United States Air and Radiation EPA340/1-91-011
EPA/340/1-91/011 nental Protection (EN-341W) September 1991
mdard Operating Procedure
for Analysis of Ink ^
Samples by Reference
Methods 24 and 24A
1445 ROSS AVENUE
, TEXAS 7520?
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EPA-340/1-91-011
STANDARD OPERATING PROCEDURE FOR
ANALYSIS OF COATING AND INK SAMPLES
BY REFERENCE METHODS 24 AND 24A
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Air and Radiation
Office of Air Quality Planning and Standards
Stationary Source Compliance Division
Washington, DC 20460
September 1991
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DISCLAIMER
This document is a draft report submitted to the Stationary Source Compliance
Division for circulation and subsequent comment on the technical adequacy of the
contents. Any view or opinions contained herein are those of the authors and do not
necessarily reflect the conclusions of the U.S. Environmental Protection Agency.
Any mention of trade names or commercial products does not constitute
endorsement or recommendation for use by the U.S. Environmental Protection
Agency.
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CONTENTS
Section Page
1. INTRODUCTION 1
2. SAMPLE HANDUNG PROCEDURES 3
3. REFERENCE METHOD 24 7
4. SOP FOR METHOD 24 ANALYSES 15
Determination of Percent Water Content in Coating Samples
by Gas Chromatography 19
Determination of Water Content in Coating by Karl Fischer
Titration 31
Determination of Percent Volatile Content in Coating
Samples 39
Determination of Density of Paint, Varnish, Lacquer, and
Related Products 43
•
Determination of Dichloromethane and 1,1,1-Trichloroethane
in Paints and Coatings by Direct Injection into a Gas
Chromatograph 47
5. REFERENCE METHOD 24A 63
6. SOP FOR METHOD 24A ANALYSES 67
7. BIBLIOGRAPHY 69
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SECTION 1
INTRODUCTION
This standard operating procedure document is prepared with the intent of
providing simple step-by-step instructions, covering all aspects of laboratory handling
and analysis of coating and ink samples, for use by EPA, State, and local regulatory
agency laboratories as well as contract laboratories nationwide. The instructions are
presented in general terms as much as possible while providing sufficient details for
accurate and precise laboratory measurements to be done. The procedures should
be used in conjunction with existing health and safety programs and in accordance
with existing EPA or other agency training guidelines.
Standard procedures are presented in this report for the handling and
physical/chemical characterization of coating and ink samples that require analysis by
EPA Reference Methods 24 or 24A (RM 24/24A) as found in 40 CFR 60, Appendix A.
This document has been expanded from an original version obtained from the
Wisconsin Occupational Health Department covering laboratory determinations of the
VOC content, water content, and density of coating and ink samples taken for
environmental compliance. For the purpose of developing consistency among
analytical laboratories nationwide, it delineates the activities deemed proper and
necessary to ensure that an accurate and precise measurement of coating or ink
sample properties are made. If the activities are conducted as described, questions
concerning the validity and reproducibility of analyses performed can be avoided.
The purpose of these standard operating procedures (SOPs) for RM 24 and RM
24A is to ensure that laboratory analyses are performed in such a way that review,
interpretation, and use of the laboratory analysis results by EPA, State, and local
regulatory agency personnel is facilitated.
The procedures cover all types of industrial coating and printing ink operations,
regardless of the method of application of coating or ink, including, for example, dip,
spray, roll, flow, electrostatic, or electro-deposition processes. Special cases involving
use of exempt solvents dichloromethane (methylene chloride) and 1,1,1-trichloroethane
(methyl chloroform) or multi-component mixture coating formulations are covered in
accordance with most recent technical and regulatory thinking, however, this is not a
regulatory but a technical procedure guideline document.
In addition to the introduction given here, Section 2 of this document contains a
summary of sample handling procedures to be followed; Section 3 contains EPA
Reference Method 24 including draft revision amendments which are being considered
to make it applicable to multi-component coatings and exempt solvents; Section 4
contains detailed SOPs for EPA Method 24 analyses for percent water content,
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percent volatile content, exempt solvent (dichloromethane and 1,1,1-trichloroethane),
and density of coatings; Section 5 contains EPA Reference Method 24A for
determination of volatile matter and density of printing inks; Section 6 contains SOP
guidance for EPA Method 24A analyses; and Section 7 contains a detailed
bibliography of documents relevant to EPA Method 24/24A analyses.
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SECTION 2
SAMPLE HANDLING PROCEDURES
There are several steps to be taken at the laboratory upon receipt of a sample
for analysis according to EPA Reference Methods 24 and 24A. These are outlined
below:
1. Inspect the shipping package for damage and proper labeling. If
improper labeling, delayed shipping, damage, spillage, or other problem
is evident, notify the sending agency by phone as soon as possible.
2. Open the shipping package and record in a laboratory notebook or
recordbook relevant observations and information from containers,
labels, shipping papers, Material Safety Data Sheets (MSDS) forms, and
Chain of Custody (C of C) documents, which should be enclosed with
the samples. Include the following:
2.1 Name of person who collected the samples, the date/time the
samples were obtained, and the date/time the samples were
shipped to the laboratory for analysis.
2.2 Name, phone number, and address of agency and person to
whom results of analyses are reported.
2.3 Facility or source identification to be coded or numbered.
2.4 Sample identification number and a brief description of the sample
and container.
2.5 Analyses required, RM 24, RM 24A, multi-component, or exempt
solvent determinations.
2.6 Describe the physical appearance of the sample on first opening
(e.g., full to top, not tightly sealed or inner seal missing,
appearance (color), type of ink/coating, odor, or presence of
residue).
2.7 Summarize MSDS information, if available, for safety and handling
purposes.
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2.8 If special multi-component sample blending or exempt solvent
determination is required, contact sending agency personnel for
instructions on set-up (hardening) time and mixing proportions.
2.9 Report problems with sampling integrity or inconsistencies in
documentation, including missing (or occasionally too much)
information on the labels or C of C forms.
2.10 Start any internal laboratory sample recordkeeping procedures
normally used to track samples.
3. After signing the C of C receipt of the samples, send the original of the
C of C documents back to the appropriate sending agency personnel for
their records and keep a copy for laboratory records.
4. Secure, the samples with a copy of the C of C documents and MSDS
forms in a locked storage cabinet dedicated to environmental samples. If
this is done by a sample custodian designated to retain custody of the
sampling pending analysis, then that person should sign the C of C
forms acknowledging receipt of the samples. Maintain samples at room
temperature, preferably at 70°F but within the range of 40 to 100°F.
During and at the end of sample analyses, there are several steps to be taken
related to disposal of waste materials from the sample and the laboratory analysis.
These are summarized below:
5. A plastic bag should be used to discard waste ink solids, rags, paper
towels, kimwipes, and other non-glass or non-sharp items. This can
normally be disposed of with industrial solid waste material.
6. A separate container (e.g., a glass bottle or metal/plastic can), should be
used for collection and eventual disposal of discarded glassware and
other sharp-edged items used in the laboratory. This may be discarded
with industrial solid waste, but must be given careful handling during
disposal.
7. A 5-gallon solvent-resistant plastic or metal container with a lid or cover
designed for flammable liquids should be stored in the hood where
analytical work is performed. It should be used to collect unused or
excess sample, reagents, and mixtures of both for periodic disposal as a
liquid waste. Fiber mesh material can be used to filter out solids from
liquid wastes that are deposited into the container. A list of compounds
which are placed in the container should be kept as a record for
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identification of the contents upon disposal. Liquid waste should be sent
out for disposal to a reputable disposal organization.
8. After analyses are completed (or approximately 30 days), the samples in
their sample containers should be attached to their MSDS forms identi-
fying the approximate composition, physical and chemical properties, and
safety hazards associated with the sample. They should then be sent
out for disposal to a reputable disposal organization. If analyses have
not been completed within 30 days, it is recommended that another
sample should be taken since the chemical/physical composition of the
existing sample may have changed significantly over the time period.
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SECTION 3
REFERENCE METHOD 24-DETERMINATION OF VOLATILE MATTER
CONTENT AND DENSITY OF PRINTING INKS AND RELATED COATINGS
EPA Reference Method 24 as it appears in 40 CFR Part 60, Appendix A (7-1-90
edition) is presented here, starting on the following page, with draft revisions under
consideration by EPA shown in bold italics. These revisions incorporate procedures to
be used with multi-component coatings and exempt solvents which are not addressed
in the 7-1-90 edition of 40 CFR 60, Appendix A.
Analysis for exempt solvents in coatings is practiced according to ASTM D4457-
85 - "Standard Test Method for Determination of Dichloromethane and 1,1,1-Trichloro-
ethane in Paints and Coatings by Direct Injection into a Gas Chromatograph." In the
draft revisions to EPA Method 24, this procedure is incorporated by reference.
Proposed guidance for handling multi-component coatings, developed for
incorporation into EPA Method 24, includes revisions to the existing text and some
additional text. In the revisions, existing Sections 3.1, 3.2, 3.3, and 3.4 have been
redesignated as Sections 3.2, 3.3, 3.4, and 3.5, respectively; Sections 5.1 and 5.2
have been revised; and new Sections 2.5, 3.1, 3.6, and 3.7 have been added, as
shown in bold italics on the following pages.
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REFERENCE METHOD 24 - DETERMINATION OF VOLATILE MATTER CONTENT,
WATER CONTENT, DENSITY, VOLUME SOLIDS, AND WEIGHT SOUS OF SURFACE
COATINGS
Current Draft Revisions Shown in Bold Italics
40 CFR Part 60, Appendix A
(7-1-90 Edition)
Final, promulgated 10/3/80
45 FR 65958
1. Applicability and Principle
1.1 Applicability. This method applies to the determination of volatile matter
content, water content, density, volume solids, and weight solids of paint,
varnish, lacquer, or related surface coatings.
•1.2 Principle. Standard methods are used to determine the volatile matter
content, water content, density, volume solids, and weight solids of paint,
varnish, lacquer, or related surface coatings.
2. Applicable Standard Methods
Use the apparatus, reagents, and procedures specified in the standard
methods below:
2.1 ASTM D1475-60 (Reapproved 1980), Standard Test Method for Density
of Paint, Varnish, Lacquer, and Related Products (incorporated by
reference-see §60.17).
2.2 ASTM D2369-81, Standard Test Method for Volatile Content of Coatings
(incorporated by reference-see §60.17).
2.3 ASTM D3792-79, Standard Test Method for Water Content of Water-
Reducible Paints by Direct Injection into a Gas Chromatograph (incorpo-
rated by reference-see §60.17).
2.4 ASTM D4017-81, Standard Test Method for Water in Paints and Paint
Materials by the Karl Fischer Titration Method (incorporated by reference-
-see§60.17).
2.5 ASTM D4457-35 Standard Test Method for Determination of Dichloro-
methane and 1,1,1-Trichloromethane in Paints and Coatings by Direct
Injection into a Gas Chromatography.
