ASTM D6886-18

This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
Designation: D6886 − 18
Standard Test Method for
Determination of the Weight Percent Individual Volatile
Organic Compounds in Waterborne Air-Dry Coatings by Gas
Chromatography
This standard is issued under the fixed designation D6886; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
during the one hour at 110°C conditions of EPA Method 24. Some or all
1. Scope
ofthesematerialsremaininthepaintfilmandthereforearenotconsidered
1.1 This test method is for the determination of the weight
volatile organic compounds according to EPA Method 24. In addition,
percent of individual volatile organic compounds in water- some compounds may decompose at the high inlet temperature of the GC.
However, note the EPAMethod 24 has poor precision and accuracy at low
borne air-dry coatings (Note 1).
levels of volatile organic compounds.
1.2 This method may be used for the analysis of coatings
NOTE 2—This method measures volatile organic compound weight of
containing silanes, siloxanes, and silane-siloxane blends. air-dry coatings directly as opposed to other methods in Practice D3960
whichmeasurethevolatileorganiccompoundweightpercentindirectly.A
1.3 This method is not suitable for the analysis of coatings
direct measurement of the weight percent particularly in low volatile
that cure by chemical reaction (this includes two-component
organic compound content waterborne coatings, generally gives better
precision. California Polytechnic State University carried out an extensive
coatings and coatings which cure when heated) because the
study for the California Air Resources Board comparing the precision of
dilution herein required will impede the chemical reaction
the direct method with the indirect method (CARB Standard Agreement
required for these types of coatings.
No. 04.329) Detailed results of this study may be found at http://
www.arb.ca.gov/coatings/arch/Final_Report_6_11_09.pdf. This study
1.4 Precision statistics for this method have been deter-
may be used to decide if the present method or other methods in Practice
mined for waterborne coatings in which the volatile organic
D3960 are preferred for a specific coating.
compound weight percent is below 5 percent. The method has
1.8 The values stated in SI units are to be regarded as
been used successfully with higher organic content waterborne
standard. No other units of measurement are included in this
coatings and with solventborne coatings (Note 2).
standard.
1.5 This method may also be used to measure the exempt
1.9 This standard does not purport to address all of the
volatile organic compound content (for example, acetone,
safety concerns, if any, associated with its use. It is the
methyl acetate, t-butyl acetate and p-chlorobenzotrifluoride) of
responsibility of the user of this standard to establish appro-
waterborne and solvent-borne coatings. Check local regula-
priate safety, health, and environmental practices and deter-
tions for a list of exempt compounds. The methodology is
mine the applicability of regulatory limitations prior to use.
virtually identical to that used inTest Method D6133 which, as
1.10 This international standard was developed in accor-
written, is specific for only exempt volatile compounds.
dance with internationally recognized principles on standard-
1.6 Volatile compounds that are present at the 0.005 weight
ization established in the Decision on Principles for the
percent level (50 ppm) or greater can be determined. A
Development of International Standards, Guides and Recom-
procedure for doing so is given in Section 9.
mendations issued by the World Trade Organization Technical
1.7 Volatile organic compound content of a coating can be
Barriers to Trade (TBT) Committee.
calculated using data from Test Method D6886 but requires
other data (see Appendix X2.)
2. Referenced Documents
NOTE 1—Data from this method will not always provide the volatile
2.1 ASTM Standards:
organic compound content of a paint film equivalent to EPA Method 24.
D1475 Test Method for Density of Liquid Coatings, Inks,
Some compounds and some semi-volatile compounds may be considered
volatile using the GC conditions specified but will not fully volatilize and Related Products
D2369 Test Method for Volatile Content of Coatings
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. For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Current edition approved Oct. 1, 2018. Published October 2018. Originally contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
ɛ1
approved in 2003. Last previous edition approved in 2014 as D6886 – 14 . DOI: Standards volume information, refer to the standard’s Document Summary page on
10.1520/D6886-18. the ASTM website.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D6886 − 18
D3792 Test Method forWater Content of Coatings by Direct 3.1.19 SPDE—solid phase dynamic extraction
Injection Into a Gas Chromatograph
3.1.20 THF—tetrahydrofuran
D3925 Practice for Sampling Liquid Paints and Related
3.1.21 TMPD-IB—2,2,4-trimethypentane-1,3-diol,
Pigmented Coatings
monoisobutyrate
D3960 PracticeforDeterminingVolatileOrganicCompound
(VOC) Content of Paints and Related Coatings
3.1.22 TMPD-DIB—2,2,4-trimethypentane-1,3-diol, di-
D4017 Test Method for Water in Paints and Paint Materials
isobutyrate
by Karl Fischer Method
3.1.23 VOC—volatile organic compound used in various air
D6133 Test Method for Acetone, p-Chlorobenzotrifluoride,
quality regulations
Methyl Acetate or t-Butyl Acetate Content of Solvent-
borne and Waterborne Paints, Coatings, Resins, and Raw
4. Summary of Test Method
Materials by Direct Injection Into a Gas Chromatograph
D7358 Test Method for Water Content of Paints by Quanti-
4.1 A known weight of coating is dispersed in methanol or
tative Calcium Hydride Reaction Test Kit
tetrahydrofuran (THF), internally standardized, and analyzed
E177 Practice for Use of the Terms Precision and Bias in
by capillary gas chromatography to give a speciated composi-
ASTM Test Methods
tion of the volatile organic compounds (Note 3). Summation of
E691 Practice for Conducting an Interlaboratory Study to
theindividualvolatileorganiccompoundweightpercentsgives
Determine the Precision of a Test Method
the total volatile organic content of the coating measured in
weight percent.
