1、Designation: D6886 12D6886 14Standard Test Method forDetermination of the Weight Percent Individual VolatileOrganic Compounds (VOCs) in Waterborne Air-Dry Coatingsby Gas Chromatography1This standard is issued under the fixed designation D6886; the number immediately following the designation indicat
2、es the year oforiginal 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
3、the weight percent of individual volatile organic compounds in waterborneair-dry coatings.coatings (Note 1).1.2 This method may be used for the analysis of coatings containing silanes, siloxanes, and silane-siloxane blends.1.3 This method is not suitable for the analysis of coatings that cure by che
4、mical reaction (this includes two-component coatingsand coatings which cure when heated) because the dilution herein required will impede the chemical reaction required for thesetypes of coatings.1.4 TheThis method can be used to determine the weight fraction VOCpercent organic content of waterborne
5、 coatings in whichthe material VOC content volatile organic compound weight percent is below 5 weight percent. The method has been usedsuccessfully with higher VOC content waterborne coatings and with solvent-bornesolventborne coatings (Note 12).1.5 TheThis method may also be used to measure the exe
6、mpt volatile organic compound content (acetone, (for example,acetone, methyl acetate, t-butylt-butyl acetate and p-chlorobezotrifluoride)p-chlorobezotrifluoride) of waterborne and solvent-borne coatings. Check local regulations for a list of exempt compounds. The methodology is virtually identical t
7、o that used in TestMethod D6133 which, as written, is specific for only exempt volatile compounds.1.6 Volatile compounds that are present at the 0.005 weight percent level (50 ppm) or greater can be determined. A procedurefor doing so is given in Section 9.1.7 Volatile organic compound content of a
8、coating can be calculated using data from Test Method D6886 but requires otherdata (see Appendix X2.)NOTE 1Data from this method will not always provide the volatile organic compound content of a paint film equivalent of EPA Method 24. Somecompounds and some semi-volatile compounds may be considered
9、 volatile using the GC conditions specified but will not fully volatilize during the onehour at 110C conditions of EPA Method 24. Some or all of these materials remain in the paint film and therefore are not considered volatile organiccompounds according to EPA Method 24. In addition, some compounds
10、 may decompose at the high inlet temperature of the GC. However, note the EPAMethod 24 has poor precision and accuracy at low levels of volatile organic compounds.NOTE 2This test method may be used for the VOC analysis of coatings containing silanes, siloxanes, and silane-siloxane blends. The test m
11、ethodis not suitable for the analysis of coatings that cure by chemical reaction (this includes two-component coatings and coatings which cure when heated)because dilution with a solvent would impede the chemical reaction required for these types of coatings. This test method measures the VOC weight
12、fraction method measures volatile organic compound weight of air-dry coatings directly as opposed to theother methods ofin Practice D3960 whichmeasure the VOC weight fraction of air-dry waterborne coatings volatile organic compound weight percent indirectly. A direct measurement of VOCtheweight frac
13、tion,percent particularly in low VOC volatile organic compound content waterborne coatings, generally gives better precision. CaliforniaPolytechnic State University carried out an extensive study for the California Air Resources Board comparing the precision of the direct method withthe indirect met
14、hod (CARB Standard Agreement No. 04.329).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 may be used to decide if the present method or theother methods ofin Practice D3960 are preferred as ananalysis method for obtaining
15、 the best possible precision for measuring the mass-based VOC content of for a specific coating.1.8 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.1.9 This standard does not purport to address all of the safety concerns, if a
16、ny, associated with its use. It is the responsibilityof the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatorylimitations prior to use.1 This test method is under the jurisdiction of ASTM Committee D01 on Paint and Related Coating
17、s, Materials, and Applications and is the direct responsibility ofSubcommittee D01.21 on Chemical Analysis of Paints and Paint Materials.Current edition approved May 1, 2012June 15, 2014. Published June 2012July 2014. Originally approved in 2003. Last previous edition approved in 20092012 asD6886 -