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3. Procedure
3.1 Multi-Component Coatings. To determine the total volatile content, water
content, and density of multi-component coatings, follow the procedures
in Section 3.7. Multi-component coatings are coatings that are packaged
in two or more parts, which are combined before application. Upon
combination a coreactant from one part of the coating chemically reacts,
at ambient conditions, with a coreactant from another part of the coating.
For all other coatings analyze as follows:
3.2 Volatile Matter Content. Use the procedure in ASTM D2369-81
(incorporated by reference-see §60.17) to determine the volatile matter
content (may include water) of the coating. Record the following
information:
W, = Weight of dish and sample before heating, g.
W2 = Weight of dish and sample after heating, g.
W3 = Sample weight, g.
Run analyses in pairs (duplicate sets) for each coating until the criterion
in Section 4.3 is met. Calculate the weight fraction of the volatile matter
(WJ for each analysis as follows:
W -W
W--^^ Eq. 24-1
Record the arithmetic average (WJ.
3.3 Water Content. For waterborne (water reducible) coatings only,
determine the weight fraction of water (WJ using either "Standard
Content Method Test for Water of Water-Reducible Paints by Direct Injec-
tion into a Gas Chromatograph" or "Standard Test Method for Water in
Paint and Paint materials by Karl Fischer Method." (These two methods
are incorporated by reference - see §60.17.) A waterborne coating is
any coating which contains more than 5 percent water by weight in its
volatile fraction. Run duplicate sets of determinations until the criterion in
Section 4.3 is met.
Record the arithmetic average (WJ.
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3.4 Coating Density. Determine the density (Dc, kg/liter) of the surface
coating using the procedure in ASTM D1475-60 (Reapproved 1980)
(incorporated by reference - see §60.17). Run duplicate sets of
determinations for each coating until the criterion in Section 4.3 is met.
Record the arithmetic average (D£.
3.5 Solids Content. Determine the volume fraction (VJ solids of the coating
by calculation using the manufacturer's formulation.
3.6 Exempt Solvent Content Determine the weight content of exempt
solvents (WJ by using ASTM Method D4457-85 (incorporated by
reference - see §60.17). Run a duplicate set of determinations.
Record the arithmetic average
Note: exempt solvents are defined as those solvents listed in 57 FR
3941, February 3, 1992. Dichloromethane and 1,1,1-trichloroethane are
listed exempt solvents and may be used in coatings.
3.7 To determine the total volatile content, water content, and density of
multi-component coatings, use the following procedures:
3.7.1 Prepare about 100 ml of sample by mixing the components in a
storage container, such as a glass jar with a screw top or a metal
can with a cap. The storage container should be just large
enough to hold the mixture. Combine the components (by weight
or volume) in the ratio recommended by the manufacturer. Tightly
close the container between additions and during mixing to
prevent loss of volatile materials. However, most manufacturers
mixing instructions are by volume. Because of possible error
caused by expansion of the liquid when measuring the volume, it
is recommended that the components be combined by weight
When weight is used to combine the components and the
manufacturer's recommended ratio is by volume, the density must
be determined by Section 3.4.
3.7.2 Immediately after mixing, take aliquots from this 100 ml sample for
determination of the total volatile content, water content, volume
solids, and density. To determine water content, follow Section
3.3. To determine density, follow Section 3.4. To determine
volume solids content, follow Section 3.5. To determine total
volatile content, use the apparatus and reagents described in
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ASTM D2369-81, Sections 3 and 4, respectively, and the following
procedures:
3.7.2.1 Weigh and record the weight of an aluminum foil
weighing dish. Add 3 ± 1 ml of suitable solvent as
specified in ASTM D2369-81 to the weighing dish.
Using a syringe as specified in ASTM D2369-81,
weigh to 1 mg, by difference, a sample of coating
into the weighing dish. For coalings believed to
have a volatile content less than 40 weight percent, a
suitable size is 0.3 ± 0.10 g, but for coatings
believed to have a volatile content greater than 40
weight percent a suitable size is 0.5 ± 0.10 g. Note:
If the volatile content determined pursuant to Section
5 is not in the range corresponding to the sample
size chosen repeat the test with the appropriate
sample size. Add the specimen dropwise, shaking
(swirling) the dish to disperse the specimen
completely in the solvent If the material forms a
lump that cannot be dispersed, discard the specimen
and prepare a new one. Similarly, prepare a
duplicate. The sample shall stand for 1 hour, but no
more than 24 hours prior to being oven dried at
110°C ± 5°C for 1 hour.
3.7.2.2 Heat the aluminum foil dishes containing the
dispersed specimens in the forced draft oven for 60
minutes at 110 ±5°C. Caution - provide adequate
ventilation, consistent with accepted laboratory
practice, to prevent solvent vapors from accu-
mulating to a dangerous level.
3.7.2.3 Remove the dishes from the oven, place immediately
in a desiccator, cool to ambient temperature, and
weight to within 1 mg.
3.7.2.4 Run analyses in pairs (duplicate sets) for each
coating mixture until the criterion in Section 4.3 is
met Calculate W, following Equation 24-1 and
record the arithmetic average.
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4.
Data Validation Procedures
4.1
4.2
Summary. Trie variety of coatings that may be subject to analysis makes
it necessary to verify the ability of the analyst and the analytical
procedures to obtain reproducible results for the coatings tested. This is
done by running duplicate analyses on each sample tested and
comparing results with the within-laboratory precision statements for
each parameter. Because of the inherent increased imprecision in the
determination of the VOC content of waterborne coatings as the weight
percent water increases, measured parameters for waterborne coatings
are modified by the appropriate confidence limits based on between-
laboratory precision statements.
Analytical Precision Statements. The within-laboratory and between-
laboratory precision statements are given below
Volatile Matter
Content, Wv
Water Content, Ww
Density, Dc
Within-laboratory
1.5% W7
2.9% Ww
0.001 kg/liter
Between-laboratory
4.7 % W7
7.5% Ww
0.002 kg/liter
4.3
4.4
Sample Analysis Criteria. For Wv and Ww, run duplicate analyses until the
difference between the two values in a set is less than or equal to the
within-laboratory precision statement for that parameter. For Dc run
duplicate analyses until each value in a set deviates from the mean of the
set by no more than the within-laboratory precision statement. After
several attempts, if it is concluded that the ASTM procedures cannot be
used for the specific coating with the established within-laboratory
precision, the Administrator will assume responsibility for providing the
necessary procedures for revising the method or precision statements
upon written request to: Director, Emission Standards and Engineering
Division, (MD-13) Office of Air Quality Planning and Standards, U.S.
Environmental Protection Agency, Research Triangle Park, NC 27711.
Confidence Limit Calculations for Waterborne Coatings. Based on the
between-laboratory precision statements, calculate confidence limits for
waterborne coatings as follows:
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To calculate the lower confidence limit, subtract the appropriate
between-laboratory precision value from the measured mean value
for that parameter.
To calculate the upper confidence limit, add the appropriate
between-laboratory precision value to the measured mean value
for that parameter.
For Wv and Dc, use the lower confidence limits, and for Ww, use
the upper confidence limit. Because Vs is calculated, there is no
adjustment for the parameter.
5. Calculations
5.1 Nonaqueous Volatile Matter.
5.1.1 Solvent-borne Coatings.
W0*WV Eq. 24-2
Where:
W0 = Weight fraction nonaqueous volatile matter, g/g.
5.1.2 Waterborne Coatings.
Wa=Wv-Ww Eq. 24-3
5.7.3 Coatings Containing Exempt Solvents.
5.2 Weight Fraction Solids.
W3*-\-Wv Eq.24-5
Where:
Ws = Weight solids, g/g.
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SECTION 4
STANDARD OPERATING PROCEDURES FOR METHOD 24 ANALYSES
PRIMARY ASTM METHODS
EPA Method 24 calls for the determination of density by ASTM D1475-60
(Reapproved 1980), volatile content by ASTM D2369-S1, and water content by either
ASTM D3792-79 (gas chromatography) or ASTM D4017-81 (Karl Rscher titration) of
coating samples taken by regulatory agency personnel. ASTM D4457-85 is
considered the best guidance presently available to determine the exempt solvent
content of coatings.
SAMPLE CHARACTERIZATION STEPS
General
It is essential to make use of all the characterization information that may be
available on the sample to proceed expeditiously. If the MSDS forms are available with
the samples (as they should be), it can be determined if a highly volatile solvent, such
as a light petroleum ether, is present or if the sample consists of more than 70-75%
volatile solvents. Otherwise, a phone call can be made to the sending agency to
determine the approximate solvent composition expected. This helps to determine the
amount of sample to be used in the volatile content analysis to obtain a good reading
on the volatile content, using ASTM D2369-81.
•
Step 1
The first step to be taken with a sample is opening and examining it in the
hood. Important points to note here include amount of sample relative to container
size (full, almost full, 3/4 full, etc.), color, viscosity, and uniformity. If questions arise at
this point because of a conflict of observation with included information, the sending
agency must be contacted to determine the proper course of action.
Step 2
If specific exempt solvent assay is requested, then the preparation of aliquots of
sample for the determination of the content of the solvent should begin right after the
sample examination. The standard test method ASTM D4457-85 for determination of
dichloromethane (methylene chloride) or 1,1,1-trichloroethane (methyl chloroform) is
being considered for incorporation into EPA Method 24. If the exempt solvent assay is
not run immediately these aliquots should be securely sealed and stored at -20 C until
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the assay is performed. At any rate, during the performance of analytical procedures,
ideally no interruptions should be allowed and sample containers should always be
kept sealed except when they must be opened to take or transfer sample material.
The results of assays for exempt solvents (and of the water assay to be done later in
the procedure) will be subtracted from the total volatile content.
Step 3
The total volatile content will be determined using ASTM D2369-81. This should
follow the previous step with minimal delay to ensure the best estimate of the total
volatile content.
Step 4
The next step in the procedure should be the analysis for water content by
either ASTM D3792-79 (gas chromatography) or ASTM D4017-81 (Karl Rscher
titration). One of two conditions should exist before this step is included: either the
sending agency specifically requests analysis for water content or the documentation
accompanying the sample indicates the presence of water. Care is taken during all
previous steps to prevent the coating sample from absorbing water. The total volatile
content reported would be too high if the sample absorbed water in the lab.
Step 5
The density determination using ASTM D1475-60 (Reapproved 1980) is always
done last because it entails use of a large quantity of sample and would provide the
maximum opportunity for sample volatilization.