2.2 Other Documents:
EPAMethod24 —DeterminationofVolatileMatterContent,
NOTE 3—Methanol can be used as a first choice as a solvent for all
waterborne coatings. THF can be used for solventborne coatings.Acetone
WaterContent,Density,VolumeSolids,andWeightSolids
may also be used for solventborne coatings but should not be used for
of Surface Coatings
waterbornecoatingsbecauseitmayreactwithammoniaandamineswhich
40 CFR 51.100 (s) List of components that EPA has classi-
are frequently found in waterborne coatings. Other solvents can be used if
fied as VOC-exempt
needed but the choice of solvent should be reported.
SCAQMD M313 Determination of Volatile Organic Com-
4.2 DirectGC/FID,GC/MSandsolidphasemicroextraction
pounds (VOC) by Gas Chromatography/Mass
(SPME) / gas chromatography of the coating may be used to
Spectrometry/Flame Ionization Detection (GC/MS/FID)
facilitate identification of the volatile compounds present in a
coating (Note 4). Table X1.1 lists the GC retention times for
3. Terminology
some of the volatile compounds which may be found in low
3.1 Acronyms:
volatile organic compound content air-dry coatings and for
3.1.1 DB—2-(2-butoxyethoxy)ethanol; Butyl Carbitol; di-
several possible internal standards, ordinarily not present in
ethylene glycol monobutyl ether
coatings, which may be used (Note 4).
3.1.2 DP—diethylene glycol monopropyl ether
NOTE 4—The analyst should consult SDS and product data sheets for
information regarding solvents which are expected in a particular coating.
3.1.3 DPM—dipropylene glycol monomethyl ether
Additional solvents, not shown on the SDS or PDS may also be present in
3.1.4 DPnB—dipropylene glycol monobutyl ether the coating. Retention times given in Appendix X1 must be verified for
each individual instrument.
3.1.5 DPnP—dipropylene glycol monopropyl ether
NOTE 5—The accuracy of the volatile organic compound weight
3.1.6 EB—2-butoxyethanol; Butyl Cellosolve; ethylene
percent determined using Test Method D6886 is dependent on the proper
glycol monobutyl ether identification of the compounds detected in the chromatogram. The
response of the FID used in the GC is dependent on the compound
3.1.7 EG—ethylene glycol
detected. The accuracy of the determination requires proper identification
(by GC/MS, by retention time, or by analyzing the sample on a GC
3.1.8 EGDE—ethylene glycol diethyl ether
column with a different stationary phase) and calibration of the GC for the
3.1.9 EP—2-propoxyethanol
compounds detected.
3.1.10 FID—flame ionization detector
4.3 The methods for analysis are:
3.1.11 GC—gas chromatograph
4.3.1 Method A—Analysis is performed using GC/FID by
3.1.12 MS—mass spectrometer
preparing and analyzing standards to determine response
factors and using these response factors for determination of
3.1.13 PG—propylene glycol
the weight concentrations of analytes.
3.1.14 PnB—propylene glycol monobutyl ether
4.3.2 Method B—Analysis is performed using GC/
3.1.15 PnP—propylene glycol monopropyl ether
microreactor/FID (which converts all carbon-containing mol-
3.1.16 RRF—relative response factor
ecules into methane prior to detection in an FID) by first
3.1.17 MRRF—microreactor relative response factor validating the system and subsequently quantifying using
tabulated response factors.
