statistical analysis of the data for estimates of the
precision statistics is simply a one-way analysis of variance
(within- and between-laboratories) carried out separately for
each level (material). Since such an analysis can be invali-
435
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MAT:
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RG. 7 Pentosans in Pulp: /i—Laboratories within Materials
dated by the presence of severe outliers, it is necessary to first
examine the consistency of the data. The following para-
graphs show, in terms of a numerical example, how the
entire program is carried out:
IS. 1.1 The calculations are illustrated with test results
from an ILS in which the concentration of glucose in serum
(see Table 1) was measured at five different concentration
levels by eight laboratories. Each laboratory obtained three
test results at each concentration level.
15.1.2 For extended calculations it is usually necessary to
retain extra significant digits in order to ensure that statisti-
cally important information is not lost in calculation by
rounding off too soon. As a general rule, retain at least two
more digits in the averages than in the reported test results
and at least three significant figures in the standard devia-
tions.
15.1.3 While the calculations described in this section are
arranged for use of a hand calculator, they also can be readily
programmed for the computer. If necessary, contact Com-
mittee E-ll for advice on computational matters, (see
15.4.2).
15.2 Table of ILS Test Results—The test results received
from the laboratories are usually best arranged in rows and
columns as in Table 1. Each column contains the data
obtained from all laboratories for one material, and each row
contains the data from one laboratory for all materials. The
test results from one laboratory on one material constitute a
cell. Thus, the cell for Laboratory 2 and Material C contains
the test results 132.92, 136.90 and 136.40. This cell is called
C2, by material and laboratory. It helps in the interpretation
of the data to arrange the materials in increasing order of the
measured values.
15.3 Worksheets—Generally, it facilitates the calculations
to prepare a separate calculation worksheet for each material,
using Table 2 as a model but making appropriate changes for
different numbers of laboratories, and test results per mate-
rial. Enter the test result data for one material (from one
column of Table 1) on a worksheet. Also enter the results of
the following calculations for that material on the same
worksheet, as illustrated in Table 2. Work on only one
material at a time.
15.4 Cell Statistics:
15.4.1 Cell A verage, x—Calculate the cell average for each
laboratory using the following equation:
(1)
where:
"x = the average of the test results in one cell,
x = the individual test results in one cell, and
n = the number of test results in one cell.
436
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Thus from Table 2 for Material A, Laboratory 1 (that is, for
Cell A1):
x = (41.03 + 41.45 + 41.37)/3 = 41.2833.
15.4.2 Cell Standard Deviation, s—Calculate the standard
deviation of the test results in each cell using the following
equation:
(x - x)2/(n - 1) (2)
The symbols have the same meaning as for Eq 1. Thus for
CellAl:
5 =
/ (41.03- 41.2833)2 + (41.45 - 41.2833)2
V +(41.37-41.2833)2]/(3-1)
= 0.2230
While Eq 2 shows the underlying calculation of the cell
standard deviation, inexpensive pocket calculators are avail-
able that calculate both the average and the standard
deviation directly. Check to be sure the calculator uses (n -
1) as the divisor in Eq 2, not n, and has adequate precision of
calculation.
15.5 Intermediate Statistics:
15.5.1 Average of the Cell Averages, x—Calculate the
average of all the cell averages for the one material using Eq
3.
P _
i
where:
Jc = the average of the cell averages for one material,
x = the individual cell averages, and
p = the number of laboratories in the ILS.
Thus for material A:
Jc = (41.2833 + 41.4400 + 41.4500 + 41.4567
+ 41.4633 + 42.0200 + 40.4567 + 42.5767)/8
= 41.5183
15.5.2 Cell Deviation, d—For each laboratory calculate
the cell deviation by subtracting the cell average from the
average of the cell averages using the following equation:
d = x-x (4)
*
Thus for cell Al:
d = 41.2833 - 41.5183 = -0.2350
15.5.3 Standard Deviation of the Cell Averages, sx—
Calculate this statistic using the following equation:
(5)
Thus for material A:
[(-0.2350)2 + (-0.0783)2
+ (-0.0683)2 + (-0.06I6)2
+ (-0,0550)2+ (0.5017)2
+ (-I.0616)2 + (l.0584)2J/(8 - I)
0.6061
15.6 Precision Statistics—While there are other precision
statistics, introduced later in this practice, the fundamental
precision statistics of the ILS are the repeatability standard
deviation and the reproducibility standard deviation. The
other statistics are calculated from these standard deviations.
15.6.1 Repeatability Standard Deviation, sr—Calculate
this statistic using the following equation:
(6)
where:
sr = the repeatability standard deviation,
s = the cell standard deviation (p of them from Eq 2), and
p = the number of laboratories.
Thus for material A:
V
= 1.0632
[(0.2230F+ (0.4851)2 + U.0608)2
+(1.8118)2 + (0.3667)2 + (1.4081)2
(1.2478)2 + (0.8225)2]/8
15.6.2 Reproducibility Standard Deviation, SR — Calculate
a provisional value of this statistic using the following
equation:
(n -
(7)
where: sx and sr are obtained from Eqs 5 and 6. The symbol,
* indicates provisional value, (for more information see
Al.1.2).
Thus for Material A:
V(0.6061)2 + (1.0632)2(3-
1.0588
Enter the larger of the values obtained by the use of Eqs 6
and 7 as the final value of SR to be used for precision
statements. In this case, Eq 6 yields the larger value.
Therefore, SR = 1.0632.
15.7 Consistency Statistics, h and k:
15.7.1 For each cell, calculate a value of h using the
following equation:
h = d/sy (8)
where:
h = the between-laboratory consistency statistic,
d = the cell deviation (i.e:, the deviation of the cell average
from the average of the cell averages, from 15.5.2), and
sx = the standard deviation of the cell averages (from
15.5.3).
Thus for Cell Al:
h = -0.2350/0.6061 =-0.39
Retain two decimal places in the computed values ofh.