SOPs FOR REFERENCE METHOD 24 ANALYSES
The following five procedures have been adapted from the pertinent ASTM
methods to provide additional detail as well as to provide step-by-step procedures to
be followed in their use under EPA Method 24. The five procecdures are presented in
the following order:
• Determination of Percent Water Content in Coating Samples by Gas
Chromatography (Adapted from ASTM D3792-79)
• Determination of Water Content in Coatings by Karl Fischer Titration
(Adapted from ASTM D4017-81)
Determination of Percent Volatile Content in Coating Samples (Adapted
from ASTM D2369-81)
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Determination of Density of Paint, Varnish, Lacquer, and Related
Products (Adapted from ASTM D1475-60)
Determination of Dichloromethan and 1,1,1-Trichloroethane in Paints and
Coatings by Direct Injection into a Gas Chromatograph (Adapted from
ASTM D4457-85)
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DETERMINATION OF PERCENT WATER CONTENT IN COATING SAMPLES BY GAS
CHROMATOGRAPHY (Adapted from ASTM D3792-79)
METHOD: The percent water content is determined by direct injection
into a gas chromatograph.
EQUIPMENT:
I. Glassware
A. A bottle of 50 ml capacity with a cap having an inert liner - one.
B. 20 ml scintillation vials with teflon inverted cone cap seals - three.
C. 10 ml serum bottles - six + four per sample.
1. Teflon coated septa - six + four per sample.
2. Aluminum caps - six + four per sample.
II. Syringes and pipettes
A. 10 ml disposable syringe with needle - one.
B. 5 ml disposable syringe with needle - two.
•
C. A 5 ml pipetting device with one disposable tip.
D. A 200 n\ Eppendorf pipettor with three disposable tips.
E. Transfer pipette (5 3/4" Pasteur type) - five per sample.
F. A 10 /*! syringe with needle.
III. Chemicals
A. Deionized water (H2O).
B. Anhydrous N,N-Dimethylformamide (DMF).
C. Anhydrous 2-propanol (i-PrOH).
D. Anhydrous n-propanol (n-PrOH).
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E. High purity, dry nitrogen (NJ.
IV. Miscellaneous
A. Rubber tubing - 18 inches.
B. Bottle cap crimper.
C. Pressure regulator for N2 tank.
V. Analytical balance - Range 0-200 grams, Reproducibility: ±0.1 mg
VI. Gas Chromatograph (GC) - e.g., HP 5890 A
A. Thermal conductivity detector.
B. Porapak Q column - 10 ft.
VII. Integrator - e.g., HP 3357 LAS or HP 3392 A.
Note: Anhydrous solvents in packaging similar to the Sure/Seal
Packaging System employed by the Aldrich Chemical Company,
Inc. allow storing and dispensing of the solvent without exposure
to atmospheric moisture. This procedure describes using
reagents packaged in that manner, but the steps described can
cause deterioration of the septa and exposure of the solvent to
atmospheric moisture. An alternative procedure would be used in
a high humidity environment or to ensure the transfer of solvents
as free of moisture as possible.
PROCEDURE:
I. General Preparation
A. Assemble equipment needed.
B. Fill a 20 ml scintillation vial with deionized water, cap it, label the vial
"H2O."
C. Label a 10 ml syringe with needle and the 50 ml bottle "DMF". One 5 ml
syringe with needle and a 20 ml scintillation vial should be labeled "i-
PrOH" and another 5 ml syringe with needle and 20 ml scintillation vial
should be labels "n-PrOH".
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D. The bottles containing anhydrous DMF, anhydrous i-PrOH and
anhydrous n-PrOH can be slightly pressurized relative to the surrounding
atmosphere with high purity, dry N2 to facilitate the withdrawal of material.
1. Attach rubber tubing to N2 supply manifold and close the other
outlets.
2. Turn on the N2 to a very gentle flow (at 3-5 psig).
3. Pressurize the DMF bottle while wearing gloves, remove the
needle from the DMF syringe and insert the needle base in the
open end of the tubing. (TAKE GREAT CARE to hold the needle
in the tube firmly or it will be released at this point like a projectile.)
4. Insert the needle in the septum of the DMF bottle and invert the
bottle.
5. When the bubbles decrease, right the bottle and remove the
needle.
6. Replace the needle on the DMF syringe.
7. Repeat the procedure for i-PrOH and n-PrOH using the
appropriate needle if needed.
8. Turn off the N2 flow.
E. Using the 10 ml syringe labelled "DMF," withdraw the approximate
amount of DMF needed (2 ml per serum bottle used in screening and
analysis). Transfer the DMF to the labeled 50 ml bottle and cap.
Preparation of Screening Samples
A. Label the 10 ml serum bottles needed for this step. One should be
labeled "DMF," another "DMF + i-PrOH + n-PrOH." Additional bottles,
one for each sample, should be labeled using the appropriate laboratory
sample number.
B. Pipet 2 ml DMF into the bottle labelled "DMF." Place septum (teflon side
down) on top of the bottle, cover both with metal cap and crimp.
1. The action of the crimping tool should be gentle but firm.
2. The cap should not move if sealed properly.
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3. If it is loose, rotate the vial 1 /4 turn and crimp again.
4. Repeat until tightly sealed.
C. Pipet 2 ml DMF, 200 n\ i-PrOH and 200 //I n-PrOH into appropriately
labeled bottle and cap as before.
D. For each sample:
1. Shake can on paint shaker for 5 minutes.
2. Pipet 2 ml DMF into bottle.
3. Weigh to nearest 1 mg on balance.
4. Remove the bottle to hood and add about 0.4 to 0.6 grams of
sample dropwise using a transfer pipette.
a. Add 10 drops of sample and reweigh.
b. Estimate how many additional drops of sample to add.
c. In the hood add the sample dropwise until the required
amount is added.
d. Reweigh to verify the amount added.
e. Make note of the total number of drops of sample added
and the weight increase.
5. Cap as before.
6. Shake vigorously.
III. Screen Samples
A. Use the DMF as the syringe rinse between every injection.
B. Flush a 10 /*! syringe with the pure DMF from its labelled bottle five times.
Dispose of the waste into a 20 ml scintillation vial set aside for waste
DMF.
C. Insert needle into DMF bottle all the way to the liquid level and repeatedly
fill and empty the syringe to expel air. Raise the needle stopping in the
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air space above the liquid. Pull the plunger to the 1 /*! mark drawing in
air.
D. Lower the needle into the liquid to be injected and pull the plunger to the
2 u\ mark. Raise the needle out of the liquid and advance the plunger to
the 4 pi mark. Verify the loading of exactly 1 /J of liquid into the syringe
before removal from the bottle.
E. When it has been verified that the volume is accurate, remove the needle
and syringe from the bottle.
F. Using the GC conditions outlined in Section IX of this procedure, inject
the contents of the syringe into the GC.
G. Hit the start buttons on the GC and the integrator.
H. Rinse the syringe with DMF at least five times disposing of the waste as
before.
I. Repeat steps A through H for the DMF + i-PrOH + n-PrOH solution and
the sample solutions.
J. The following information should be noted for each sample:
1. The presence of solids which made filling the syringe difficult and
what .steps had to be used to fill the syringe. Options include the
following:
a. Allowing the solids to settle, insert the needle into the air
space. Advance the plunger to the 1 //I mark drawing in air
and then carefully invert the sample and load the sample.
b. Centrifugation using a Dynac tabletop centrifuge (or
comparable equipment) at 70% maximum speed for five
minutes. The samples are in long narrow tubes with screw
caps. After centrifugation, the supernatant is transferred to
a small bottle and then capped.
c. Filtration, if used, is a last resort. Cleaning the filter in any
quantitatively accurate way is difficult.
2. Approximate water content. For samples with little or no water,
0.6 g of material can be used later when preparing for analysis.
Page 23
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Those with enough water to overwhelm the detector should be
prepared using 0.3 g, 0.2 g or 0.1 g as necessary.
3. Look for potential interference with i-PrOH elution. If the sample
contains i-PrOH or peaks that would interfere with its
quantification, select an alternative internal standard. Examine the
elution peak of n-PrOH. If its elution position is free of
interference, use it instead. In extreme cases ethanol may be
used.
IV. Prepare Internal Standard
A. Make the internal standard selection based on the screening results.
B. Since in most cases either i-PrOH or n-PrOH will be satisfactory, using
the labelled syringe withdraw the approximate amount of internal
standard needed (1 ml + 0.75 ml per sample).
V. Prepare Blanks
A. Label one 10 ml serum bottle B-1 and a second one B-2.
B. Add 2.0 ml DMF with the appropriate pipettor to B-1.
•4
C. Weigh the bottle, using gloves or tissue when handling to prevent finger
prints. Record the weight to the nearest 0.1 mg.
D. Using the Eppendorf pipettor add 200 n\ + 5 drops of the selected
internal standard.
E. Weigh and record as before.
F. Seal well and shake to mix.
G. Repeat steps B through F using B-2.
VI. Prepare References
A. Label one 10 ml serum bottle R-1 and a second one R-2.
B. Follow steps B through E of the blank preparation procedure described
above using the R-1 bottle.
C. With the Eppendorf pipette and a clean tip add 200 ^l deionized H2O.
Page 24
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D. Weigh, record the weight, seal well and shake.
E. Repeat steps B through D using R-2.
VII. Prepare Samples
A. Label three 10 ml serum bottles for each sample with the unique sample
identification number and add a different letter (A, B, or C) to each to
make each bottle label unique.
B. Mix paint or coating for five minutes on the paint shaker if it was not
mixed recently.
C. Follow steps B through E of the blank preparation procedure using the
_A bottle.
D. Modify the total weight of coating to be added using the data noted
during the screening. The relationship of the number of drops to the
weight noted during the sample screen preparation will help here. Add
the sample now.
E. Weigh, record the weight and cap the bottle immediately.
F. Mix the sample vigorously.
G. Repeat steps C through for the B and C bottles.
H. Repeat steps B through G for the other samples.
VIII. Analyze Samples
A. Use B-1 as the syringe rinse between every injection.
B. Fill a 10 //I syringe with B-1 five times, disposing of the liquid in the waste
DMF vial.
C. Draw in 1 n\ of B-1 as described earlier.
D. Using the GC conditions outlined in section IX of this procedure, inject
the contents of the syringe into the GC.
E. Hit the start buttons on both the GC and the integrator.
Page 25
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F. Rinse the syringe with B-1 five times, regardless of what was injected to
clear the syringe of potential solid deposits.
G. When the GC is ready for the next injection, rinse the syringe again with
B-1 five times.
H. Repeat steps C through G for each of the following: B-2, R-1, R-2, and
the three bottles (A, B, and C) prepared for the paints or coatings being
analyzed.
IX. ' GC Conditions
A. Use a Hewlett Packard 5890 A gas chromatograph (or comparable
equipment) with a thermal conductivity detector (TCD).
B. Column.
1. Packing Porapak Q
2. Dimensions 10 ft-4 mm ID
3. Column Material . Glass-1/4" OD
C. Use a Hewlett Packard 3357 Laboratory Automation System backed up
by a Hewlett Packard 3392A integrator or equivalent equipment.