18、03 (2009).D6886 12. DOI: 10.1520/D6886-12.10.1520/D6886-14.This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indication of what changes have been made to the previous version. Becauseit may not be technically possible to adequately depict all chang
19、es accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current versionof the standard as published by ASTM is to be considered the official document.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. Uni
20、ted States12. Referenced Documents2.1 ASTM Standards:2D1475 Test Method For Density of Liquid Coatings, Inks, and Related ProductsD2369 Test Method for Volatile Content of CoatingsD3792 Test Method for Water Content of Coatings by Direct Injection Into a Gas ChromatographD3925 Practice for Sampling
21、Liquid Paints and Related Pigmented CoatingsD3960 Practice for Determining Volatile Organic Compound (VOC) Content of Paints and Related CoatingsD4017 Test Method for Water in Paints and Paint Materials by Karl Fischer MethodD6133 Test Method for Acetone, p-Chlorobenzotrifluoride, Methyl Acetate or
22、t-Butyl Acetate Content of Solventborne andWaterborne Paints, Coatings, Resins, and Raw Materials by Direct Injection Into a Gas ChromatographD7358 Test Method for Water Content of Paints by Quantitative Calcium Hydride Reaction Test KitE177 Practice for Use of the Terms Precision and Bias in ASTM T
23、est MethodsE691 Practice for Conducting an Interlaboratory Study to Determine the Precision of a Test Method2.2 Other Documents:EPA Method 24 Determination of Volatile Matter Content, Water Content, Density, Volume Solids, and Weight Solids ofSurface Coatings40 CFR 51.100 (s) List of components that
24、 EPA has classified as VOC-exempt3. Terminology3.1 Abbreviations:Acronyms:3.1.1 EGDEethylene glycol diethyl ether3.1.2 DB2-(2-butoxyethoxy)ethanol; Butyl Carbitol;3 diethylene glycol monobutyl ether3.1.3 EB2-butoxyethanol; Butyl Cellosolve;4 ethylene glycol monobutyl ether3.1.4 EGethylene glycol3.1.
25、5 FIDflame ionization detector3.1.6 F-VOCformulation data calculated volatile organic compound in g/(L-water)3.1.6 GCgas chromatograph3.1.7 PGpropylene glycol3.1.9 % RSDpercent relative standard deviation3.1.8 SPMEsolid phase microextraction3.1.9 SPDEsolid phase dynamic extraction3.1.10 Std DevTMPD-
26、IBstandard deviation2,2,4-trimethypentane-1,3-diol, monoisobutyrate3.1.11 TXTMPD-DIB2,2,4-trimethypentane-1,3-diol, monoisobutyratediisobutyrate3.1.12 VOCvolatile organic compound used in various air quality regulations3.1.15 X-VOCexperimental volatile organic compound in g/(L-water)4. Summary of Te
27、st Method4.1 A known weight of coating is dispersed in methanol or tetrahydrofuran (THF) internally standardized, and analyzed bycapillary gas chromatography to give a speciated composition of the volatile organic compounds and(Note 3 exempt organiccompounds, if any, present in the coating. ). Summa
28、tion of the individual volatile organic compound weight fractionspercents givesthe total VOC volatile organic content of the coating measured in weight percent (percent.Note 2).NOTE 3Methanol shouldcan be used as a first choice as a solvent for all waterborne coatings. THF shouldcan be used for solv
29、entborne coatings.Acetone may also be used for solventborne coatings but should not be used for waterborne coatings because it may react with ammonia and amines whichare frequently found in waterborne coatings. Using the provisions of Practice Other solvents can D3960, the VOC content of coatings me
30、asured in g/Lminus water, or other units, may be determined. Since the determination of weight percent VOC in the present method is by direct measurement, eitherthe water fraction (Test Method be used if needed but the choice of solvent should D3792 or Test Method D4017) or the nonvolatile fraction
31、(Test MethodD2369) may be determined indirectly in the application of Practice be reported.D3960. Since precision is better for the determination of the nonvolatilecontent, this is the preferred method for the indirect calculation of water content in this test method. The equations for calculating c
32、oating VOC contentwhen no exempt volatile compounds are present are:2 For referencedASTM standards, visit theASTM website, www.astm.org, or contactASTM Customer Service at serviceastm.org. For Annual Book of ASTM Standardsvolume information, refer to the standards Document Summary page on the ASTM w
33、ebsite.3 Butyl Carbitol is a registered trademark of The Dow Chemical Company.4 Butyl Cellosolve is a registered trademark of The Dow Chemical Company.D6886 142VOC5 fVOCDP!1212fNV 2fVOC!DP/DW!#(1)orVOC5 fVOCDP!12fWDP/DW!#(2)where:DP, fNV, fVOC, and fW = coating density, nonvolatile fraction, VOC fra