15.7.2 For each cell, use the following equation to calcu-
late a value of k.
k = s/s, (9)
where:
k = the within-laboratory consistency statistic,
s = the cell standard deviation for one laboratory (from
15.4.2), and
sr = the repeatability standard deviation of the material
(from 15.6.1).
Thus for CellAl:
k = 0.2230/1.0632 = 0.21
Retain two decimal places in the computed values of k.
15.8 Other Materials — Repeat the steps described in 15.4
through 15.7 for each material, entering the calculation
results on separate worksheets.
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TABLE 12 Critical Values of h and * at the 0.5 % Significance Level*
Critical
value of
h
1.15
1.49
1.74
1.92
2.05
2.15
2.23
2.29
2.34
2.38
2.41
2.44
2.47
2.49
2.51
2.53
2.54
2.56
2.57
2.58
2.59
2.60
2.61
2.62
2.62
2.63
2.64
2.64
P
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
Critical values of *
Number of replicates, n
2
1.72
1.95
2.11
2.22
2.30
2.36
2.41
2.45
2.49
2.51
2.54
2.56
2.57
2.59
2.60
2.61
2.62
2.63
2.64
2.65
2.66
2.66
2.67
2.67
2.68
2.68
2.69
2.69
3
1.67
1.82
1.92
1.98
2.03
2.06
2.09
2.11
2.13
2.14
2.15
2.16
2.17
2.18
2.19
2.20
2.20
2.21
2.21
2.21
2.22
2.22
2.23
2.23
2.23
2.23
2.24
2.24
4
1.61
1.73
1.79
1.84
1.87
1.90
1.92
1.93
1.94
1.96
1.96
1.97
1.98
1.98
1.99
1.99
2.00
2.00
2.00
2.01
2.01
2.01
2.01
2.02
2.02
2.02
2.02
2.02
5
1.56
1.66
1.71
1.75
1.77
1.79
1.81
1.82
1.83
1.84
1.84
1.85
1.86
1.86
1.86
1.87
1.87
1.87
1.88
1.88
1.88
1.88
1.88
1.89
1.89
1.89
1.89
1.89
6
1.52
1.60
1.65
1.68
1.70
1.72
1.73
1.74
1.75
1.76
1.76
.77
.77
.77
.78
.78
.78
.79
.79
.79
1.79
1.79
1.79
1.80
1.80
1.80
1.80
1.80
7
1.49
1.56
1.60
1.63
1.65
1.66
1.67
1.68
1.69
1.69
1.70
1.70
1.71
1.71
1.71
1.72
1.72
1.72
1.72
1.72
1.72
1.73
1.73
1.73
1.73
1.73
1.73
1.73
8
1.47
1.53
1.56
1.59
1.60
1.62
1.62
1.63
1.64
1.64
1.65
1.65
1.66
1.66
1.66
1.66
1.67
1.67
1.67
1.67
1.67.
1.67
1.67
1.68
1.68
1.68
1.68
1.68
9
1.44
1.50
1.53
1.55
1.57
1.58
1.59
1.59
1.60
1.60
1.61
1.61
1.62
1.62
1.62
1.62
1.62
1.63
1.63
1.63
1.63
1.63
1.63
1.63
1.63
1.63
1.64
1.64
10
1.42
1.47
1.50
1.52
1.54
1.55
1.56
1.56
1.57
1.57
1.58
1.58
1.58
1.58
1.59
1.59
1.59
1.59
159
1.59
1.59
.60
.60
.60
.60
.60
.60
1.60
* The above critical values for the h and * consistency statistics were calculated from Student's (and the F-ratio using the following relationships:
h = f laboratories (p) and on the number of replicate test results
n) per laboratory per material. The 0.5 % level was chosen
>ased on the judgment and experience that the 1.0 %
esulted in too many cells being flagged and the 0.1 % level
in too few. For further discussion see Annex Al.
17.1.1 Obtain from Table 12 the appropriate critical
values. For the glucose in serum example, the respective
critical h and k values are 2.15 and 2.06. In Tables 3 and 4
circle those values that exceed the critical values and
underline those values that approach the critical values. On
each graph draw a horizontal line for each critical value: two
for h, since there are both positive and negative values of h,
and one for k, as shown in Figs. 1 to 4.
17.1.2 The h and k graphs and the marked tables give a
picture of the overall character of the variability of the test
method as well as singling out particular laboratories or cells
that should be investigated.
17.2 Plots by Laboratory—In order to evaluate the differ-
ences between laboratories, use the following guidelines.
17.2.1 h Graph—There are three general patterns in these
plots. In one, all laboratories have both positive and negative
h values among the materials. In the second, the individual
laboratories tend to be either positive or negative for all
materials and the number of negative laboratories equals the
number of positive laboratories, more or less. Neither of
these patterns is unusual or requires investigation, although
they may tell something about the nature of the test method
variability. In the third pattern, one laboratory, with all h
values positive (or negative), is opposed to all the other
laboratories, with substantially all the h values negative (or
positive). Such a pattern calls for an investigation of that
laboratory.
438
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FIG. 8 Pentosans in Pulp: k—Materials within Laboratories
17.2.1.1 Another kind of pattern to look for occurs within
one laboratory, in which the h values for low property levels
are of one sign, and for high property levels are of the
opposite sign. If the values are extreme, this behavior should
be investigated.
17.2.2 k Graph—Here the primary pattern to look for is
that of one laboratory having large k values (or very small k
values) for all or most of the materials. High k values
represent within-laboratory imprecision. Very small k values
may indicate a very insensitive measurement scale or other
measurement problem.
17.3 Plots by Material—When a plot by laboratory shows
several h or k values near the critical value line, look at the
corresponding plot by material to see how that laboratory
differs from the rest for a given material. Often a vertical line
that seems strong in the plot by laboratory, because of its
relation to the lines for the other materials, will turn out to
be reasonably consistent with the other laboratories for the
same material. Contrarywise, the h or k value for the one
laboratory may be revealed as strongly different from the
values for the other laboratories in the plot by material. If so,
this behavior should be investigated.