D. GC parameters.
1. Flows
a. Column 45 cc/min
b. Total (column + ret): 112 cc/min
2. Oven
a. Equilibrium time 0.25 min
b. Initial oven temperature 90°C
(for a new column) 70°C
c. Initial time 0.00 min
d. Rate 20°C/min
Page 26
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e. Rnal oven temperature 210°C
f. Final time 24.00 min
3. Run length 30.00 min
4. Signal 1
a. Range 4
b. Zero 0.0
c. Attenuation 0
5. Injector
a. Injector A temperature 220°C
6. Detector
a. Detector A TCD ON (+)
b. Detector temperature 240°C
7. Purge ON
E. Integrator parameters.
1. Zero 20
2. Attenuation 2 4
3. Chart speed 0.5 cm/min
4. Peak width 0.16
5. Threshold 5
6. Area reject 100
7. Time table
a. INTG # 10 13.50 min
Page 27
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b.
INTG # 10
18.80 min
X.
F.
G.
H.
To start GC turn on oven temperature and detector. When both lights
are off, temperatures are at set points and the GC is ready.
When finished with analyses, turn off the detector and the oven.
GC maintenance.
1. Change the septum each day. Remember to turn off the detector
and the oven while making the change.
2. Make sure that the nut holding the septum in place is tightly
turned.
3. Make sure the TCD is turned off for the night.
Data
The following data should be recorded (I.S. is internal standard):
Sample
Weights
B1
B2
R1
R2
A
B
C
WtVial + DMF
(9)
+ I.S.
(g)
+ Water
(g)
+ Sample
(g)
Page 28
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Where:
Wt Vial + DMF
+ IS
+ Water
+ Sample
gross weight of vial and DMF solvent.
(Wt. Vial + DMF) + weight of internal
standard added.
(+ IS) + weight of water added to reference
sample R1 and R2.
(+ IS) + weight of paint or coating added to
each of A, B, or C for analysis
Sample Areas:
B1
B2
R1
R2
A
B
_C
Water Area
I.S. Area
DMF Area
Where:
Water Area = G.C. area counts for water
I.S. Area = G.C. area counts for the internal standard
DMF Area = G.C. area counts for the DMF solvent
XI. Calculations
A,, = Respective areas
W,, = Respective weights
VMFJ
Page 29
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Where:
i = Chemical compound
j = Blank or reference standard number (1 or 2)
B = area of the water peak in the blank
R = Response factor of water
Calculations are best performed by computer on a spreadsheet in conjunction
with an automated data acquisition system for analytical input from the gas
chromatograph system.
XII. Notes
A. Whenever a coating sample contains more than 40% H2O, a new sample
should be prepared using 0.4 g, 0.2 g or 0.1 g of coating.
B. If some compound elutes late and interferes with subsequent runs,
increase the Final Time of the chromatograph run sufficiently to elute the
substance prior to the start of the next run. A Final Time in the range of
25 minutes is usually sufficient to purge the column.
Page 30
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DETERMINATION OF WATER CONTENT IN COATINGS BY KARL FISCHER TITRATION
(Adapted from ASTM D 4017-81)
METHOD: The water content of coating materials is determined by dissolving the
sample in a suitable solvent and titrating it directly with standardized Karl
Fischer reagent to an electrometric end point.
EQUIPMENT:
I. Glassware/Labware
A. Reagent bottle top volumetric dispensers for chemicals which must be
maintained under anhydrous conditions.
II. Syringes
A. A 100 n\ syringe with needle - one.
B. A 10 ml disposable syringe without needle, but equipped with a cap -
one.
C. A 1 ml disposable syringe without needle, but equipped with a cap -
one.
III. Chemicals
A. Water, Type II reagent grade conforming to ASTM Specification D1193 is
best. (This calls for the use of distilled water with a conductivity of less
than 1.0 //mho/cm at 25 °C.) Freshly deionized (Dl) water may also be
used.
B. Karl Fischer Reagent (KFR), A solution which is available from suppliers
of laboratory chemicals and which contains iodine, sulfur dioxide, and
pyridine dissolved in ethylene glycol monomethyl ether. Methanol is not
generally used because 1) it may not dissolve many common resins, 2)
methanol reacts with some resins to produce water, and 3) methanol
may participate in water-forming esterification reactions in the presence
of certain mineral acids (for example, in the formation of acetals and
ketals from reaction with aldehydes and ketones), respectively, or may
participate in side reactions with certain amines and siloxanes.
C. Pyridine, reagent grade. Available from suppliers of laboratory
chemicals.
Page 31
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D. 1-Ethyipiperidine, reagent grade. Available from suppliers of laboratory
chemicals.
IV. Miscellaneous
A. Safety Equipment. Auxiliary laboratory equipment should include
provisions for hood ventilation of benchtop work space as well as
ventilation of the general laboratory area, storage for chemical reagents,
and storage for solvents and coatings and inks which present a
flammability risk because of their volatile solvent content.
V. Analytical Balance, Range: 0-20Q grams, Reproducibility: ± 0.1 mg.
VI. Karl Fischer Apparatus, manual or automatic, encompassed by the detailed
description given in ASTM Standard E 203-75 Test Method for Water Using Karl
Fischer Reagent. Apparatus should be equipped with a 20-25 ml buret with 0.1
ml divisions. A 1 ml microburet with 0.01 divisions may be obtained for analysis
of samples containing less than 0.5% water by weight.
PROCEDURE:
I. General Preparation
A. Assemble equipment needed.
1. Check Karl Fischer Apparatus being used. Clean titration vessel if
needed with fresh pyridine and discard waste liquid into a
dedicated and sealed waste disposal container (e.g., a 5 gallon
can with safety lid) which is stored in the hood. Perform
preliminary equipment checkout steps (following equipment
manufacturer's instructions).
2. Clean up work area, removing waste paper, solvent, chemical
reagent, or used labware materials.
3. Follow manufacturer's maintenance and setup instructions for the
Karl Fischer Apparatus being used.
B. Assemble Reagents.
1. Safety Precautions. The Karl Fischer Reagent (KFR) used in this
procedure contains four toxic compounds, namely iodine, sulfur
dioxide, pyridine, and ethylene glycol monomethyl ether. 1-
ethylpiperidine used as a catalyst for the reagent should be
Page 32
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considered equally toxic to pyridine and therefore handled with the
same care. All operations including dispensing of reagents should
be carried out in a hood. Rubber gloves and a face shield should
be worn when handling and transferring chemicals. Care must
exercised to avoid inhalation or skin contact.
2. MSDS (Material Safety Data Sheet) instructions. All reagents used
should be supplied with MSDS forms which contain physical,
chemical, and safety guideline/emergency information. The MSDS
sheets should be available in the same laboratory area where the
equipment is used. Particular attention should be paid to the
recommended emergency procedures to be followed in the event
of spillage or accidental inhalation or physical contact with the
chemicals being used.
3. Maintain anhydrous conditions. Follow instructions regarding
maintenance of purity and stability of reagent chemicals that are
provided by laboratory chemical suppliers. Do not leave
containers open or exposed to excessive sunlight or other extreme
conditions of temperature, humidity, or in potential contact with
other reactive materials. Use volumetric safety dispensers for
reagent bottles which are available from laboratory equipment
suppliers.
II. Standardize Karl Fischer Reagent
A. Charge Karl Fischer Apparatus with reagents.
1. Charge a clean, dry titration vessel (containing a magnetic stirring
bar) with pyridine to a level sufficient to cover the electrode sensor
tip plus 1 ml of 1 -ethylpiperidine catalyst per 20 ml of pyridine.
The 5% volumetric proportion of the catalyst yields the best
titration performance. This step may be accomplished
automatically by different apparatus but the net result should be
the same as outlined above. The magnetic stirrer should be on at
this time to provide mixing of the titration vessel solution. The
stirring rate should be vigorous but the end point electrodes
should remain fully submerged in the solution and excess bubble
formation should be avoided.
2. Charge the Karl Fischer Reagent (KFR) dispensing buret with KFR
to a point where an initial reading can be taken of the volumetric
level. Follow manufacturer's instructions if automatic or digital
dispensing provisions are included in the apparatus being used.
Page 33
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B. Pretitrate pyridine/1-ethylpiperidine solution to the end point indicated by
the equipment manufacturer by adding KFR from the dispensing buret to
cause the end point to hold for at least 30 seconds. Record the
volumetric level in the buret.
C. Adjust the Karl Fischer apparatus for maximum electrode sensitivity and
minimum titration rate. Follow manufacturer's guidelines.
D. Weigh the water standard specimen. Fill the 100 /d syringe with Type II
reagent grade distilled water and weigh the syringe and water to the
nearest 0.1 mg. Record the weight in grams to the fourth decimal place.
E. Inject the water standard from the 100 ^l syringe into the titration vessel
using the appropriate sample port in the Karl Fischer apparatus. If
necessary, immediately replace the sample port stopper to reseal the
titration vessel.
F. Titrate the water standard to the end point using the KFR dispensing
buret to cause the end point to hold for at least 30 seconds and record
the KFR volumetric level.
G. Weigh the empty syringe to the nearest 0.1 mg and record the weight in
grams to the fourth decimal place.
H. Calculate F (=Karl Fischer titre) in grams H2O per ml of Karl Fischer
Reagent used.
I. Calculation formula:
F = J/P
Where:
F = KFR titre
J = water added, grams
P = KFR used, ml
The value of F should be calculated and recorded to four significant
figures. Typical values of F are in the range of 0.004000 to 0.006000
grams/ml corresponding to a KFR titre volume, P of 12.5 to 8.33 ml,
respectively for a 50 n\ (approximately 0.05 gram) water standard
specimen or sample, J.
Page 34
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G. Repeat the standardization until replicate values of F agree within 1%.
Determine the mean of at least two such determinations. Carry out
calculations retaining at least one extra decimal figure beyond that of the
acquired data. Round off figures after final calculations.
Perform Screening Specimen Analysis
A. Prepare the titration vessel and KFR buret as described in Steps II. A and
II. B (except using the 25 ml buret for dispensing the KFR). Best results
are obtained wrth fresh solvent solution, that is containing no previously
titrated specimen in the vessel.
3. Mix the coating or mk sample container thoroughly (e.g., in a bench
scale paint shaker/mixer for a period of five mmutes_)
C. Draw a sample of the coating or ink using a 1 ml or 10 ml syringe (with
cap) applying the specimen size guidelines given in Table 1:
Expected Water,
(%)
0.5 - 1.0
1 -2
3 - 10
10 -30
30 - 70
> 70
Approximate Specimen
Weight
(g)
5
2 - 5
1 - 2
0.4 - 1.0
0.1 -0.4
0.1
Approximate Titrant
Volume at 5 mg/ml titr
(ml)
5 - 10
10-20
10 -20
20-25
15-25
20
Remove the syringe from the sample container, pull the plunger out a
little further, wipe the excess material off the syringe, and replace the cap
on the syringe tip. Weigh the filled syringe to the nearest 0.1 mg.
Reseal the sample container.
