ASTM D6886-03

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Designation:D6886–03
Standard Test Method for
Speciation of the Volatile Organic Compounds (VOCs) in
Low VOC Content Waterborne Air-Dry Coatings by Gas
Chromatograpy
This standard is issued under the fixed designation D 6886; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (e) indicates an editorial change since the last revision or reapproval.
1. Scope MethylAcetateor t-ButylAcetateContentofSolventborne
and Waterborne Paints, Coatings, Resins, and Raw Mate-
1.1 This test method is for the determination of the weight
rials by Direct Injection into A Gas Chromatograph
percent of individual volatile organic compounds in low VOC
D 6438 Test Method for Acetone, Methyl Acetate, and
content waterborne latex air-dry coatings. The method is
Parachlorobenzotrifluoride Content of Paints, and Coat-
intendedprimarilyforanalysisofwaterbornecoatingsinwhich
ings by Solid Phase Microextraction-Gas Chromatogra-
the material VOC content is below 5 weight percent. The
phy
method has been used successfully with higher VOC content
E 177 Practice for Use of the Terms Precision and Bias in
waterborne coatings.
ASTM Test Methods
1.2 This method may also be used to measure the exempt
E 691 Practice for Conducting an Interlaboratory Study to
volatile organic compound content (acetone, methyl acetate,
Determine the Precision of a Test Method
andp-chlorobezotrifluoride)ofwaterbornecoatings.Themeth-
odology is virtually identical to that used in Test Method
3. Terminology
D 6133 and similar to that used in Test Method D 6438.
3.1 Abbreviations:
1.3 Volatile compounds that are present at the 0.05 weight
3.1.1 CW/DVB—Carbowaxy/divinylbenzene
percent level or greater can be determined. Solid phase
3.1.2 DB—2-(2-butoxyethoxy)ethanol; Butyl Carbitoly;
microextraction will detect volatile compounds at lower levels.
diethylene glycol monobutyl ether
1.4 This standard does not purport to address all of the
3.1.3 EB—2-butoxyethanol; Butyl Cellosolvey; ethylene
safety concerns, if any, associated with its use. It is the
glycol monobutyl ether
responsibility of the user of this standard to establish appro-
3.1.4 EG—ethylene glycol
priate safety and health practices and determine the applica-
3.1.5 FID—flame ionization detector
bility of regulatory limitations prior to use.
3.1.6 F-VOC—formulation data calculated volatile organic
2. Referenced Documents compound in g/(L-water)
3.1.7 GC—gas chromatograph
2.1 ASTM Standards:
3.1.8 PG—propylene glycol
D 1475 Test Method for Density of Liquid Coatings, Inks,
2 3.1.9 % RSD—percent relative standard deviation
and Related Products
3.1.10 SPME—solid phase microextraction
D 2369 Test Method for Volatile Content of Coatings
3.1.11 Std Dev—standard deviation
D 3792 Test Method for Water Content of Coatings by
3.1.12 TX—2,2,4-trimethypentane-1,3-diol, monoisobu-
Direct Injection Into a Gas Chromatograph
tyrate; Texanoly
D 3925 Practice for Sampling Liquid Paints and Related
3.1.13 VOC—volatile organic compound
Pigmented Coatings
3.1.14 X-VOC—experimental volatile organic compound in
D 3960 Practice for Determining Volatile Organic Com-
g/(L-water)
pound (VOC) Content of Paints and Related Coatings
D 4017 Test Method forWater in Paints and Paint Materials
4. Summary of Test Method
by Karl Fischer Method
4.1 A known weight of coating is dispersed in tetrahydro-
D 6133 Test Method for Acetone p-Chlorobenzotrifluoride
furan(THF),internallystandardized,andanalyzedbycapillary
gas chromatography to give a speciated composition of the
1 volatile organic compounds and exempt organic compounds, if
This test method is under the jurisdiction of ASTM Committee D01 on Paint
and Related Coatings, Materials, andApplications and is the direct responsibility of
Subcommittee D01.21 on Chemical Analysis of Paints and Paint Materials.
Current edition approved March 10, 2003. Published May 2003.
2 3
Annual Book of ASTM Standards, Vol 06.01. Annual Book of ASTM Standards, Vol 14.02.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
D6886–03
any, present in the coating. Summation of the individual 6. Apparatus
volatile organic compound weight fractions gives the total
6.1 SPME Sampling Apparatus and Fibers, manual
VOC content of the coating measured in weight percent (Note
SPMEholdersfittedwitha70µmCarbowaxy/Divinylbenzene
1).
(CW/DVB) StableFlex fiber assembly.