18. Investigation
18.1 Clerical and Sampling Errors—Examine the labora-
tory report for each flagged cell. Try to locate where each test
result in the flagged cell begins to deviate from the others. Is
it in the original observations? Are the data rounded prema-
turely? Are the calculations correct? Then, look for signs of
mislabeling of test units such that the test result for one
material was reported as belonging to another material.
Check these errors with the laboratories: do not assume them
to be so.
18.2 Procedural Errors:
18.2.1 Study the laboratory reports again looking for
deviations from either the test method or the protocol. For
instance, variations in the number of significant digits
reported in the test results may be a sign of incorrect
rounding, or that the equipment in one laboratory is
different from the rest. Also, study the event log for special
comments relating to the flagged cells.
19. Task Group Actions
19.1 General—If the investigation disclosed no clerical,
sampling or procedural errors, the unusual data should be
retained, and the precision statistics based on them should be
published. If, on the other hand, a cause was found during
the investigation, the task group has several options to
consider. If the laboratory clearly and seriously deviated
from the test method, the test results for that laboratory must
be removed from the ILS calculations. However, despite the
danger of the recalcitrant laboratory having prior knowledge,
439
-------
E691
3 4~
§
u
2.5
2 "
1
.5
0 -
_
11
.11.1
LlL
Jl
1
111
11
I
LAB: 1234567 1234567 1234567 1234567 1234567 1234567 1234567 1234567 1234567
MAT: ABC
FIG.
D
E
F G H I
9 Pentosans in Pulp: k— Laboratories within Materials
2.03
it may be appropriate to ask the laboratory to retest one or
more materials following the correct procedure, and then
include the new set of test results in the ILS calculations. Of
course, if the data have changed, recalculation of the h and k
values must be made and the data consistency examined
again.
19.2 Exception—When a large number of laboratories
have participated in the ILS and no cause for some unusual
cell values have been found during the investigation, it may
be appropriate to delete a cell from the study if all of the
other laboratories are in substantial agreement. The number
of laboratories that can be considered large enough to
support deletion of data without an identified cause cannot
be stated exactly. Any action which results in discarding
more than five percent of the ILS data likely will lead to the
presentation of precision data that the test method cannot
deliver in routine application.
19.3 Test Method Vagueness—One of the important
things to be on the alert for during a laboratory investigation
is for vagueness in the test method standard that permits a
wide range of interpretation leading to loss of precision.
Particular elements to check are lack of measurement
tolerances, diversity of apparatus and insufficient direction
for operator technique. These problems can be the basis for a
revision of the standard.
20. Examples of Interlaboratory Studies
20.1 Glucose in Serum—The ILS is described in 15.1.1.
20.1.1 h Statistic—The overall impression given by Figs.
1 and 2 and Table 3 is one of reasonable consistency for
variation among laboratories. Only Laboratory 4 stands out
with large values for Materials B and C. The graph for
Material C, in Fig. 2, shows that Laboratory 4 is distinctly
different from the other laboratories. The graph for Material
B, however, does not single out Laboratory 4.
20.1.2 k Statistic—Laboratories 2 and 4 stand out in Fig.
3 and Table 4. The laboratory plot, in Fig. 3, indicates
Laboratory 4 has three high values, but a look at the material
plots (Fig. 4) for A and B suggests that Laboratory 4 is not
out of line for these two materials. On the other hand, the
plot for Material C shows Laboratory 4 is different. Simi-
larly, the plot for Material E shows Laboratory 2 is different
for this material.
20.1.3 Cells and Test Results—Cells C4 and E2 should be
investigated. A look at Table 1 reveals that the second test
results of 148.30 in C4 and of 309.40 in E2 are the particular
values to be investigated.
20.1.4 Action—If the data from Laboratory 4 were typed,
the result 148.30 in Cell C4 could have been a typographical
error. We have no way of knowing this today, many years
after this study was made. We will suppose, however, that the
task group did indeed call the laboratory and did find that
440
-------
E691
1.2
.8 -
.2 -
4-
-t-
4-
4-
4-
0 24 6 8 10 12 14 16 18 20
Averages
FIG. 10 Pentosans in Pulp: Standard Deviations of Reproducibility (O) and Repeatability (•) Versus Average
the number should have been 138.30. However, let us
suppose that for Cell E2 the task group could find no
explanation of the apparently high value of 309.40. In such a
case they should retain the value.
20.1.5 Recalculation—Tables 5 and 6 show the recalcu-
lated consistency statistics resulting from correcting Cell C4.
The discussion of the glucose in serum data is continued in
Section 21.
20.2 Pentosans in Pulp—Seven laboratories tested nine
materials, obtaining three test results per material as shown
in Table 8.
20.2.1 h Statistic—At first glance no one laboratory is
singled out for attention by Fig. 6 or Table 9. For Material A
Laboratory 7 is different and for Material C, Laboratory 1.
On further inspection of the laboratory plot for Laboratory 7
we note the first five materials are negative and the last four
positive. Keeping in mind that the first five materials are
close together in property level while the last two are much
higher in property level, one can see that Laboratory 7 has a
different response to property level than the other laborato-
ries. Laboratory 6 shows the reverse response, but not as
strongly.
20.2.2 k Statistic—From Fig. 8 and Table 10, it is obvious
that Laboratory 1 is different from the rest with five
materials greatly exceeding, and one near, the critical value
line. In addition, Laboratory 7 is different for Material H.
20.2.3 Cells and Test Results—Both Laboratories 1 and 7
should be investigated in depth. Examination of the cell data
for Laboratory 1 in Table 8 suggests special attention should
be given to test results 2 in A, 3 in B, 2 in C, 3 in D, 3 in E,
and 1 in G, but there appears to be an overall problem in
within-laboratory variability. On the other hand, Laboratory
7 has a different problem in not agreeing with the other
laboratories at the two extremes of property level. For
Material A the Laboratory 7 test results are less than half the
values obtained by the other laboratories, while for Material
I the test results are about 10 % higher than the rest. This
variation with property level should be explored.