Inject the sample into the titration vessel containing the pretitrated
pyndine solution (after removing the syringe cap) and immediately reseal
the vessel, if necessary. A high stirring rate should be employed and at
least 2 minutes (preferably 5 minutes) should be allowed for the sample
to dissolve before starting the titration. Pull the plunger back out of the
syringe and replace the cap.
Page 35
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F. Reweigh the emptied syringe to the nearest 0.1 mg and calculate the
specimen weight by difference.
G. Calculation:
% water = (milliliters KFR used x F x 100)/(grams of sample)
IV. Perform the Sample Analysis
A. Adjust the specimen size based on findings of the screening analysis and
repeat the determination. The % water is determined by obtaining a
duplicate set of measurements and taking the average of the two results,
at a minimum.
B. If the calculation shows that 0.1 to 0.5 % water is present in the sample,
repeat the procedure using a 1 gram specimen and a 1 ml microburet for
KFR titration.
V. Notes
A. Accuracy-Repeatability/Reproducibility
1. Repeatability - Two results, each the mean of duplicate
determinations, obtained by the same operator on different days
should be considered suspect if they differ by more than 4.7 %
relative.
2. Reproducibility - Two results, each the mean of duplicate
determinations, obtained by operators in different laboratories
should be considered suspect if they differ by more than 15.0 %
relative.
B. Interferences
1. The possibility of interfering side reactions or the formation of
byproducts which prevent accurate determination of water content
is always possible. This method has been developed to minimize
those potential problems but if they are suspected, it should be
reported.
2. It is essential to use care and follow precise procedures when
dissolving and mixing the specimen samples to obtain a
homogeneous and therefore representative sample of the coating
or ink.
Page 36
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3. All reagents used should be less than one year old and from a
reliable laboratory reagent supplier. Contamination of reagents
and solutions may cause significant reproducibility problems.
C. Maintenance
1. Contamination of the KFR burets, the reagent reservoir glassware,
the titration vessel, and the coating of the sensing electrodes are
all potential problems to inspect for and to prevent by performing
periodic cleaning.
2. Clean the titration vessel by rinsing with fresh pyridine. Do not
use methanol or other solvents.
3. Maintain anhydrous conditions (dryness) in the titration vessel by
checking that drying tubes are in good condition and are tightly
connected. Replace desiccant when indicator color changes
through half the tube.
4. Follow manufacturer's guidelines regarding electrode performance
response and cleaning.
D. Disposal of Waste
1. A separate waste container, such as a 5 gallon solvent can with lid
should be maintained for spent or used reagents resulting from
the use and cleaning of the titration vessel. This should be
emptied for periodic disposal as a hazardous laboratory waste by
a reputable disposal organization.
Page 37
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Page 38
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DETERMINATION OF PERCENT VOLATILE CONTENT IN COATING SAMPLES (Adapted
from ASTM D2369-81)
METHOD: The percent volatile content (including water) as a weight fraction is
determined by measuring the weight loss of a known sample quantity,
which has been heated for one hour (60 minutes) at 110°C in a forced-
draft oven.
EQUIPMENT:
I. Glassware
A. Bottles of 50 ml capacity with a cap having an inert liner - two.
II. Syringes and Pipets
A. 5 ml disposable syringes without needle - one per sample.
B. A 10 ml pipette - one per sample.
III. Chemicals
A. Deionized water (H20).
B. Toluene.
IV. Miscellaneous
A. Aluminum foil weighing dishes - three per sample.
V. Analytical balance - Range: 0-200 grams, Reproducibility: ±0.1 mg
VI. Vacuum Oven and Vacuum Pump
VII. Desiccator
PROCEDURE:
I. General Preparation
A. Assemble equipment needed.
B. Put toluene in one of the 50 ml bottles and deionized water in the other.
Page 39
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Preparation of Samples
A. Inscribe an identification mark on each of three aluminum weighing
dishes (e.g. A, B, C) for each coating. Remember to add an identifying
mark to separate the coatings if more than one is under study.
B. Preheat the pans in the vacuum oven for 30 minutes at 110°C.
C. Place the dishes in a desiccator to cool to ambient temperature (about
15 minutes).
D. Weigh the dishes and record the weight.
E. For each coating:
1. Shake can on paint shaker for 5 minutes.
2. Add 3 ml ± 1 ml of suitable solvent (toluene or water) to each of
the three weighing dishes using the 10 ml pipettor.
3. Using the information obtained from the screening of samples
prior to determination of water content, estimate volatile content
and proceed.
4. Add to each weighing dish 0.6 ml of coating if it has a volatile
content less than 50 weight % or 0.8 ml if it has a volatile content
greater than 50 weight %.
a. Use a 5 ml disposable syringe.
b. Fill the syringe with coating.
c. Weigh the filled syringe to the nearest 0.1 mg and record
the weight.
d. Add an aliquot of the sample to the first dish, reweigh the
syringe and record the weight.
e. Add an aliquot of the sample to the second dish, reweigh
the syringe and record the weight.
f. Repeat this for the third dish.
Page 40
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5. Heat the prepared weighing dishes in the vacuum oven for 60
minutes at 110 ± 5°C with the vacuum valve cracked open but the
vent wide open (indicated vacuum barely detectable on vacuum
gauge, corresponding to 0.1 to 1" Hg vacuum).
6. Remove the dishes from the oven and place them immediately in a
desiccator, cool to ambient temperature about 15 minutes and
weigh them to the nearest 0.1 mg.
111.
Data
The following data is recorded:
Samples
A
B
C
Pan Wt.
(9)
Initial Wt.
Sample +
Syr
(9)
Final Wt.
Sample +
Syr.
(g)
Final Wt.
Pan +
Sample
(g)
Final Wt.
Sample.
(g)
VI.
Calculations
%VOC = Percent volatile matter in coating.
W, = Weight of the ith item.
-W
~ '*
InltSmpb+Syr
100
'Sa/npfe
Page 41
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DETERMINATION OF DENSITY OF PAINT, VARNISH, LACQUER, AND RELATED
PRODUCTS (Adapted from ASTM D1475-60 (Reapproved 1980))
METHOD: The density of the liquid at 25°C expressed in gm/ml and Ibs/gal is
determined by the following procedure. The accurately known absolute
density of distilled (or deionized) water is used to calibrate the volume of
a container. The same container is filled with sample liquid and weighed.
All measurements are taken after the container and contents equilibrate
at 25°C. .
EQUIPMENT:
I. Glassware
A. Container for boiling and storing distilled water.
B. Pycnometer - three per sample.
II. Syringes and Pipettes
A. A 25 ml pipette - three per sample.
III. Chemicals
A. Deionized water (H2O).
•
IV. Miscellaneous
A. Constant temperature bath held at 25°C ±0.1°C.
B. Desiccator.
V. Analytical Balance - Range: 0-200 grams, Reproducibility: ±0.1 mg
PROCEDURE:
I. General Preparation
A. Assemble equipment needed.
B. Freshly boil deionized water for use in the calibration step.
Page 43
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II. Determine Tare Weight of the Dry Pycnometers
A. Clean and dry the pycnometers and bring each of them to a constant
weight.
1. Strong acid or strong base cleaners and nonresidual solvents may
be used with glass containers.
2. For maximum accuracy, continue rinsing, drying, and weighing
until the difference between two successive weighing does not
exceed 0.001% of the weight of the container (0.0003 g for a 30 g
pycnometer).
3. Fingerprints on the container will change the weight and must be
avoided.
4. Record the weight. This and all subsequent references to
recording of information refer to the written account kept in the
data books for environmental samples.
III. Calibration of Pycnometers
A. Fill the pycnometers with the freshly boiled distilled water (or freshly
boiled deionized water) at a temperature below 25°C.
B. Immediately remove excess overflowed water or water held in
depressions by wiping dry with absorbent material.
C. Avoid occluding air bubbles in the container.
D. Bring the container and contents to 25°C using the constant temperature
bath.
E. Remove the excess overflow by wiping carefully with absorbent material.
Avoid wicking of water out of the orifice.
F. Dry the outside of the pycnometers.
G. Immediately weigh the filled pycnometers to the nearest
0.001% of its weight (0.0003 g for a 30 g pycnometer).
H. Record the weight.
Page 44
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IV.
V.
Density of the Sample
A. For each coating:
1. Shake can on paint shaker for 5 minutes if that has not been done
recently.
B. Repeat III using the sample instead of distilled water and using the 25 ml
pipette to load the pycnometer.
Data
The following data is recorded:
Samples
A
B
C
Pyc#
Pyc Wt.
(g)
Pyc +
Sample Wt.
(g)
Pyc Vol.
(ml)
VI. Calculations.
For the calibration:
y.
0.997072
Obtain the mean of at least three determinations.
Where:
V = volume of the pycnometer, ml.
N = weight of the pycnometer and water, g.
M = weight of the dry pycnometer, g.
0.997072 = absolute density of water at 25°C, g/ml
Page 45
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For the density determination:
and D=Dm*K
Where:
Dm = density, g/ml and D = density, Ib/gal.
W = weight of the filled pycnometer, g.
w = weight of empty pycnometer, g.
V = volume determined above, ml.
K = 8.345404
Page 46
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DETERMINATION OF DICHLOROMETHANE AND 1,1,1-TRICHLOROETHANE IN PAINTS
AND COATINGS BY DIRECT INJECTION INTO A GAS CHROMATOGRAPH (Adapted
from ASTM D4457-85)
METHOD: The percent dichloromethane and 1,1,1-trichloroethane content of
coating material is determined by dissolving the sample in a suitable
solvent and injecting it directly into a gas chromatograph. An internal
standard is added to the sample in a known quantity before
chromatography-for calibration.
EQUIPMENT:
I. Glassware/Labware
A. Reagent dispensing buret, 100 ml capacity - one.
B. 20 ml scintillation vials with teflon inverted cone cap seals - five per
sample.
C. 25 ml vials capable of being septum sealed - six + four per sample.
1. Teflon coated septa - six + four per sample.
2. Aluminum caps - six + four per sample.
II. Syringes and pipettes
A. 20 ml disposable syringes with needle - two.
B. 10 ml disposable syringes with needle - six.
C. 10 ml Eppendorf or equivalent volumetric pipettors with eight disposable
tips - one.
D. Transfer pipettes for dropwise addition of samples.
E. A 10 n\ syringe with needle.
III. Chemicals
A. Anhydrous N,N-Dimethylformamide (DMF), reagent grade.
Page 47
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B. Anhydrous 1-propanol (or 1-PrOH, n-propanol), gas chromatography
spectrophotometric grade.
C. Anhydrous 2-propanol (or 2-PrOH, isopropanol), gas chromatography
spectrophotometric grade.
D. 1,1,1 - Trichloroethane (or TCE, methyl chloroform), reagent grade (see
E. Dichloromethane (or DCE, methylene chloride), reagent grade (see E).
F. Halogenated hydrocarbon stabilizers - Commercial grades of TCE and
DCE contain stabilizers. Obtain the same solvent used in the coating or
find the type and quantity of stabilizer used and add it to the pure
solvent.
o
G. Carrier gas, Nitrogen (NJ of 99.995% or higher purity. High purity
Helium may also be used.