6.2 Gas Chromatograph, FID Detection with Electronic
NOTE 1—Using the provisions of Practice D 3960, the VOC content of
Data Acquisition System—Any capillary gas chromatograph
coatings measured in g/Lminus water, or other units, may be determined.
equipped with a flame ionization detector and temperature
Since the determination of weight percent VOC in the present method is
programming capability may be used. Electronic flow control,
by direct measurement, either the water fraction (Test Method D 3792 or
Test Method D 4017) or the nonvolatile fraction (Test Method D 2369) which gives a constant carrier gas flow, is highly recom-
may be determined indirectly in the application of Practice D 3960. The
mended.
equationsforcalculatingregulatoryVOCcontentwhennoexemptvolatile
6.3 Standard FID Instrument Conditions:
compounds are present are:
Detector Flame ionization
Columns Primary column: 30 m by 0.25 mm 5 % phenyl/95 % methyl
f ~D !
VOC P
siloxane (PMPS) (Note 4) , 1.0 µm film thickness.
VOC 5 (1)
1 2 @~1 2 f 2 f !~D /D !#
NV VOC P W Confirmatory Columns: 30 m by 0.25 mm polydimethylsiloxane
(PDMS), 0.25 µm film thickness; 30 m by 0.25 mm
CarbowaxY (CW), 0.25 µm film thickness.
or
Carrier Gas Helium
f ~D ! Flow Rate 1.0 mL per min, constant flow (24.9 cm/s at 40°)
VOC P
VOC 5 (2)
Split Ratio Variable
1 2 @f ~D /D !#
W P W
Temperatures, °C
Inlet 260°
where:
Detector 270°
D ,f ,f , and f = coating density, nonvolatile fraction,
P NV VOC W
Initial 40° for 4 min
VOC fraction, and water fraction, respec-
Rate 10° per min to 250°, hold 5 min
tively.
NOTE 4—The column designated as PMPS is commercially available
from several vendors by the following designations: DB-5, SPB-5, HP-5,
4.2 DirectGC/FID,GC/MSandsolidphasemicroextraction
AT-5, CP Sil 8CB, RTx-5, BP-5.
/ gas chromatography (SPME/GC) of the coating may be used
to facilitate identification of the volatile compounds present in
7. Reagents and Materials
a coating. Table X1.1 lists the GC retention times for the
7.1 Purity of Reagents—Reagent grade chemicals shall be
volatile compounds which may be found in low VOC content
used in all tests. Unless otherwise indicated, all reagents shall
waterborne air-dry coatings. Table X1.1 also lists possible
conform to the available specifications of the Committee on
internal standards for use in the analysis and minor volatile
Analytical Reagents of the American Chemical Society. Other
components which are sometimes found in waterborne coat-
grades may be used, provided it is first ascertained that the
ings (Note 2).
reagent is of sufficiently high purity to permit its use without
lessening the accuracy of the determination.
NOTE 2—The analyst should consult MSDS and product data sheets for
possible information regarding solvents which may be present in a 7.2 Carrier Gas, helium of 99.995 % or higher purity.
particularcoating.SPME/GCmaybeusedtoascertainthatdecomposition
7.3 Tetrahydrofuran (THF), HPLC grade.
volatiles are not measured.
7.4 1-Propanol, p-fluorotoluene, cyclohexanol,
p-chlorotoluene and p-cymene, 99 + mole %.
5. Significance and Use
7.5 The volatile organic compounds listed in Table X1.1.
7.6 Fluorocarbon-faced septum vials, 20 mL and 40 mL
5.1 InusingPracticeD 3960tomeasuretheregulatoryVOC
capacity.
content of coatings, precision tends to be poor for low VOC
content waterborne coatings because the VOC weight fraction
8. Column and Fiber Conditioning
is determined indirectly.The present method first identifies and
8.1 The capillary columns should be conditioned according
then quantifies the weight fraction of individual VOCs directly
to the manufacturer’s recommendation. The columns may then
in low VOC content waterborne air-dry coatings. The total
be used indefinitely without further conditioning.
VOC weight fraction can be obtained by adding the individual
8.2 TheSPMEfibershouldbeconditionedandusedaccord-
weight fraction values (Note 3).
ing to the manufacturer’s recommendation.
NOTE 3—An effort is currently underway in California to consider
8.3 The SPME fiber should be inserted into a 260°C
changing mass-based VOC regulations for architectural coatings to
injection port for 30 s prior to each sampling event.
reactivity-based VOC regulations. In California, reactivity based regula-
tions have already been implemented for aerosol coatings, that is,
9. Preparation of Standards
MIR-indexed regulations (California Air Resources Board). Reactivity
9.1 Prepare a stock mixture of ethylene glycol (EG), pro-
based regulations would require knowing the weight fractions of each
pylene glycol (PG), ethylene glycol monobutyl ether (EB),
individual volatile compound present in a coating.
p-cymene (CY) [or other suitable internal standard], diethylene
5.2 SPME/GC makes it possible to identify very low levels
of volatile compounds in a coating and could serve to make it
possible to identify the presence of hazardous air pollutants 4
Available from the Supelco Company, Supelco Park, Bellefonte, PA 16823-
(HAPs). 0048.