20.2.4 Action—Note that Laboratory 7 reported test re-
sults to three significant digits for all property levels while all
the other laboratories reported to two decimal places. This
difference in reporting would have been a good place to start
the inquiry of this laboratory. It might be the indication of
apparatus differences, or perhaps a sign that the laboratory
may have disregarded other requirements of the test method
or interlaboratory protocol. The apparently poor within-
laboratory precision of Laboratory 1, if determined to be due
to improper test equipment or poor maintenance of test
environment, might have required omitting this laboratory's
data from the analysis, but with so few laboratories in the
ILS and no physical evidence, the task group should retain
this laboratory's data in the analysis.
PRECISION STATEMENT INFORMATION
21. Repeatability and Reproducibility
21.1 General—Once the task group has concluded which
cells are sufficiently inconsistent to require action, and
action has been taken, the statistics of 15.4 through 15.6 are
recalculated (see also 20.1.5). Using the corrected statistics,
441
-------
E691
calculate for each material the 95 % repeatability and
reproducibility limits (see Practice E 177) according to the
following Eqs 10 and 11:
r=2Asr (10)
* = 2.85* (11)
21.2 Prepare a table for the corrected precision statistics as
shown in Tables 7 and 11.
21.3 Variation of Precision Statistics with Property Level:
21.3.1 Quite often the values of sr and SR will be found to
vary with the values of the property level x. This type of
response is the case for both examples as can be seen in Figs.
5 and 10, that are based on Tables 7 and 11 respectively. The
manner in which the statistics vary with the property level
should be shown in presenting the precision information in
the precision statement of the test method. The statistician
should recommend the most appropriate relationship to
present, using Practice E 177 as a guide.
21.4 Precision Statement—Table 7 or 11 (with the
column for sx omitted) is a useful format for the presenta-
tion of the precision statement of the test method as required
by Section A21 of the "Form and Style of ASTM Standards
(Bluebook)". Having obtained the required precision infor-
mation in accordance with this practice, the final form of the
precision statement may be prepared in accordance with
Practice E 177.
21.5 Conclusion—The precision statistics obtained by an
ILS such as described in this practice must not be treated as
exact mathematical quantities which are applicable to all
circumstances and uses. The small number of laboratories
and of materials included in the usual ILS guarantees that
there will be times when differences greater than predicted by
the ILS results will arise, sometimes with considerably
greater or smaller frequency than the 95 % probability limit
would imply. The repeatability limit and the reproducibility
limit should be considered as general guides, and the
associated probability of 95 % as only a rough indicator of
what can be expected. If more precise information is needed
in specific circumstances, those laboratories directly involved
in a material comparison must conduct interlaboratory
studies specifically aimed at the material of interest.5
5 Following the ASTM Research Report format guide, prepare a research report
on the ILS to be Hied at ASTM Headquarters.
ANNEX
(Mandatory Information)
Al. THEORETICAL CONSIDERATIONS
Al.l Underlying Assumptions of ILS
A 1.1.1 Within-Laboratory Variability—The cell standard
deviation is a measure of the within-laboratory variability of
each individual laboratory. All laboratories are assumed to
have essentially the same level of variability when following
the specified repeatability conditions. This assumption is not
always fulfilled. However, the shorter the period of time in
which the test results for a particular material are to be
obtained by the laboratories the more likely the validity of
this assumption. Therefore, the laboratory cell variances can
generally be pooled by averaging the squares of the cell
standard deviations. The square root of this average within-
laboratory variance is the repeatability standard deviation sr
A 1.1.2 Between-Laboratory Variability:
A 1.1.2.1 Variability of Laboratory Means—The test re-
sults obtained on a particular material at any particular
laboratory are considered part of a population having a
normal distribution with a standard deviation equal to the
repeatability standard deviation but with a mean that may be
different for each laboratory. The laboratory means are also
assumed to vary according to a normal distribution, whose
mean is estimated by the average of all ILS test results for a
given material, and whose standard deviation is designated
by SL. (The effect of a single outlying laboratory on this
assumption will be less if there are enough laboratories.) For
the ILS calculations, SL is estimated from the standard
deviation of the cell - averages, s& and the repeatability
standard deviation, sr is as follows:
(sL)2 + (sr)2/n (Al.l)
Where (sr)2 is the pooled variance for the cell averages of one
material, and n is the number of test results per cell. (ss)2 is
the observed variance of the average of the cell averages.
When (sL)2 calculates to less than zero, SL is taken equal to
zero.
A 1.1.2.2 Reproducibility Standard Deviation—The vari-
ance among individual test results obtained in different
laboratories is the sum of the within-laboratory variance and
the between-laboratory variance of the laboratory means.
Thus, the reproducibility variance is given by Eq A 1.2 as
follows:
(sRf = (sr)2 + (sL)2 (A1.2)
Substituting Eq Al.l into Eq A 1.2 produces Eq A 1.3:
(SR? = (s,)2 + (sy)2 - (sr)2/n (A1.3)
Simplifying and taking the square root gives Eq A 1.4 as
follows (and Eq 7):
(A1.4)
When SR calculates to less than sn SR is set equal to sr
A1.2 Consistency Statistics
A 1.2.1 Critical Values—The derivation of the equations
for calculating critical values of h and k are given in A 1.2.2
and A 1.2.3. In each case critical values were calculated at
three significance levels, 1 %, 0.5 %, and 0.1 %. Of these
three only the 0.5 % critical values were chosen for flagging
as described in Section 17. This choice is based on the
judgment from experience that the 1 % values are too
442
-------
E691
sensitive (flag too many) and the 0.1 % values are not
sensitive enough for flagging adequately in the analysis of
ILS data.
A1.2.2 Between-Laboratory Consistency:
A1.2.2.1 The consistency statistic h is an indicator of how
one laboratory's cell average, for a particular material,
compares with the average of the other laboratories. The
critical values for the comparison are calculated with an
equation derived from an unpaired Mest as given by Eq A1.5
as follows:
!)] (A 1.5)
where:
/ = observed Student's t value,
xc - cell average being tested,
x* - average of all cell averages except the one being tested,
ss* = standard deviation of all the cell averages except the
one being tested, and
p = number of laboratories in the ILS.