IV. Miscellaneous
A. Rubber tubing - 18 inches.
B. Bottle cap crimper.
C. Safety Equipment. Auxiliary laboratory equipment should include
provisions for hood ventilation of benchtop work space as well as
ventilation of the general laboratory area, storage for chemical reagents,
and storage for solvents and coatings and inks which present a
flammability risk because of their volatile solvent content.
V. Analytical Balance, Range: 0-200 grams, Reproducibility: ±0.1 mg.
VI. Gas Chromatograph (GC) - e.g., HP 5890 A
A. Thermal conductivity detector.
B. Porapak column - 4 ft.
PROCEDURE:
I. General Preparation
A. Assemble equipment needed.
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1. Clean up work area, removing waste paper, solvent, chemical
reagent, or used labware materials.
B. Assemble reagents.
1. Safety Precautions. All operations including dispensing of
reagents should be carried out in a hood. Rubber gloves and a
face shield should be worn when handling and transferring
chemicals. Care must exercised to avoid inhalation or skin
contact.
2. MSDS (Material Safety Data Sheet) instructions. All reagents used
should be supplied with MSDS forms which contain physical,
chemical, and safety guideline/ emergency information. The
MSDS sheets should be available in the same laboratory area
where the equipment is used. Particular attention should be paid
to the recommended emergency procedures to be followed in the
event of spillage or accidental inhalation or physical contact with
the chemicals being used.
3. Maintain anhydrous conditions. Follow instructions regarding
maintenance of purity and stability of reagent chemicals that are
provided by laboratory chemical suppliers. Do not leave
containers open or exposed to excessive sunlight or other extreme
conditions of temperature, humidity, or in potential contact with
other reactive materials. Use volumetric safety dispensers for
reagent bottles which are available from laboratory equipment
suppliers.
C. Fill a 20 ml scintillation vial with dichloromethane, cap it and label the vial
"DCM." Fill a 20 ml scintillation vial with 1,1,1-trichloroethane, cap it and
label it TCE."
D. One 20 ml syringe with needle and a 20 ml scintillation vial should be
labeled "1-PrOH" and another 20 ml syringe with needle and 20 ml -
scintillation vial should be labeled "2-PrOH". Set aside one 20 ml
scintillation vial, label it "Waste DMF," loosely cover it with a septum and
cap, but do not seal it.
E. If the bottles containing anhydrous DMF, anhydrous 1-PrOH and
anhydrous 2-PrOH are not slightly pressurized relative to the surrounding
atmosphere then that must be done now. (This is needed to facilitate the
withdrawal of material.)
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1. Attach rubber tubing to N2 supply manifold and close the other
outlets.
2. Turn on the N2 to a very gentle flow.
3. To pressurize the DMF bottle, wearing gloves remove the needle
from the DMF syringe and insert the needle base in the open end
of the tubing. (TAKE GREAT CARE to hold the needle in the tube
firmly or it will be released at this point like a projectile.)
4. Insert the needle in the septum of the DMF bottle and invert the
bottle.
5. When the bubbles decrease, right the bottle and remove the
needle.
6
6. Replace the needle on the DMF syringe.
7. Repeat the procedure for 1-PrOH and 2-PrOH using the appro-
priate needle if needed.
8. Turn off the N2 flow.
F. Check that the 100 ml dispensing buret is mounted on the DMF reagent
bottle and that sufficient DMF reagent is present to do the analysis
(approximately 20 ml for each 25 ml vial used in screening and analysis).
Preparation of Screening Samples
A. Label the 25 ml vials capable of being septum sealed that are needed for
this step. One should be labeled "DMF," another "DMF + 1-PrOH + 2-
PrOH." Additional vials, one for each sample, should be labeled using
the appropriate laboratory sample number.
B. Weigh the vial labeled "DMF" to 0.1 mg, dispense 17 ml DMF into the
bottle and weigh the vial again to determine the amount of DMF added.
Place septum-teflon side down-on top of the vial, cover both with metal
cap and crimp.
1. The action of the crimping tool should be gentle but firm.
2. The cap should not move if sealed properly.
3. If it is loose, rotate the vial turn and crimp again.
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4. Repeat until tightly sealed.
C. Dispense 17 ml DMF, then pipet 2 ml + 10 drops 1-PrOH and 2 ml + 10
drops 2-PrOH into appropriately labeled vial obtaining weights of each of
the three components added to 0.1 mg and cap as before.
D. For each screening sample:
1. Shake can on paint shaker for 5 minutes.
2. Dispense 17 ml DMF into the sample vial.
3. Weigh to the nearest 1 mg on the analytical balance.
4. Remove the bottle to hood and add about 4 ml of sample
dropwise using a 10 ml disposable syringe.
a. Add 10 drops of sample using a transfer pipette and
reweigh.
b. Estimate how many additional drops of sample to add to
bring the total sample addition amount up to 5 g.
c. In the hood add the sample dropwise until the required
amount is added.
d. Reweigh to verify the amount added.
e. Make note of the total number of drops of sample added
and the weight increase.
5. Cap as before.
6. Shake vigorously.
Screen samples
A. Use the DMF from the 25 ml septum sealed vial as the syringe rinse
between every injection.
B. Flush a 10 n\ syringe with the pure DMF from its labelled bottle five times.
Dispose of the waste into a 20 ml scintillation vial set aside for waste
DMF and cover loosely with a septum and cap.
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C. Insert needle into DMF vial but stop in the air space above the liquid.
Pull the plunger to the 1 /il mark drawing in air and then lower the needle
into the liquid and pull the plunger to the 2 n\ mark. Raise the needle out
of the liquid and advance the plunger to the 4 //I mark. Verify the loading
of exactly 1 n\ of liquid into the syringe before removal from the bottle.
D. When it has been verified that the volume is accurate, remove the needle
and syringe from the vial.
E. Using the GC conditions outlined in the GC section of this procedure,
inject the contents of the syringe into the GC.
F. Hit the start buttons on the GC and the integrator.
G. Rinse the syringe with DMF at least five times disposing of the waste as
before.
H. Repeat steps A through F for the DMF + 1-PrOH + 2-PrOH solution and
the sample solutions. If there is any doubt of the elution times of 1-PrOH
or 2-PrOH, the pure components can be injected into the gas
chromatograph for positive determination.
I. The following information should be noted for each sample:
1. The presence of solids which made filling the syringe difficult and
what steps had to be used to fill the syringe, including:
a. Allowing the solids to settle, insert the needle into the air
space. Advance the plunger to the 1 fj\ mark drawing in air
and then carefully invert the sample and load the sample.
b. Centrifugation using a laboratory tabletop centrifuge (or
comparable equipment) at 70% maximum speed for five
minutes. The samples are in long narrow tubes with screw
caps. After centrifugation, the supernatant is transferred to
a small bottle and it is then capped.
c. Filtration if used is a last resort. Cleaning the filter in any
quantitatively accurate way is difficult.
2. Approximate exempt solvent content. For samples with little or no
exempt solvent present, 5 g of material can be used later when
preparing for analysis. Those with enough dichloromethane or
Page 52
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1,1,1-trichloroethane to overwhelm the detector should be
prepared using 3 g, 2 g, or 1 g as necessary.
3. Look for potential interference with 1-PrOH elution. If the sample
contains 1 -PrOH or peaks that would interfere with its
quantification, select an alternative internal standard. Examine the
eJution peak of 2-PrOH. If its elution position is free of
interference, use it instead. In extreme cases, ethanol, other
alcohols, esters, or hydrocarbons may be used.
IV. Prepare internal standard (IS)
A. Make the internal standard selection based on the screening results.
B. Since in most cases either 1 -PrOH or 2-PrOH will be satisfactory, use the
labeled syringe to withdraw the approximately 20 ml amount of internal
standard needed (10 ml + 7.5 ml per sample) and charge it to the
labeled 20 ml scintillation vial.
V. Prepare Blanks
A. Label one 25 ml vial B-1 and a second one B-2.
B. Add 17 ml DMF from the reagent dispenser to B-1.
C. Weigh the bottle, using gloves or tissue when handling to prevent finger
prints. Record the weight to five decimal places.
D. Using the Eppendorf (or equivalent) pipettor add 2.5 ml of the selected
internal standard.
E. Weigh and record as before.
F. Seal well and shake to mix.
G. Repeat steps B through F using B-2.
VI. Prepare References
A. Label one 25 ml vial R-1 and a second one R-2.
B. Follow steps B through E of the blank preparation procedure using the
R-1 bottle.
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C. With the Eppendorf (or equivalent) pipette and a clean tip add 2.7 ml of
dichloromethane.
D. Weigh and record the weight.
E. With the Eppendorf (or equivalent) pipette and a clean tip add 2.7 ml of
1,1,1 -trichloroethane.
F. Weigh and record the weight.
G. Seal well and shake.
H. Repeat steps B through G using R-2.
VII. Prepare Samples
A. Label three 25 ml vials for each sample with the unique sample
identification number and add a different letter (A, B, or C) to each to
make each bottle.
B. Mix paint or coating for five minutes on the paint shaker if it was not
mixed recently.
C. Follow steps B through E of the blank preparation procedure using the
_A bottle.
D. Modify the total weight of coating to be added using the data noted
during the screening. The relationship of the number of drops to the
weight noted during the sample screen preparation will help here. Add
the sample now using a fresh 10 ml disposable syringe.
E. Weigh, record the weight and cap the bottle immediately.
F. Mix the sample vigorously.
G. Repeat steps C through F for the B and C bottles.
H. Repeat steps B through G for the other samples.
VIII. Analyze Samples
A. Use B-1 as the syringe rinse between every injection.
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B. Fill a 10 fj,\ syringe with B-1 five times disposing of the liquid in the waste
DMF vial.
C. Draw in 1 /d of B-1 as described earlier.
D. Using the GC conditions outlined in the GC section of this procedure,
inject the contents of the syringe into the GC.
E. Hit the start buttons on both the GC and the integrator.
F. Rinse the syringe with B-1 five times regardless of what was injected to
clear the syringe of potential solid deposits.
G. When the GC is ready for the next injection, rinse the syringe again with
B-1 five times.
H. Repeat steps C through G for each of the following: B-2, R-1, R-2, and
the three bottles (A, B, and C) prepared for the paints or coatings being
analyzed.
IX. GC Conditions
A. Use a Hewlett Packard 5890 A gas chromatograph (or comparable
equipment) with a thermal conductivity detector (TCD).
