1、Designation: D6886 18Standard Test Method forDetermination of the Weight Percent Individual VolatileOrganic Compounds in Waterborne Air-Dry Coatings by GasChromatography1This standard is issued under the fixed designation D6886; the number immediately following the designation indicates the year ofo
2、riginal adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1. Scope1.1 This test method is for the determination of the weightperce
3、nt of individual volatile organic compounds in water-borne air-dry coatings (Note 1).1.2 This method may be used for the analysis of coatingscontaining silanes, siloxanes, and silane-siloxane blends.1.3 This method is not suitable for the analysis of coatingsthat cure by chemical reaction (this incl
4、udes two-componentcoatings and coatings which cure when heated) because thedilution herein required will impede the chemical reactionrequired for these types of coatings.1.4 Precision statistics for this method have been deter-mined for waterborne coatings in which the volatile organiccompound weigh
5、t percent is below 5 percent. The method hasbeen used successfully with higher organic content waterbornecoatings and with solventborne coatings (Note 2).1.5 This method may also be used to measure the exemptvolatile organic compound content (for example, acetone,methyl acetate, t-butyl acetate and
6、p-chlorobenzotrifluoride) ofwaterborne and solvent-borne coatings. Check local regula-tions for a list of exempt compounds. The methodology isvirtually identical to that used in Test Method D6133 which, aswritten, is specific for only exempt volatile compounds.1.6 Volatile compounds that are present
7、 at the 0.005 weightpercent level (50 ppm) or greater can be determined. Aprocedure for doing so is given in Section 9.1.7 Volatile organic compound content of a coating can becalculated using data from Test Method D6886 but requiresother data (see Appendix X2.)NOTE 1Data from this method will not a
8、lways provide the volatileorganic compound content of a paint film equivalent to EPA Method 24.Some compounds and some semi-volatile compounds may be consideredvolatile using the GC conditions specified but will not fully volatilizeduring the one hour at 110C conditions of EPA Method 24. Some or all
9、of these materials remain in the paint film and therefore are not consideredvolatile organic compounds according to EPA Method 24. In addition,some compounds may decompose at the high inlet temperature of the GC.However, note the EPAMethod 24 has poor precision and accuracy at lowlevels of volatile
10、organic compounds.NOTE 2This method measures volatile organic compound weight ofair-dry coatings directly as opposed to other methods in Practice D3960which measure the volatile organic compound weight percent indirectly.Adirect measurement of the weight percent particularly in low volatileorganic c
11、ompound content waterborne coatings, generally gives betterprecision. California Polytechnic State University carried out an extensivestudy for the California Air Resources Board comparing the precision ofthe direct method with the indirect method (CARB Standard AgreementNo. 04.329) Detailed results
12、 of this study may be found at http:/www.arb.ca.gov/coatings/arch/Final_Report_6_11_09.pdf. This studymay be used to decide if the present method or other methods in PracticeD3960 are preferred for a specific coating.1.8 The values stated in SI units are to be regarded asstandard. No other units of
13、measurement are included in thisstandard.1.9 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is theresponsibility of the user of this standard to establish appro-priate safety, health, and environmental practices and deter-mine the applicabili
14、ty of regulatory limitations prior to use.1.10 This international standard was developed in accor-dance with internationally recognized principles on standard-ization established in the Decision on Principles for theDevelopment of International Standards, Guides and Recom-mendations issued by the Wo
15、rld Trade Organization TechnicalBarriers to Trade (TBT) Committee.2. Referenced Documents2.1 ASTM Standards:2D1475 Test Method for Density of Liquid Coatings, Inks,and Related ProductsD2369 Test Method for Volatile Content of Coatings1This test method is under the jurisdiction of ASTM Committee D01
16、on Paintand Related Coatings, Materials, and Applications and is the direct responsibility ofSubcommittee D01.21 on Chemical Analysis of Paints and Paint Materials.Current edition approved Oct. 1, 2018. Published October 2018. Originallyapproved in 2003. Last previous edition approved in 2014 as D68
17、86 141. DOI:10.1520/D6886-18.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.Copyright ASTM International, 10