In this relationship / has p-2 degrees of freedom. Three
further equations are required in order to express h in terms
of/ from Eq A1.5. These follow as Eqs A1.6, A1.7, and A1.8:
x" = (px-xc)/(p-\) (A1.6)
-p(x-xc)2/((P-\)(p-2)] (A1.7)
h = d/Sy = (xc - x)/sy (A 1.8)
Each of these equations is derived by simple algebraic
operations from the definitions of symbols accompanying Eq
A 1.5 and Table 2. Combining them with Eq A 1.5 results in
Eq A1.9 as follows:
h = (p- \)t/Jp(t2+p-2) (A1.9)
A1.2.2.2 The critical values of h were calculated by Eq
A 1.9 using published values of Student's / at the 0.5 %
two-tailed significance levels (6). The values obtained are
given in Table 12.
A1.2.3 Within-Laboratory Consistency:
A 1.2.3.1 The consistency statistic, k, is an indicator of
how one laboratory's within-laboratory variability, under
repeatability conditions, on a particular material, compares
with all of the laboratories combined. Values of & larger than
1 indicate greater within-laboratory variability than the
average for all laboratories. Since such variation among
laboratories is expected, critical values of k have been
calculated to aid in the decision of whether the cell standard
deviation of one laboratory is sufficiently different from the
rest of the laboratories as to require investigation.
A 1 .2.3.2 A valid test for determining whether a particular
cell variance is inconsistent relative to the variances of the
other laboratories is to calculate the F-ratio of the one cell
variance to the pooled variance of all the other laborato-
ries — excluding the variance being tested. This is shown in
Eq A 1.10 as follows:
where:
s2 = cell variance of cell being tested,
S = summation of all other variances,
;
(s,)2 = cell variances other than the one being tested, and
p = the number of laboratories.
The consistency statistic k is defined by Eq A 1.11 and the
repeatability variance by Eq A 1.1 2 as follows:
k = s/sr (Al.ll)
Combining Eqs. A 1.10, Al.ll and Al. 12 results in EqAl. 13
as follows:
A1.2.3.3 The degrees of freedom for F in Eq Al. 10 are n
— 1 and (p — 1) (n — 1). The upper critical values of A: are
calculated from the upper critical values of F at the 0.5 %
significance level for selected combinations of numbers of
test results and laboratories. The values of A: given in Table
12 were obtained using SAS's BETAINV (inverse beta func-
tion) and using IMSL's routine MDFI (for the F cdf inverse).
443
-------
APPENDIX D
LABORATORY DATA SHEETS
-------
Laboratory 1 Data Sheets
-------
Standard Data Sheet
Standard Data Sheet
6/16/99
Standard
0.50%
5%
50%
5% QCCS
Vial Wt. (me)
2206
2185
2167.6
2191.4
ViaH- Water Wt(mg)
3189.9
3124.7
2663.5
3133.3
Vtel+Water+2-BE Wl. (ma)
3195.3
3169.2
3111
3178.2
Water Wt. (mo)
983.9
939.7
495.9
941.9
2-BE St. (mo)
5.4
44.5
447.5
44.9
Wt. %of2-BE
0.55
4.52
47.43
4.55
Pagel
-------
Calibration Data Sheet
Calibration Data Sheet
6/16/9010:22
Nominal Btd.
0.50%
5%
50%
Coating+Uner Wt. (mg)
507.8
497.7
461.4
Ltoer WMmg)
483.3
472.8
460.7
Massstd. (mg)
24.5
24.9
20.7
StdWt%of2-BE
0.55
4.52
47.43
Corrected std. mass (mg)
0.133730921
1.125838244
9.819005724
FID response
84871.8
842399
7023017.8
RF
634646.045
748241.592
715247.348
%RSD
8.35553096
Average Rf*
Standard Dev. »
699378.328
58436.7727
Page 2
-------
QCCS Data Sheet
QCCS Data Sheet
6/16/9910:22
Sample
QCCS-1
QCCS-2
QCCS-3
Coating +liner Wt. (mg)
515.9
466.4
475.5
Liner Wt
t
mfl)
(96.1
441.5
450.8
Mass (mg)
19.il
24.9
24.7
FIO area
643723
814765
786751
2-BEMass(mg)
0.920421143
1.164963911
1.124928336
Wt%2-BE
4.6485916
4.6786502
4.5543657
Mean Measured Cone. (% 2-BE)= 4.6272025
True Cone. (% 2-BE)» 4.55
Accuracy^ 1016954
%RSD»M.4013709|
Page 3
-------
Paint Results Data Sheet
6/16/9910:22
Paint
MS1-8659A
MS1-6659A
MS 1-6859 A
1403-0100
1403-0100
1403-0100
4206-0100
4206-0100
4206-0100
4020-1000
4020-1000
4020-1000
Sample
1
2
3
1
2
3
1
2
3
1
2
3
Sample Wl (mo)
8.3
28
26.5
33.4
32.7
32.4
34.2
33
27.1
34.2
36.5
33.1
FID Area
1023484
3213238.3
3027846.2
1166877
1138307.2
1149891.2
2815372.8
2768373.3
2286738.5
10179725
1083998.3
972907.9
VOCmass(m0)
1.463419667
4.594420746
4.32933947
1 .654160484
1.627598618
1.644161899
4,025536233
3.958334408
3.269674521
1.455539097
1.549945511
1.391103872
Wt. % VOCfunconrected)
17.63156225
16.40864552
16.33713007
4.95254636
4.977365803
5.074573762
11.77057378
11.99495275
12.06521964
4.255962271
4.246426057
4.20273073
RS(avfl)
1.019
1.019
1.019
0.8365
0.6365
0.8365
1.239
1.239
1.239
1.359
1.359
1.359
Wt. % VOC (corrected)
17.30280888
16.10269433
16.03251234
5.920557513
5.950228097
6.066436058
9.500059547
9.661156376
9.737868955
3.131688734
3.124669652
3.092517094
Page 4
-------
sj99qg BJBQ
-------
-------
Standard Data Sheet
Standard
0.50%
5%
50%
5% QCCS
Date
4-/M7
fc-'Y-?*
&-"f-n
*-.*-? 1
Vial Wt
?.A?ro
c?. 27 ?*.