B. Column.
1. Packing Porapak R
2. Dimensions 4 ft-4 mm ID
3. Column Material Glass-1/4" CD
C. GC parameters.
1. Flows
a. Column 45 cc/min
b. Total (column + ref.) 100 cc/min
2. Oven
a. Equilibrium time 0.25 min
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b. Initial oven temp. 90°C
(for a new column) 70°C
c. Initial time 0.00 min
d. Rate 20°C/min
e. Final oven temperature 210°C
f. Final time 24.00 min
3. Run length 30.00 min
4. Signal 1
a. Range 4
b. Zero 30.0
c. Attenuation 0
5. Injector
a. Injector A temperature 220°C
6. Detector
a. Detector A TCD ON (+)
b. Detector temperature 240°C
7. Purge ON
D. Integrator parameters.
1. Zero 20
2. Attenuation 2 4
3. Chart speed 0.5 cm/min
4. Peak width 0.16
5. Threshold 5
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X.
6. Area reject
7. Time table
a.
b.
INTO # 10
INTO # 10
100
13.50 min.
18.80 min.
E. To start GC turn on oven temperature and detector. When both lights
are off, temperatures are at set points and the GC is ready.
F. When finished turn off the detector and the oven.
G. GC maintenance.
1. Change the septum each day. Remember to turn off the detector
and the oven while making the change.
2. Make sure that the nut holding the septum in place is tightly
turned.
3. Make sure the TCD is turned off for the night.
Data.
The following data should be recorded:
Sample
Weights
B1
B2
R1
R2
A
B
C
Wt
Vial + DMF
(9)
+ I.S.
(g)
+ dichloro-
methane
(g)
+ 1,1,1-
trichloro-
ethane
(g)
+ Sample
(g)
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Where:
Wt Vial + DMF =
+ IS =
+ dichloromethane =
+ 1,1,1-trichloroethane =
+ Sample =
gross weight of vial and DMF solvent.
(Wt Vial + DMF) + weight of internal
standard added.
(4- IS) + weight of dichloromethan added
to the reference samples R1 and R2.
(+ dichloromethane) + weight of 1,1,1-
trichloromethane added to reference
samples R1 and R2.
(+ IS) -i- weight of paint or coating sample
added to each of A, B, or C for analysis.
Sample
Areas
B1
B2
R1
R2
A
B
__C
Dichloro-
. methane
Area
1,1,1 -tri-
chlorometh-
ane Area
I.S. Area
DMF Area
Where:
Dichloromethane Area =
1,1,1 -Trichlorormethane Area =
IS Area =
DMF Area =
G.C. Area counts for
dichlormethane.
G.C. Area counts for 1,1,1-trichloro-
methane.
G.C. Area counts for the internal
standard.
G.C. Area counts for the DMF
solvent.
XI. Calculations
A,, = Respective areas
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W,, = Respective weights
= AESJ
O *•*•*
-------
Calculations are best performed by computer on a spreadsheet in conjunction
with an automated data acquisition system for analytical input from the gas
chromatograph system.
Xll. Notes
A. Whenever a coating sample contains more than 40% of either
dichloromethane or 1,1,1-trichloroethane, a new sample should be
prepared using 3 g, 2 g, or 1 g of coating.
B. If some compound elutes late and interferes with subsequent runs,
increase the Rnal Time sufficiently to elute the substance prior to the
start of the next run. A Final Time in the range of 25 minutes is usually
sufficient to purge the column.
C. Accuracy-Repeatabiiity/Reproducibility for 1,1,1-trichloroethane.
1. Repeatability - Two results, each the mean of duplicate
determinations, obtained by the same operator on different days
should be considered suspect if they differ by more than 3.0%
relative.
2. Reproducibility - Two results, each the mean of duplicate
determinations, obtained by operators in different laboratories
should be considered suspect if they differ by more than 8.1%
relative.
D. Accuracy-Repeatability/Reproducibility for Dichloromethane.
1. Repeatability - Two results, each the mean of duplicate
determinations, obtained by the same operator on different days
should be considered suspect if they differ by more than 3.0%
relative.
2. Reproducibility - Two results, each the mean of duplicate
determinations, obtained by operators in different laboratories
should be considered suspect if they differ by more than 17.9%
relative.
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E. Interferences.
1. The possibility of interfering side reactions or the formation of
byproducts which may prevent accurate determination of
dichloromethane and 1,1,1-trichloroethane content is always
possible. This method has been developed to minimize those
potential problems but if they are suspected, it should be reported.
2. It is essential to use care and follow precise procedures when
dissolving and mixing the specimen samples to obtain a
homogeneous and therefore representative sample of the coating
or ink.
3. All reagents used should be less than one year old and from a
reliable laboratory reagent supplier. Contamination of reagents
and solutions may cause significant r»eproducibility problems.
F. Maintenance.
1. Contamination of the glassware/labware, syringes and pipettes,
reagent bottles, and dispensers are all potential problems to
inspect for and to prevent by performing periodic cleaning.
2. Maintain anhydrous conditions (dryness) in reagent vessels and
glassware/labware by keeping seals and lids in place and tightly
connected.
3. Follow manufacturer's guidelines regarding reagent bottle and
syringe/pipettor/dispenser handling and cleaning.
G. Disposal of waste.
1. A separate waste container, such as a 5 gallon solvent can with lid
should be maintained for spent or used reagents from use and
cleaning of the titration vessel. This should be emptied for
periodic disposal as a hazardous laboratory waste by a reputable
disposal organization.
Page 61
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Page 62
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SECTION 5
REFERENCE METHOD 24A-DETERMINATION OF VOLATILE MATTER
CONTENT AND DENSITY OF PRINTING INKS AND RELATED COATINGS
1. Applicability and Principle
1.1 Applicability. This method applies to the determination of the volatile
organic compound (VOC) content and density of solvent-borne (solvent
reducible) printing inks or related coatings.
1.2 Principle. Separate procedures are used to determine the VOC weight
fraction and density of the coating and the density of the solvent in the
coating. The VOC weight fraction is determined by measuring the weight
loss of a known sample quantity which has been heated for a specified
length of time at a specified temperature. The density of both the coat-
ing and solvent are measured by a standard procedure. From this
information the VOC volume fraction is calculated.
2. Procedure
2.1 Weight Fraction VOC.
2.1.1 Apparatus.
2.1.1.1 Weighing Dishes. Aluminum foil, 58 mm in diameter
by 18 mm high, with a flat bottom. There must be at
least three weighing dishes per sample.
2.1.1.2 Disposable Syringe. 5ml.
2.1.1.3 Analytical Balance. To measure to within 0.1 mg.
2.1.1.4 Oven. Vacuum oven capable of maintaining a
temperature of 120 ±2°C and an absolute pressure
of 510 ±51 mm Hg for 4 hours. Alternatively, a
forced draft oven capable of maintaining a tempera-
ture of 120 ±2°C for 24 hours.
2.1.2 Analysis. Shake or mix the sample thoroughly to assure that all
the solids are completely suspended. Label and weigh to the
nearest 0.1 mg a weighing dish and record this weight (MX1).
Page 63
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Remove a sample of the coating using a 5-ml syringe without a
needle. Weigh the syringe and sample to the nearest 0.1 mg and
record this weight (MCY1). Transfer 1 to 3 g of the sample to the
tared weighing dish. Reweigh the syringe and sample to the
nearest 0.1 mg and record this weight (MCY2). Heat the weighing
dish and sample in a vacuum oven at an absolute pressure of 510
±51 mm Hg and a temperature of 120 ±2°C for 4 hours.
Alternatively, heat the weighing dish and sample in a forced draft
oven at a temperature of 120 ±2°C for 24 hours. After the
weighing dish has cooled, reweigh it to the nearest 0.1 mg and
record the weight (M^. Repeat this procedure for a total of three
determinations for each sample.
2.2 Coating Density. Determine the density of the ink or related coating
according to the procedure outlined in ASTM D1475-60 (Reapproved
1980), (incorporated by reference - see §60.17).
2.3 Solvent Density. Determine the density of the solvent according to the
procedure outlined in ASTM D1475-60 (Reapproved 1980). Make a total
of three determinations for each coating. Report the density D0 as the
arithmetic average of the three determinations.
3. Calculations
3.1 Weight Fraction VOC. Calculate the weight fraction volatile organic
content W0 using the following equation:
Report the weight fraction VOC W0 as the arithmetic average of the three
determinations.
3.2 Volume Fraction VOC. Calculate the volume fraction volatile organic
content V0 using the following equation:
W D
y =_ll£Jl£ Eq. 24A-2
Page 64
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4. Bibliography
4.1 Standard Test Method for Density of Paint, Varnish, Lacquer, and Related
Products. ASTM Designation D1475-60 (Reapproved 1980).
4.2 Teleconversation. Wright, Chuck, Inmont Corporation with Reich, R. A.,
Radian Corporation. September 25, 1979. Gravure Ink Analysis.
4.3 Teleconversation. Oppenheimer, Robert, Gravure Research Institute with
Burt, Rick, Radian Corporation, November 5, 1979. Gravure Ink Analysis.
Page 65
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Page 66
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SECTION 6
STANDARD OPERATING PROCEDURES FOR METHOD 24A ANALYSES
APPLICATION OF EPA METHOD 24A
EPA Method 24A is performed on publication rotogravure inks for New Source
Performance Standard (NSPS) compliance. These inks are viscous, solvent-based
formulations which frequently must be transferred from sample containers with small or
large blade spatulas. Although not needed to measure weight fraction VOC, to
determine the volume fraction VOC, it is necessary to have a separate sample of the
ink solvent for density measurement. There are no dispersing agent which are
presently recommended to prevent incorporation of solvent compounds into the
hardened dry residue remaining after oven treatment performed for VOC weight
percent measurement.
VOC DETERMINATION
The determination of the VOC weight fraction is otherwise clearly described in
the method and SOP for Method 24 given in Section 4. No additional instructions are
considered necessary.
DENSITY DETERMINATION
In the process of making ink density determinations by ASTM D1475-60
(Reapproved 1980), it is critical to carefully pack the heavy coating into the
pycnometer using small and large blade spatulas without allowing air bubbles or void
spaces to be formed. It is also important to thoroughly clean the outside of the
pycnometer and carefully avoid weighing errors which can significantly affect the
accuracy of the VOC weight fraction determination. Otherwise, SOP guidance for use
of ASTM D1475-60 with Method 24, given in Section 4, is applicable for use with
Method 24A as well.
Page 67
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Page 68
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SECTION 7
BIBLIOGRAPHY
ASTM Procedures in Order of ASTM Number
1. Standard Specification for Industrial Grade Toluene, ASTM D362-S4. 1990
Annual Book of ASTM Standards, Volume 6.03. Philadelphia, PA, 1990.
2. Standard Specification for Reagent Water, ASTM D1193-77. 1990 Annual Book
of ASTM Standards, Volume 6.03. Philadelphia, PA, 1990.
3. Standard Test Method for Water in Volatile Solvents (Fischer Reagent Titration
Method), ASTM D1364-87. 1990 Annual Book of ASTM Standards, Volume
6.03. Philadelphia, PA, 1990.
4. Standard Test Method for Density of Paint, Varnish, Lacquer, and Related
Products, ASTM D1475-85. 1990 Annual Book of ASTM Standards, Volume
6.01. Philadelphia, PA, 1990.
5. Standard Test Method for Volatile Content of Coatings, ASTM D2369-87. 1990
Annual Book of ASTM Standards, Volume 6.01. Philadelphia, PA, 1990.