D6886–03
glycol monobutyl ether (DB), and Texanol (TX) by weighing ~AA!~MI!~100!
%X 5 (4)
~AI!~RF!~MC!
one or two grams of each into an appropriate vial. The weight
of each component should be approximately the same and
where:
determined to 0.1 mg. Mix the contents.
X = one of several possible volatile compounds in the
9.2 Transfer approximately 100 µLof the stock mixture to a
coating,
septum-capped vial containing 10 mL of THF and mix the
RF = relative response factor of compound X,
contents (Note 5).This solution will contain each of the known
AA = peak area of compound X,
analytes at a concentration of approximately 2 mg/mL.
MI = weight of internal standard in 10 mL THF,
AI = peak area of internal standard, and
NOTE 5—The solvents EG, PG, EB, DB andTexanol are widely used in
MC = weight of coating.
themanufactureoflowVOCcontentwaterborneair-drycoatingsandmay
be expected as highly probable components of these coatings. The
NOTE 7—If volatile compounds other than those in the standard (9.1)
tetrahydrofuran solvent must be analyzed by GC to determine if possible
are present in the coating, the identity should be confirmed by retention
impurities interfere/coelute with the analytes being tested.
time comparison with authentic material and the relative response factor
should be determined as outlined in 9.1-9.3. Commercial Texanol may
9.3 Chromatographthesolutionin9.2byinjecting1µLinto
contain small amounts of 2,2,4-trimethylpentane-1,3-diol which elutes
the PMPS column using the chromatographic conditions given
approximately 0.5 min before butyl carbitol. Acetone and isopropyl
in 6.3. Calculate the relative response factors for each of the
alcohol have nearly the same retention time on a 5 % phenyl/95 % PDMS
analytes relative to the p-cymene internal standard using the
column and if either is found, their identities should be confirmed on a
relationship: different column. Isobutyl alcohol coelutes with the solvent (THF) and
must be determined on a different column. SPME (11.2) is especially
AA * MI
useful for confirming the presence of isobutyl alcohol since no THF is
RF 5 (3)
AI * MA
used in this procedure.
where:
11. Solid Phase Microextraction Procedure
RF = relative response factor,
AA = area of analyte, 11.1 Since a dispersion of coating in THF is injected into a
MI = weight of internal standard (from 9.1),
relatively hot GC injection port, peaks representing decompo-
AI = area of internal standard, and
sition products may be observed and should not be considered
MA = weight of analyte (from 9.1).
asVOCs.Solidphasemicroextractionallowssamplingofmost
VOCs at low temperature and may be used to determine if GC
10. Paint Analysis
peaks observed in the direct GC analysis (Section 10) are
actual VOCs or decomposition products. If desired, the SPME
10.1 Using a 100 mL volumetric flask, make up a concen-
procedure may be used prior to direct analysis to determine
trated standard solution containing p-cymene (or other suitable
which VOCs are present in the coating. If GC/MS is available,
internal standard) in THF at a concentration of approximately
the SPME procedure is especially useful for identification of
1 g per 100 mL and known to the nearest 0.1 mg.
VOCs and exempt compounds present in a coating sample.
10.2 Using standard quantitative dilution techniques, dilute
11.2 Place approximately 5 to 10 g of liquid waterborne
the concentrated standard solution to give a working standard
coating into a 40 mL fluorocarbon-faced septum vial. If using
solution such that the internal standard concentration is near 1
a smaller vial, reduce the coating amount. Close the vial with
mg per mL. Calculate the actual concentration.
a fluorocarbon-faced septum cap and heat to 55 to 60°C in an
10.3 Pipette10mLofworkingstandardsolutionintoa20or
oven or other suitable heat source (oil bath, water bath, heated
40 mL vial and close with a fluorocarbon-faced septum cap.
metal block). Do not let the contents contact the inside face of
Using a disposable 1 mLsyringe, add approximately 0.6 to 0.8
the septum cap. Insert the SPME fiber through the septum cap
g of the well-mixed paint through the septum cap and weigh to
and sample the headspace for 3 to 4 min using a conditioned
0.1 mg (Note 6). Mix the contents vigorously by shaking for 1
CW/DVB SPME fiber. Desorb the fiber for 10 s onto the
min followed by sonication for 5 min. Let the vial stand to
capillary column and obtain the gas chromatogram using the
permit pigments, if any, to settle.
standard chromatographic conditions described in 6.3. Identify
NOTE 6—The paint should be drawn into the syringe without an the volatile components present in the liquid paint using
attached syringe needle. Excess paint is wiped from the syringe and the
retention time values given in Table X1.1. The peaks found by
needle is then attached for paint transfer. The mass of the paint may be
this SPME procedure should correspond to the peaks found by
determined by either the difference in the weight of the filled and empty
the direct procedure. If peaks found in the direct procedure are
syringe or by the difference in the weight of the vial before and after
not found by
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