34、ction, and water fraction, respectively.4.2 Direct GC/FID, GC/MS and solid phase microextraction / gas chromatography (SPME/GC) of the coating may be used tofacilitate identification of the volatile compounds present in a coating. coating (Note 4). Table X1.1 lists the GC retention timesfor some of
35、the volatile compounds which may be found in low VOC volatile organic compound content air-dry coatings and forseveral possible internal standards, ordinarily not present in coatings, which may be used (Note 34).NOTE 4The analyst should consult MSDS and product data sheets for possible information r
36、egarding solvents which may are expected in a particularcoating. Additional solvents, not shown on the MSDS or PDS may also be present in a particular the coating. Retention times given in X1.1AppendixX1 must be verified for each individual instrument.NOTE 5The accuracy of the volatile organic compo
37、und weight percent determined using Test Method D6886 is dependent on the proper identificationof the compounds detected in the chromatogram. The response of the flame ionization detector (FID) used in the GC is dependent on the compounddetected. The accuracy of the determination requires proper ide
38、ntification (by GC/MS, by retention time, or by analyzing the sample on a GC columnwith a different stationary phase) and calibration of the GC for the compounds detected.5. Significance and Use5.1 In using Practice D3960 to measure the VOC volatile organic compound content of waterborne coatings, p
39、recision tendsto can be poor for low VOC volatile organic compound content air-dry coatings whenif the VOC volatile organic weightfractionpercent is determined indirectly. The present method firstdirectly identifies and then quantifies the weight fractionpercentof individual VOCs directly volatile o
40、rganic compounds in air-dry coatings. coatings (Note 6). The total VOC volatile organicweight fractionpercent can be obtained by adding the individual weight fractionpercent values (Note 47).NOTE 6The present method may be used to speciate solvent-borne air-dry coatings. However, since these normall
41、y contain high, and often complex,quantities of solvent, precision tends to be better using theother methods contained in Practice D3960, where the VOCvolatile fraction is determined bya direct weight loss determination.5.2 SPME/GC makes it possible to identify very low levels of volatile compounds
42、in a coating and could serve to make itpossible to identify the presence of hazardous air pollutants (HAPs).NOTE 7Detectable compounds may result from thermal decomposition in a hot injection port or from reaction with the extraction solvent. If it canbe shown that a material is a decomposition prod
43、uct, or is the result of a reaction with the extraction solvent, then results for that compound should bediscounted from the volatile measured by Test Method D6886.6. Apparatus6.1 Gas Chromatograph, FID Detection or Mass Spectrometry Detection with Electronic Data Acquisition SystemAnycapillary gas
44、chromatograph equipped with a flame ionization detector or mass spectrometer and temperature programmingcapability may be used. Electronic flow control, which gives a constant carrier gas flow, is highly recommended. Note thatprecision and accuracy have only been evaluated using GC with FID detectio
45、n.D6886 1436.2 Standard GC/FID and GC/MS Instrument Conditions:6.2.1 See Table 1.Instrument Conditions FID GC/MSDetector Flame ionization 70 eV electron impact massspectrometerColumns Primary column:30 by 0.25 mm5 % phenyl/95 % methylsiloxane (PMPS),A1.0 m film thicknessPrimary column:30 by 0.25 mm%
46、 phenyl/95 % methylsiloxane (PMPS),A1.0 m film thicknessConfirmatory Columns:30 by 0.25 mmpolydimethylsiloxane (PDMS),0.25 m film thickness;30 by 0.25 mmCarbowax (CW),0.25 m film thickness.Confirmatory Columns:30 by 0.25 mmpolydimethylsiloxane (PDMS),0.25 m film thickness;30 by 0.25 mmCarbowax (CW),
47、0.25 m film thickness.Carrier Gas Helium HeliumFlow Rate 1.0 mL per min,constant flow(24.9 cm/s at 40)1.0 mL per min,constant flow(24.9 cm/s at 40)Split Ratio 50 to 1 50 to 1Temperatures, C,Primary ColumnInlet 260 260Detector 270 270Initial 50 for 4 min 50 for 4 minRate 20 per min to 250,hold 6 min
48、(total run time = 20 min)20 per min to 250,hold 6 min (total run time = 20 min)Temperatures, C,Confirmatory ColumnsInlet 260 260Detector 270 270Initial 40 for 4 min 40 for 4 minRate 10 per min to 250, hold 25min 10 per min to 250, hold 25minSource 230Quadrupole 230Transfer Line 260Scanning Parameter
49、s Mass 29400 amuA 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 thedesignations Supelcowax 10, DB-Wax, HP-Wax, AT-Wax, CP-Wax 52 CB, Rtx-Wax, BP-20.NOTE 8Some coatings may contain high-boiling components which elute from the GC capillary column