18、0 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United StatesThis international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for theDevelopment of International Standards, Guides and R
19、ecommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.1D3792 Test Method for Water Content of Coatings by DirectInjection Into a Gas ChromatographD3925 Practice for Sampling Liquid Paints and RelatedPigmented CoatingsD3960 Practice for Determining Volatile
20、 Organic Compound(VOC) Content of Paints and Related CoatingsD4017 Test Method for Water in Paints and Paint Materialsby Karl Fischer MethodD6133 Test Method for Acetone, p-Chlorobenzotrifluoride,Methyl Acetate or t-Butyl Acetate Content of Solvent-borne and Waterborne Paints, Coatings, Resins, and
21、RawMaterials by Direct Injection Into a Gas ChromatographD7358 Test Method for Water Content of Paints by Quanti-tative Calcium Hydride Reaction Test KitE177 Practice for Use of the Terms Precision and Bias inASTM Test MethodsE691 Practice for Conducting an Interlaboratory Study toDetermine the Prec
22、ision of a Test Method2.2 Other Documents:EPAMethod 24 Determination of Volatile Matter Content,Water Content, Density, Volume Solids, and Weight Solidsof Surface Coatings40 CFR 51.100 (s) List of components that EPA has classi-fied as VOC-exemptSCAQMD M313 Determination of Volatile Organic Com-poun
23、ds (VOC) by Gas Chromatography/MassSpectrometry/Flame Ionization Detection (GC/MS/FID)3. Terminology3.1 Acronyms:3.1.1 DB2-(2-butoxyethoxy)ethanol; Butyl Carbitol;3di-ethylene glycol monobutyl ether3.1.2 DPdiethylene glycol monopropyl ether3.1.3 DPMdipropylene glycol monomethyl ether3.1.4 DPnBdiprop
24、ylene glycol monobutyl ether3.1.5 DPnPdipropylene glycol monopropyl ether3.1.6 EB2-butoxyethanol; Butyl Cellosolve;4ethyleneglycol monobutyl ether3.1.7 EGethylene glycol3.1.8 EGDEethylene glycol diethyl ether3.1.9 EP2-propoxyethanol3.1.10 FIDflame ionization detector3.1.11 GCgas chromatograph3.1.12
25、MSmass spectrometer3.1.13 PGpropylene glycol3.1.14 PnBpropylene glycol monobutyl ether3.1.15 PnPpropylene glycol monopropyl ether3.1.16 RRFrelative response factor3.1.17 MRRFmicroreactor relative response factor3.1.18 SPMEsolid phase microextraction3.1.19 SPDEsolid phase dynamic extraction3.1.20 THF
26、tetrahydrofuran3.1.21 TMPD-IB2,2,4-trimethypentane-1,3-diol,monoisobutyrate3.1.22 TMPD-DIB2,2,4-trimethypentane-1,3-diol, di-isobutyrate3.1.23 VOCvolatile organic compound used in various airquality regulations4. Summary of Test Method4.1 A known weight of coating is dispersed in methanol ortetrahyd
27、rofuran (THF), internally standardized, and analyzedby capillary gas chromatography to give a speciated composi-tion of the volatile organic compounds (Note 3). Summation ofthe individual volatile organic compound weight percents givesthe total volatile organic content of the coating measured inweig
28、ht percent.NOTE 3Methanol can be used as a first choice as a solvent for allwaterborne coatings. THF can be used for solventborne coatings. Acetonemay also be used for solventborne coatings but should not be used forwaterborne coatings because it may react with ammonia and amines whichare frequently
29、 found in waterborne coatings. Other solvents can be used ifneeded but the choice of solvent should be reported.4.2 Direct GC/FID, GC/MS and solid phase microextraction(SPME) / gas chromatography of the coating may be used tofacilitate identification of the volatile compounds present in acoating (No
30、te 4). Table X1.1 lists the GC retention times forsome of the volatile compounds which may be found in lowvolatile organic compound content air-dry coatings and forseveral possible internal standards, ordinarily not present incoatings, which may be used (Note 4).NOTE 4The analyst should consult SDS
31、and product data sheets forinformation regarding solvents which are expected in a particular coating.Additional solvents, not shown on the SDS or PDS may also be present inthe coating. Retention times given in Appendix X1 must be verified foreach individual instrument.NOTE 5The accuracy of the volat
32、ile organic compound weightpercent determined using Test Method D6886 is dependent on the properidentification of the compounds detected in the chromatogram. Theresponse of the FID used in the GC is dependent on the compounddetected. The accuracy of the determination requires proper identification(b
33、y GC/MS, by retention time, or by analyzing the sample on a GCcolumn with a different stationary phase) and calibration of the GC for thecompounds detected.4.3 The methods for analysis are:4.3.1 Method AAnalysis is performed using GC/FID bypreparing and analyzing standards to determine responsefacto