;?.*'*?
;.*72^
Vial+H2O Wt
2.g^/o
3.7?^
3^7>7
3.t«fcr
Vial+H2O+
2-BE Wt
^.^ir
l.»7^°
J ^ / (* ^
"5 ^9 o / /^*
H2OWt
(mg)
/. 5- <) (,*
/.r/7o
.7r^
/.S-2V1
2-BE Wt
(mg)
..o«r
.0-7^
,-l^t
.o?oo
Wt % 2-BE
.ST%
y.<}?7 "7.
yl.^*?.
s:s-2%
Analyst:
-------
QCCS Data Sheet
Tor
Date
^'fff
(,-^1*7
6-if-?7
Sample
QCCS-1
QCCs-2
QCCS-3
Coating+
Liner
Wt
Liner
Wt
•
Massss
(mg)
o?r.v
A r-^
c^r./
Rfid
/ «*V^-6
1 3 v«7r^.>
;4<-?Vf»-Z^
l/OC ^^^
2-BE Mass
(mg)
/.uv
].&'*'
I-3-Z-3
^- ^^^
^^^
Wt % 2-BE
t-5/
4.?^
r.i?
Mean Measured Conc.(X)=
Analyst:
-------
Calibration Data Sheet
Date
Nominal
Std %
0.5
Coating+
Liner
Wt
Liner
Wt
Mass,,
|/c (mg)
Standard
.00
Mass,
Average RF (RF) =
RF
(area unit/mg)
%RSD
// o j
Analyst:
for
PATRICK J. CAILAHAN
-------
Calibration Data Sheet
Date
fc-n-
Nominal
Std %
0.5
Coating*
Liner
Wt
Liner
Wt
(mg)
Standard
Mass,
.IV'
X RM
Average RF (RF) =
RF
(area unit/mg)
%RSD
Analyst:
PATRICK J. CALLAJIAN
-------
Paint Results Data Sheet
VOC mass,, (mg) Wt% VOCU
Wt% VOCC
(Rfid/RF) (uncorrected) (corrected)
Analyst:
-------
-------
Standard Data Sheet
Standard
Date
Vial Wt
Vial+HO Wt
Vial+H2O+
2-BE Wt
H2OWt
(mg)
2-BE Wt
(mg)
Wt % 2-BE
0.50%
fc-ZMl
I32-- 1
5%
(/O
50%
SI .03
5% QCCS
. 7
13 i/tf -1-
Analyst:
-------
Calibration Data Sheet
Date
Nominal
Std %
0.5
Coating+
Liner
Wt
Liner
Wt
Massu
(mg)
2,5". 0
Standard
Wt % 2-BE
i
Mass,
(nig)
R
fid
Average RF (RF) =
RF
(area unit/mg)
%RSD
Analyst:
-------
QCCS Data Sheet
Date
Sample
Coating+
Liner
Wt
Liner
Wt
Mass
(mg)
2-BE Mass
(mg)
Wt % 2-BE
QCCS-1
$•.00
6-w -
QCCs-2
(•it
Analyst:
Ho
Mean Measured Conc.(X)=
be
PATRICK J. CALLA1IAM
-------
Paint Results Data Sheet
Analyst:
-------
BJBQ \>
-------
QCCS Data Sheet
Date
7/15/99
7/15/99
7/15/99
Sample
QCCS-1 (P)
QCCS-2 (P)
QCCS-3 (P)
Coating+
Liner
Wt
NA
NA
NA
Liner
Wt
NA
NA
NA
Massss
(mg)
23.6
27.7
22.9
Rfid
236495.7
335728.2
269210.9
2-BE Mass
(mg)
1.09
1.55
1.25
Wt % 2-BE
4.62
5.59
5.46
Mean Measured Conc.(X)=
Accuracy= 103.2 PASSED
%RSD= 10.09 PASSED
NA = Noi applicable. Our lab uses the- wre function on ilie balance.
NOTE: Also ran 2 BLANKS: Blank 1 = Clean Liner: Blank 2 = Liner containing 25.8 mg DI water
No areas reported for either blank.
-------
Standard Data Sheet
Standard
0.50%
5%
50%
5%QCCS-1(P)
5% QCCS-2(B)
Date
7/15/99
7/15/99
7/15/99
7/15/99
7/15/99
Vial Wt
NA
NA
NA
NA
NA
Vial+H2O Wt
NA
NA
NA
NA
NA
Vial+H2O+
2-BE Wt
NA
NA
NA
NA
NA
H2OWt
(mg)
4974.8
1899.8
1000.3
1899.7
1901.1
2-BE Wt
(mg)
24.6
101.6
1006.0
101.3
100.8
Wt % 2-BE
0.49
5.08
50.14
5.06
5.04
Analyst:
NA = Not applicable. Our lab uses the tare function on the balance.
-------
Calibration Data Sheet
Date
7/16/99
7/16/99
7/16/99
Nomina
Std %
0.5
Coating+
Liner
Wt
NA
NA
Liner
Wt
NA
NA
Massss
(mg)
27.1
24.6
23.5
Standard
Wt % 2-BE
0.49
5.08
50.14
Mass
0.13
1.25
11.78
24128.0
270304.6
2905986.0
Average RF (RF) =
RF
(area unit/mg)
185600.0
216243.7
246688.
216177.3
PASSED
Analyst:
NA = Not applicable. Our lab uses the tare function on the balance.