3.1.18 SPME—solid phase microextraction
4.3.3 Method C—Analysis is performed using GC/MS.This
methodismostoftenusedinconjunctionwitheitherMethodA
or Method B, for identification of analytes. Precision statistics
Butyl Carbitol is a registered trademark of The Dow Chemical Company.
Butyl Cellosolve is a registered trademark of The Dow Chemical Company. have not been determined for using GC/MS for quantification.
D6886 − 18
of a reaction with the extraction solvent, then results for that compound
5. Significance and Use
should be discounted from the volatile measured by Test Method D6886.
5.1 In using Practice D3960 to measure the volatile organic
compound content of waterborne coatings, precision can be 6. Apparatus
poor for low volatile organic compound content air-dry coat-
6.1 Gas Chromatograph, with Electronic Data Acquisition
ings if the volatile organic weight percent is determined
System FID Detection, FID/Microreactor Detection. or Mass
indirectly. The present method directly identifies and then
Spectrometry Detection—Any capillary gas chromatograph
quantifies the weight percent of individual volatile organic
equipped with a flame ionization detector microreactor flame
compounds in air-dry coatings (Note 6). The total volatile
ionization detector, or mass spectrometer and temperature
organic weight percent can be obtained by adding the indi-
programming capability may be used. Electronic flow control,
vidual weight percent values (Note 7).
which gives a constant carrier gas flow, is highly recom-
NOTE 6—The present method may be used to speciate solvent-borne
mended. Note that a full precision study has only been
air-dry coatings. However, since these normally contain high, and often
completed for GC with FID detection (Tables X1.2-X1.4). A
complex, quantities of solvent, precision tends to be better using other
preliminary precision study has been completed for GC/
methods contained in Practice D3960, where the volatile fraction is
determined by a direct weight loss determination.
Microreactor/FID (Table X1.5).
NOTE 7—Detectable compounds may result from thermal decomposi-
6.2 Standard GC/FID, GC/Microreactor/FID, and GC/MS
tion in a hot injection port or from reaction with the extraction solvent. If
it can be shown that a material is a decomposition product, or is the result Instrument Conditions:
A
GC/FID GC/Microreactor /FID GC/MS
Instrument Conditions
Method A Method B Method C
B
Detector Flame ionization Microreactor/flame ionization 70 eV electron impact mass spectrometer
Microreactor Air Supply Flow Rate 2.5 mL per min
Microreactor Hydrogen Supply Flow 35 mL per min
Rate
Microreactor Temperature, °C, 450°
Source Temperature, °C, 230°
Quadrupole Temperature °C, 150°
Transfer Line Temperature°C, 260°
Scanning Parameters Mass 29 to 400 amu
FID Air Flow Rate 350 mL per min 350 per min
FID H Air Rate 35 mL per min 1.5 per mL
C
Columns Primary column: 30 m by 0.25 mm 5 % phenyl/95 % methyl siloxane (PMPS) ,C 1.0 µm film thickness
Confirmatory columns: 30 m by 0.25 mm polydimethylsiloxane (PDMS), 0.25 µm film thickness;
30 m by 0.25 mm Carbowax (CW), 0.25 µm film thickness
Carrier Gas Helium
Flow Rate 1.0 mL per min, constant flow (24.9 cm/s at 40°)
D
Split Ratio 50 to 1
Temperatures, °C,
Primary Column
Inlet 260°
Detector 270°
Initial 50° for 4 min
Rate 20° per min to 250°, hold 6 min (total run time = 20 min)
Temperatures, °C,
Confirmatory Columns
Inlet 260°
Detector 270°
Initial 40° for 4 min
Rate 10° per min to 250°, hold 25 min (total run time = 50 min)
A
The microreactor (for example, Polyarc, a registered trademark of Activated Research Company) is a two-step oxidation-reduction reactor that converts organic
compounds to methane prior to detection in an FID.
B
Any mass spectrometer may be used. The conditions specified are for a quadrupole mass spectrometer and are listed as a reference only.
C
The column designated as PMPS is commercially available from several vendors by the following designations: DB-5, SPB-5, HP-5, AT-5, CP Sil 8 CB, RTx-5, BP-5.
The column designated as PDMS is available by the designations DB-1, SPB-1, HP-1,AT-1, CP Sil 5 CB, Rtx-1. The column designated as Carbowax is available by the
designations Supelcowax 10, DB-Wax, HP-Wax,AT-Wax, CP-Wax 52 CB, Rtx-Wax, BP-20. Inert versions (or other equivalent designations) of the columns listed above
are recommended because they may provide better peak shapes.
D
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