34、rs and using these response factors for determination ofthe weight concentrations of analytes.4.3.2 Method BAnalysis is performed using GC/microreactor/FID (which converts all carbon-containing mol-ecules into methane prior to detection in an FID) by firstvalidating the system and subsequently quant
35、ifying usingtabulated response factors.4.3.3 Method CAnalysis is performed using GC/MS. Thismethod is most often used in conjunction with either MethodAor Method B, for identification of analytes. Precision statisticshave not been determined for using GC/MS for quantification.3Butyl Carbitol is a re
36、gistered trademark of The Dow Chemical Company.4Butyl Cellosolve is a registered trademark of The Dow Chemical Company.D6886 1825. Significance and Use5.1 In using Practice D3960 to measure the volatile organiccompound content of waterborne coatings, precision can bepoor for low volatile organic com
37、pound content air-dry coat-ings if the volatile organic weight percent is determinedindirectly. The present method directly identifies and thenquantifies the weight percent of individual volatile organiccompounds in air-dry coatings (Note 6). The total volatileorganic weight percent can be obtained
38、by adding the indi-vidual weight percent values (Note 7).NOTE 6The present method may be used to speciate solvent-borneair-dry coatings. However, since these normally contain high, and oftencomplex, quantities of solvent, precision tends to be better using othermethods contained in Practice D3960, w
39、here the volatile fraction isdetermined by a direct weight loss determination.NOTE 7Detectable compounds may result from thermal decomposi-tion in a hot injection port or from reaction with the extraction solvent. Ifit can be shown that a material is a decomposition product, or is the resultof a rea
40、ction with the extraction solvent, then results for that compoundshould be discounted from the volatile measured by Test Method D6886.6. Apparatus6.1 Gas Chromatograph, with Electronic Data AcquisitionSystem FID Detection, FID/Microreactor Detection. or MassSpectrometry DetectionAny capillary gas ch
41、romatographequipped with a flame ionization detector microreactor flameionization detector, or mass spectrometer and temperatureprogramming capability may be used. Electronic flow control,which gives a constant carrier gas flow, is highly recom-mended. Note that a full precision study has only beenc
42、ompleted for GC with FID detection (Tables X1.2-X1.4). Apreliminary precision study has been completed for GC/Microreactor/FID (Table X1.5).6.2 Standard GC/FID, GC/Microreactor/FID, and GC/MSInstrument Conditions:Instrument ConditionsGC/FID GC/MicroreactorA/FID GC/MSMethod A Method B Method CDetecto
43、r Flame ionization Microreactor/flame ionization 70 eV electron impact mass spectrometerBMicroreactor Air Supply Flow Rate 2.5 mL per minMicroreactor Hydrogen Supply FlowRate35 mL per minMicroreactor Temperature, C, 450Source Temperature, C, 230Quadrupole Temperature C, 150Transfer Line TemperatureC
44、, 260Scanning Parameters Mass 29 to 400 amuFID Air Flow Rate 350 mL per min 350 per minFID H2Air Rate 35 mL per min 1.5 per mLColumns Primary column: 30 m by 0.25 mm 5 % phenyl/95 % methyl siloxane (PMPS)C,C 1.0 m film thicknessConfirmatory columns: 30 m by 0.25 mm polydimethylsiloxane (PDMS), 0.25
45、m film thickness;30 m by 0.25 mm Carbowax (CW), 0.25 m film thicknessCarrier Gas HeliumFlow Rate 1.0 mL per min, constant flow (24.9 cm/s at 40)Split RatioD50 to 1Temperatures, C,Primary ColumnInlet 260Detector 270Initial 50 for 4 minRate 20 per min to 250, hold 6 min (total run time = 20 min)Temper
46、atures, C,Confirmatory ColumnsInlet 260Detector 270Initial 40 for 4 minRate 10 per min to 250, hold 25 min (total run time = 50 min)AThe microreactor (for example, Polyarc, a registered trademark of Activated Research Company) is a two-step oxidation-reduction reactor that converts organiccompounds
47、to methane prior to detection in an FID.BAny mass spectrometer may be used. The conditions specified are for a quadrupole mass spectrometer and are listed as a reference only.CThe column designated as PMPS is commercially available from several vendors by the following designations: DB-5, SPB-5, HP-
48、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 thedesignations Supelcowax 10, DB-Wax, HP-Wax, AT-Wax, CP-Wax 52 CB, Rtx-Wax, BP-20. Inert versions (or othe
49、r equivalent designations) of the columns listed aboveare recommended because they may provide better peak shapes.DJennings Cup inlet liners with no glass wool are the recommended inlet liner type because they provide good reproducibility and complete volatilization of analytes acrossa large range in boiling points. An injection volume of 0.5 L is recommended with the Jennings Cup liner. Any inlet liner that provides complete volatilization of analytesmay be used.NOTE 8Some coatings may contain high-boiling components w