ONE-POINT CALIBRATION CHECK:
Date
7 17 99
Nomina
Std %
5
Coating+
Liner
Wt
NA
Liner
Wt
NA
Massss
(mg)
24.7
Standard
Wt % 2-BE
5.04
Mass,
(mg)
1.24
R«d
278022.5
RF
(area unit mg)
224211.7
c/c DIFF
-3.72
PASSED
-------
QCCS Data Sheet
Date
7/15/99
7/15/99
7/15/99
Sample
QCCS-1 (B)
QCCS-2 (B)
QCCS-3 (B)
Coating+
Liner
Wt
NA
NA
NA
Liner
Wt
NA
NA
NA
Massss
(mg)
25.1
22.8
24.3
Rfid
317896.0
296018.9
306215.3
2-BE Mass
(mg)
1.47
1.37
1.42
Wt % 2-BE
5.86
6.01
5.84
Mean Measured Conc.(X)
117.1 FAILED
<>RSD= 1.58 PASSHD
Analvst: -
NA = Not applicable. Our lab uses the tare function on the balance.
-------
Paint Results Data Sheet
VOC mass,, (mg) Wt% VOC
(Rf,d/RF) (uncorrected)
7/16/99
7/16/99
7/16/99
MS1-6659A
MS1-6659A
MS1-6659A
1
2
3
11.4
25.4
23.7
388357.3
933023.0
853080.8
216177.3
216177.3
216177.3
1.80
4.32
3.95
15.79
17.01
16.67
15.51
16.71
16.38
7/16/99
7/16/99
7/16/99
1403-0100
1403-0100
1403-0100
1
2
3
30.7
26.2
31.4
274039.9
232522.6
285352.9
216177.3
216177.3
216177.3
1.27
1.08
1.32
4.14
4.12
4.20
4.94
4.92
5.01
7/16/99
7/16/99
7/16/99
4206-0100
4206-0100
4206-0100
1
2
3
31.6
35.8
28.3
885611.6
1007103.4
778731.1
216177.3
216177.3
216177.3
4.10
4.66
3.60
12.97
13.02
12.72
10.52
10.56
10.32
7/16/99
7'16/'99
7/16/99
4020-1000
4020-1000
4020-1000
1
2
3
27.9
36.0
30.0
223743.8
297978.4
245374.1
216177.3
216177.3
216177.3
1.04
1.38
1.14
3.73
3.83
3.80
2.72
2.80
2.78
Analyst:
-------
BJBQ 5
-------
QCCS Data Sheet
Date
Sample
(Joatmg+
Liner
Wt
I
I
Liner
Wt
2-BE Mass
(mg)
Wt%2-BE
QCCS-1
QCCS-2
15.0
Mean Measured Conc.(X)=
Analyst:
R
-------
Calibration Data Sheet
Date
Nominal
Std %
Coating+
Liner
Wt
Liner
Wt
Massu
(mg)
25.0
Standard
Wt % 2-BE
Mass,
(mg)
0.135
R
fid
\\V77H0.0
Average RF (RF) =
RF
(area unit/mg)
%RSD
Analyst:
-------
Calibration Data Sheet
Date
Nominal
Std %
0.5
Coating+
Liner
Wt
Liner
Wt
Mass,,
(mg)
Standard
Wt%2-BE
Mass,
(nig)
R,
fid
Average RF (RF) =
RF
(area unit/mg)
%RSD
/\nalyst:
-------
Paint Results Data Sheet
Analyst:
cr.vj-.::::.}
-------
BJBQ 9
-------
Standard Data Sheet
Standard
0.50%
5%
50%
5% QCCS
Date
8/19/99
8/19/99
8/19/99
8/19/99
Vial Wt
2.3290
2.3006
2.2817
2.3036
Vial+H2OWt
(gm)
3.9156
3.7645
3.1059
3.8868
Vial+H2(H
2-BE Wt
(gin)
3.9245
3.8473
3.9304
3.9673
H2OWt
(rag)
1,586.6
1,463.9
824.2
1,583.2
2-BE Wt
(ing)
8.9
82.8
824.5
80.5
Wt%2-BE
0.5578
5.3533
50.0091
4.8386
Analyst:
-------
Calibration Data Sheet
•X
Date
8/19/99
8/19/99
8/19/39
Nominal
Sld%
0.5
Coaling+
Liner
w<
U«0
05531
0.4845
0.4790
Liner
Wt
(gm)
0.5279
0.4594
0.4548
Mass
25.2
25.1
24.2
Standard
Wt%2-BE
0.5578
5.3533
50.0091
Mass,
(mg)
0.1406
1.3437
12.1022
93,772.3
952,916.4
9,462,017.0
Average RF (RF) =
RF
(areanrrit/nig)
667,107.0
709,1849
781,8416
719,378.2
.t.
I-1
T.
r
u
c
c
u
0
AiuJyst:
-------
QCCS Data Sheet
Date
8/19/99
8/19/99
8/19/99
Sample
QCCS-l
QCCS-2
QCCS-3
Coating+
Liner
Wt
(gm)
0.4787
0.4931
0.5626
Liner
Wt
= 4.8386
Analyst:
-------
Calibration Data Sheet
Date
Nominal
Std%
Coaling*
Liner
Wt
Liner
Wt
Mass,
(mg)
Standard
Wt%2-BE
Mass.
RF
(area unit/ing)
8/20/99
0.5530
OJ277
253
0.5578
0.1411
73,804.6
522^79.2
8/20/99
0.4146
0.4592
25.4
5.3533
1.3597
1,021,429.0
751,195.3
8/20/99
0.4789
0.4547
24.2
50.0091
12.1022
10,045,310.0
Avenge RF (RF) =
830,039.8
701,404.8
Analyst:
-------
QCCS Data Sheet
Date
8/25/99
Sample
QCCS-1
QCCS-2
QCCS-3
Coating*
Liner
Wt
(gm)
0.4760
\
Liner
Wt
(gm>
0.4510
.'