6. Standard Test Method for Volume Nonvolatile Matter in Clear or Pigmented
Coatings, ASTM D2697-86. 1990 Annual Book of ASTM Standards, Volume
6.01. Philadelphia, PA, 1990.
7. Standard Guide for Determining Volatile and Nonvolatile Content of Paint and
Related Coatings, ASTM D2832-83. 1990 Annual Book of ASTM Standards,
Volume 6.01. Philadelphia, PA, 1990.
8. Standard Specification for 2-Ethoxyethyl Acetate (99% Grade), ASTM D3728-88.
1990 Annual Book of ASTM Standards, Volume 6.03. Philadelphia, PA, 1990.
9. Standard Test Method for Water Content of Water-Reducible Paints by Direct
Injection Into a Gas Chromatograph, ASTM D3792-86. 1990 Annual Book of
ASTM Standards, Volume 6.01. Philadelphia, PA, 1990.
10. Standard Practice for Sampling Liquid Paints and Related Pigmented Coatings,
ASTM D3925-81. 1990 Annual Book of ASTM Standards, Volume 6.01.
Philadelphia, PA, 1990.
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11. Standard Practice for Determining Volatile Organic Compound (VOC) Content of
Paints and Related Coatings, ASTM D3960-89. 1990 Annual Book of ASTM
Standards, Volume 6.01. Philadelphia, PA, 1990.
12. Standard Practice for Interlaboratory Testing of Paint and Related Materials,
ASTM D3980-88. 1990 Annual Book of ASTM Standards, Volume 6.01.
Philadelphia, PA, 1990.
13. Standard Test Method for Water in Paints and Paint Materials by Karl Fischer
Method, ASTM D4017-88. 1990 Annual Book of ASTM Standards, Volume
6.01. Philadelphia, PA, 1990.
14. Manual Sampling of Petroleum and Petroleum Products, ASTM D4057-81. 1990
Annual Book of ASTM Standards, Volume 5.03. Philadelphia, PA, 1990.
15. Standard Test Method for Determination of Dichloromethane and 1,1,1-
Trichloroethane in Paints and Coatings by Direct Injection into a Gas
Chromatograph, ASTM D4457-85. 1990 Annual Book of ASTM Standards,
Volume 6.03. Philadelphia, PA, 1990.
16. Specification for Gravity Convection and Forced-Ventilation Ovens, ASTM E145-
68. 1990 Annual Book of ASTM Standards, Volume 14.02. Philadelphia, PA,
1990.
17. Practice for Determining the Precision Data of ASTM Methods for Analysis and
Testing of Industrial Chemicals, ASTM E180-85. 1990 Annual Book of ASTM
Standards, Volume 15.05. Philadelphia, PA, 1990.
18. Standard Test Method for Water Using Karl Fischer Reagent, ASTM E203-75.
1990 Annual Book of ASTM Standards, Volume 15.05. Philadelphia, PA, 1990.
19. Standard Practice for Sampling Industrial Chemicals, ASTM E300-86. 1990
Annual Book of ASTM Standards, Volume 6.02. Philadelphia, PA, 1990.
20. Excerpts from Standard Practice for Use of the International System of Units
(SI) (the Modernized Metric System), ASTM E380-89. 1990 Annual Book of
ASTM Standards, Volume 6.01. Philadelphia, PA, 1990.
21. Standard Practice for Conducting an Interlaboratory Study to Determine the
Precision of a Test Method, ASTM E691-87. 1990 Annual Book of ASTM
Standards, Volume 6.01. Philadelphia, PA, 1990.
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22. Standard Guide for ASTM Standard Specification Quality Statements, ASTM
E1267-88. 1990 Annual Book of ASTM Standards, Volume 6.01. Philadelphia,
PA, 1990.
Other Literature/Bibliographical References
23. Federal Test Method Standard No. 141c, Paint, Varnish, Lacquer, and Related
Materials; Methods of Inspection, Sampling, and Testing. General Services
Administration, January 24, 1986.
24. EPA-340/1-84-001 a, VOC Sampling and Analysis Workshop, Volume I VOC
Reference Methods. U.S. EPA, OAQPS, SSCD, Washington, DC, September
1983.
25. EPA-340/1-86-016, A Guideline for Surface Coating Calculations. U.S. EPA,
OAQPS, SSCD, Washington, DC, July 1986.
26. EPA 340/1-88-003, Recordkeeping Guidance Document for Surface Coating
Operations and the Graphics Arts Industry, U.S. EPA, SSCD, Washington, DC,
May 1989.
27. EPA-450/2-77-008, Control of Volatile Organic Emissions from Existing Station-
ary Sources - Volume II: Surface Coating of Cans, Coils, Paper, Fabrics,
Automobiles, and Light-Duty Trucks. U.S. EPA, OAQPS, Research Triangle
Park, NC, May 1977.
28. EPA-450/3-84-019, Procedures for Certifying Quantity of Volatile Organic
Compounds Emitted by Paint, Ink, and Other Coatings. U.S. EPA, OAQPS,
ESED, Research Triangle Park, NC, December 1984.
29. EPA-600/4-77-027b, Quality Assurance Handbook for Air Pollution
Measurement Systems: Volume III. Stationary Source Specific Methods. U.S.
EPA, EMSL, Research Triangle Park, NC, November 1976.
30. EPA-600/9-76-005, Quality Assurance Handbook for Air Pollution Measurement
Systems: Volume I. Principles. U.S. EPA, EMSL, Research Triangle Park, NC,
December 1984.
^ 31. Code of Federal Regulations, General Provisions, Performance Tests, 40 CFR
60.8 Subpart A, Washington, DC, 1989.
*,
f
32. Code of Federal Regulations, General Provisions, Incorporation by Reference,
40 CFR 60.17 Subpart A, Washington, DC, 1989.
Page 71
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33. Standards of Performance for Surface Coating of Metal Furniture, 40 CFR 60
Subpart EE, Washington, DC, 1989.
34. Standards of Performance for Automobile and Light-Duty Truck Surface Coating
Operations, 40 CFR 60 Subpart MM, Washington, DC, 1989.
35. Standards of Performance for the Graphic Arts Industry: Publication
Rotogravure Printing, 40 CFR 60 Subpart QQ, Washington, DC, 1989.
36. Standards of Performance for Pressure Sensitive Tape and Label Surface
Coating Operations, 40 CFR 60 Subpart RR, Washington, DC, 1989.
37. Standards of Performance for Industrial Surface Coating: Large Appliances, 40
CFR 60 Subpart SS, Washington, DC, 1989.
38. Standards of Performance for Metal Coil Surface Coating, 40 CFR 60 Subpart
TT, Washington, DC, 1989.
39. Standards of Performance for the Beverage Can Surface Coating Industry, 40
CFR 60 Subpart WW, Washington, DC, 1989.
40. Standards of Performance for the Rubber Tire Manufacturing Industry, 40 CFR
60 Subpart BBB, Washington, DC, 1989.
41. Standards of Performance for Flexible Vinyl and Urethane Coating and Printing,
40 CFR 60 Subpart FFF, Washington, DC, 1989.
42. Standards of Performance for Magnetic Tape Coating Facilities, 40 CFR 60
Subpart SSS, Washington, DC, 1989.
43. Standards of Performance for Industrial Surface Coating: Surface Coating of
Plastic Parts for Business Machines, 40 CFR 60 Subpart TTT, Washington, DC,
1989.
44. Code of Federal Regulations, Reference Methods 24 AND 24A, 40 CFR 60,
Appendix A, Washington, DC 1989.
45. Manual on Determination of Volatile Organic Compounds in Paints, Inks, and
Related Coating Products, J. John Brezinski, ed., ASTM Manual Series: MNL 4,
1989.
Page 72
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I
(Pit
TECHNICAL REPORT DATA
read Imovcnons on me reverse Of fore comnietmii
1. REPORT NQ.
EPA-340/1-91-011
3. RECIPIENT'S ACCESSION NO.
4. TITLE ANO SUBTITLE
Standard Operating Procedure for Analysis of Coating and
Ink Samples by Reference Methods 24 a.nd 24A
5. REPORT DATE
Seotember
ft. PERFORMING ORGANIZATION CODE
7. AUTHQR(S)
Bruce A. Olson, Melinda K. Wood, John T. Chehaske
3. PERFORMING ORGANIZATION REPORT NO.
91-133-T4/S
9»PEflFORMINO ORGANIZATION NAME ANO AOQRESS
* Pacific Environmental Services, Inc.
'"SoO Herndon Parkway, Suite 200
Herndon, Virginia 22070-5225
10. PROGRAM ELEMENT NO.
WA 91-133
11 CONTRACT/GRANT NO.
68-02-4464
12. SPONSORING AGENCY NAME ANO ADDRESS
U.S. Environmental Protection Agency
Office of Air Quality Planning and Standards
Stationary Source Compliance Division
Washington, D.C. 20460
13. TYPE OF REPORT ANO PERIOD COVERED
Final __
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
SSCD, Organic Chemicals Section, 401
Washington, D.C. 20460 Phone: (703)
M St., S.W.
308-3663
See a so:
;EN-34W1) EPA/1-91-010: Sampling
EPA/1-91-012: References
18. ABSTRACT
Standard procedures are presented in this report for the handling and physical/
chemical characterization of coating and ink samples that require analysis by EPA
Reference Methods 24 or 24A (RM 24/24A) as found in 40 CFR 60, Appendix A. For the
purpose of developing consistency among analytical laboratories nationwide, it
delineates the activities deemed proper and necessary to ensure that an accurate and
precise measurement of coating or ink sample properties are made. If the activities are
conducted as described, questions concerning the validity and reproducibility of analyses
performed can be avoided.
This Standard Operating Procedure (SOP) covers all types of industrial coating
and printing ink operations, regardless of the method of application of coating or ink,
including, for example, dip, spray, roll, flow, electrostatic, or electro-deposition
processes. Special cases involving use of exempt solvents dichloromethane (methylene
chloride) and 1,1,1-trichloroethane (methyl chloroform) or multi-component mixture
coating formulations are covered in accordance with most recent technical and regulatory
thinking, however, this is not a regulatory but a technical procedure guideline document.
17.
KEY WORDS ANO DOCUMENT ANALYSIS
a. DESCRIPTORS
w Air Pollution Sampling
v Coatings VOC
Inks ASTM Methods
N Analysis
Solvents
18. OISTRI8UTION STATEMENT
b.lOENTIFIERS/OPGN £NOED TERMS
Analysis of Coatings
and Inks
19. SECURITY CLASS / Tins fltporll
Unclassified
20. SECURITY CLASS iTlut parr;
Unclassified
c. COSATi Field Group
73
22. PRICE j
EPA f**m 2220-1 (H«». 4—77) »<*cvious COITION is OMOUCTK
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