MasSy
(mg)
25.0
Rfid
848,260.4
2-BEMass
(mg)
1.2094
Wt % 2-BE
4.8375
Analyst:
J. CALLA!.1:.?!
/I -1 .-)
'
^ , . /- _
— r~i rv I
-------
Paint Results Data Sheet
Wt% VOCC
(corrected)
8/25/99
8/25/99
8/25/99
MS1-6659A
MS1-6659A
MS1-6659A
1
2
3
36.5
31.9
38.8
4,307,566.4
3,713,699.8 ^
4,615,410.2
701,404.8
701,404.8
701,404.8
6.1413
5.2947
6.5802
16.83
16.60
16.96
16.50 S
16.28 /"
16.63 /
8/25/99
8/25/99
1403-0100
1403-0100
46.5
39.6
1,337,259.7
1,143,124.7
701,404.8
701,404.8
1.9065
1.6298
4.10
4.12
4.89
4.91
8/25/99
1403-0100
51.1
1,466,773.8
701,404.8
2.0912
4.09
4.88
8/25/99
8/25/99
8/25/99
4206-0100
4206-0100
4206-0100
1
2
3
33.1
52.1
41.6
2,835,984.2
4,623,064.2
3,654,292.4
701,404.8
701,404.8
701,404.8
4.0433
6.5911
5.2100
12.22
12.65
12.52
9.85
10.20
10.09
8/25/99
8/25/99
8/25/99
4020-1000
4020-1000
4020-1000
1
2
3
58.0
52.6
61.6
1,615,703.8
1,438,136.9
1,690,767.1
701,404.8
701,404.8
701,404.8
2.3035
2.0504
2.4105
3.97
3.90
3.91
2.92
2.86
2.88
Analyst:
-------
TECHNICAL REPORT DATA
(Pleat read Instruction on the rtvene be fort completing)
1. REPORT NO.
EPA-454/R-99-040
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
Evaluation of the Water-based Coating Method (ATD-FID)
Round Robin Study
9. REPORT DATE
September 1999
6. PERFORMING ORGANIZATION COOK
7. AUTHOR(S)
8. PERFORMING ORGANIZATION" REPORT NO.
EMAD
9. PERFORMING ORGANIZATION NAME AND ADDRESS
10. PROGRAM ELEMENT NO..
11. CONTRACT/GRA.NT NO. •
Battelle Memorial, Inc.
FPA Hnnt.f Rfi-n-q
12. SPONSORING AGENCY NAME AND ADDRESS
U.S. Environmental Protection Agency
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
Final Report •
14. SPONSORING AGENCY CODE
. EPA/200/04
IS. SUPPLEMENTARY NOTES
16. ABSTRACT
The purpose of this project was to conduct an interlaboratory study to evaluate the
draft water-based caoting method. A total of six laboratories participated in the
interlaboratory study. Each of the laboratories was required to.analyze four
different water-based coatings following the procedure described in the draft method.
The results from the participating laboratories were analyzed using the statistical
procedure described in ASTM E 691, Standard Practice for Conducting an Interlaboratory
Study to Determine the Precision of a Test Method.
Method Evaluation
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS C. COSATI Field/Group
Method Evaluation of
Water-based Coating
Method
18. DISTRIBUTION STATEMENT
Release Unlimited
19. SECURITY CLASS I Tins Keporn
21. NO. OF
200
20. SECURITY CLASS (Thispagei
22. PRICE
EPA Form 2220-1 (R«»- 4-77) PREVIOUS eoirtON is OBSOLETE
-------
INSTRUCTIONS
1. REPORT NUMBER
Insert the tPA report number is it appears on the cover of the publication.
2. LEAVE BLANK
3. RECIPIENTS ACCESSION NUMBER
Reserved for use by each report recipient.
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Title should indicate clearly and briefly the subject coverage of (ho report, and be displayed prominently. Svl subtitle, if uwd. in smaller
type or otherwise subordinate it to main title. When a report is prepared in more than one volume, repeat iho primary liltc.add volume
number and include rabtitk for the specific title.
5. REPORT DATE : ^p.r,
Each report shall cany a date indicating at least month and year. Indicate the hasis on which ii was selected (e.g.. Jateofim*. title of
approval, dale of preparation, tie.).
6. PERFORMING ORGANIZATION CODE
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zation.
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11. CONTRACT/GRANT NUMBER
Insert contract or grant number under whkh report was prepared.
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14. SPONSORING AGUNCY CODE
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15. SUPPLEMENTARY NOTES
Enter information not included elsewhere but useful, such as: Prepared in cooperation with. Translation of, ('resettled al conlercmv "I.
To be published in. Supersedes, Supplements, etc.
16. ABSTRACT
Include a brief (200 words or less/ factual summary of the most significant information contained in the report. It lite report contains a
significant bibliography or literature survey, mention it here.
17. KEY WORDS AND DOCUMENT ANALYSIS
(a) DESCRIPTORS • Select from the Thesaurus of Engineering and Scientific Terms the proper authorised terms dial identify the major
concept of the research and are sufficiently specific and precise to be used as index entries lor calaloiiint!.
(b) IDENTIFIERS AND OPEN-ENDED TERMS • Use identifiers for project namts. code names, equipment designators, etc. Use open-
ended terms written in descriptor form for those subjects for which no descriptor exists.
(c) COSATI HELD GROUP -Field and group assignments are to be taken from the 1965 COSATI Subject Catcpory List. Since the ma-
jority of documents are multidisciplinary in nature, the Primary Held/Group assignments) will be specific discipline, area of human
endeavor, or type of physical object. The application^) will be cross-rclcrcnccd with secondary I icld/< iroup assignments that will follow
the primary posting(s).
18. DISTRIBUTION STATEMENT
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22. PRICE
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EPA Form 2220-1 (R«v. 4-77) (R«w««)
-------
TECHNICAL ttETORT DATA
(Pleat read Instructions on tht reverse before completing)
1. REPORT NO.
EPA-454/R-99-040
2.
3. RECIPIENT'S ACCESSION NO..
4. TITLE AND SUBTITLE
Evaluation of the Water-based Coating Method (ATD-FID)
Round Robin Study
5. REPORT DATE
September 1999
S. PERFORMING OROANIZAT1OWCODI
7. AUTHOR
------- |