ASTM D6438-99
(Test Method)Standard Test Method for Acetone, Methyl Acetate, and Parachlorobenzotrifluoride Content of Paints, and Coatings by Solid Phase Microextraction-Gas Chromatography
Standard Test Method for Acetone, Methyl Acetate, and Parachlorobenzotrifluoride Content of Paints, and Coatings by Solid Phase Microextraction-Gas Chromatography
SCOPE
1.1 This test method is for the determination of acetone, methyl acetate, or parachlorobenzotrifluoride (PCBTF), or combination of any of the three, in paints and coatings, by solid phase microextraction (SPME) headspace sampling, and subsequent injection into a gas chromatograph. It has been evaluated for cellulose nitrate, acrylic, and urethane solvent-borne systems. The established working range of this test method is: acetone, 28 to 90%; methyl acetate, 12 to 22%; parachlorobenzotrifluoride, 10 to 17%. There is no reason to believe that it will not work ouside these ranges. A minor modification of this test method would make it suitable for the analysis of the same analytes in water-borne coatings (see Note 1).
Note 1-Water-borne paints are internally standardized and diluted with water followed by addition of solid sodium chloride.
1.2 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.
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Designation: D 6438 – 99
Standard Test Method for
Acetone, Methyl Acetate, and Parachlorobenzotrifluoride
Content of Paints, and Coatings by Solid Phase
Microextraction-Gas Chromatography
This standard is issued under the fixed designation D 6438; 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 PCBTF parachlorobenzotrifluoride,
(4-chlorobenzotrifluoride)
1.1 This test method is for the determination of acetone,
MCBTF metachlorobenzotrifluoride
methyl acetate, or parachlorobenzotrifluoride (PCBTF), or
(3-chlorobenzotrifluoride)
combinationofanyofthethree,inpaintsandcoatings,bysolid
SPME solid phase microextraction
phase microextraction (SPME) headspace sampling, and sub-
VOC volatile organic compound
sequent injection into a gas chromatograph. It has been
PEG/DVB polyethylene glycol/divinylbenzene
evaluated for cellulose nitrate, acrylic, and urethane solvent-
FID flame ionization detector
borne systems. The established working range of this test
MS mass selective or mass spectral
method is: acetone, 28 to 90 %; methyl acetate, 12 to 22 %;
SIM selected ion monitoring
parachlorobenzotrifluoride, 10 to 17 %. There is no reason to
GC gas chromatograph
believe that it will not work outside these ranges. A minor
Sr repeatability standard deviations
modification of this test method would make it suitable for the
SR reproducibility standard deviations
analysisofthesameanalytesinwater-bornecoatings(seeNote
r repeatability, 95 % confidence limit
1).
R reproducibility, 95 % confidence limit
NOTE 1—Water-borne paints are internally standardized and diluted
with water followed by addition of solid sodium chloride.
4. Summary of Test Method
1.2 This standard does not purport to address all of the
4.1 A suitable aliquot of whole solvent-borne paint is
safety concerns, if any, associated with its use. It is the
internally standardized and diluted with dioctyl phthalate. The
responsibility of the user of this standard to establish appro-
headspace of this solution is sampled with an SPME fiber,
priate safety and health practices and determine the applica-
which is then thermally desorbed in the injection port of a gas
bility of regulatory limitations prior to use.
chromatograph onto a suitable capillary column. Either a flame
ionization or mass specific detector may be used to measure
2. Referenced Documents
peak areas of analytes and internal standards.
2.1 ASTM Standards:
5. Significance and Use
D 3925 Practice for Sampling Liquid Paints and Related
Pigmented Coatings
5.1 In order to calculate the volatile organic content (VOC)
D 6133 Test Method for Acetone Content of Solvent-
of paints containing EPA exempt solvents, it is necessary to
Reducible and Water-Reducible Paints, Coatings, Resins,
know the acetone, methyl acetate, or parachlorobenzotrifluo-
and Raw Materials by Direct Injection into A Gas Chro-
ride content. This gas chromatographic test method provides a
matograph
simple and direct way for measuring these solvents. Each
E 180 Practice for Determining the Precision of ASTM
analyte is measured with respect to a unique internal standard.
Methods forAnalysis and Testing of Industrial Chemicals
For acetone, the internal standard used is acetone-d6, for
methyl acetate it is methyl acetate-d3, and for PCBTF it is
3. Terminology
metachlorobenzotrifluoride (MCBTF). These unique analyte/
3.1 Abbreviations:
internal standard pairs behave very nearly as single solvents
with respect to evaporation rate and adsorption rate onto a
1 coated silica fiber (SPME) but are separable on a gas chro-
This test method is under the jurisdiction of ASTM Committee D-1 on Paint
matograph (GC) capillary column. The only critical analytical
and Related Coatings, Materials, andApplications and is the direct responsibility of
Subcommittee D01.21 on Chemical Analysis of Paints and Paint Materials.
techniquerequiredforsuccessfullyperformingthistestmethod
Current edition approved Sept. 10, 1999. Published November 1999.
is the ability of an analyst to weigh a paint sample and internal
Annual Book of ASTM Standards, Vol 06.01.
standard,correspondingtotheanalyteofinterest,intoaseptum
Annual Book of ASTM Standards, Vol 15.05.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
D6438–99
TABLE 2 MS Instrument Conditions
capped vial. After weighing, solvent evaporation has no effect
onthefinalvalueofthedetermination.Sincewholepaintisnot Detector: Electron ionization or mass selective
Detection Mode: Selected ion monitoring (SIM) of ions m/e 58, 64,
injected into the gas chromatograph, the analytical system is
74, 77, and 180
never compromised.
Dwell Time: 100 milliseconds or less
Solvent Delay: 0.0 min
6. Apparatus Column: 25 m 3 0.20 mm 5 % phenyl/95 % methyl
polydimethylsiloxane
6.1 Manual SPME Holder, fitted with partially crosslinked
Carrier Gas: Helium
Flow Rate: 1.0 mL per minute (20 cm per second)
polyethylene glycol/divinylbenzene (PEG/DVB) fiber assem-
Split Ratio: 200 to 1
bly, 65–µm film thickness.
A
Fiber desorption time: 5 to 6 s
6.2 Gas Chromatograph, FID Detection—Anycapillarygas
Temperatures, °C
Inlet 260°
chromatograph equipped with a flame ionization detector may
Detector 280°
be used. Temperature programming capability is desirable, but
Initial 40° for 2 min
isothermal operations may be utilized.
Rate 1 10° per minute to 90°, hold 1 min
Rate 2 40° per minute to 240°, hold 1 min
6.2.1 For FID instrument conditions, see Table 1.
A
If the fiber desorption is carried out longer than 5 or 6 s, the acetone peaks
exhibittailing.A5to6–sdesorptiontimetransfers98to99 %oftheanalytestothe
TABLE 1 FID Instrument Conditions
capillary column. The fiber may be cleaned by inserting it into the GC inlet for 15
Detector: Flame ionization s after analytes of interest have eluted.
Column: 60 m 3 0.25 mm 100 % polyethylene glycol, 0.5-µm
film thickness
Carrier Gas: Helium
Flow Rage: 1.0 mL per minute (20 cm per second) 7.3 The SPME fiber should be inserted into a 260° C
Split Ratio: 200 to 1
injection port for 30 s prior to daily use.
A
Fiber desorption time: 5 to 6 s
Temperature, ° C
Inlet 260° 8. Reagents and Materials
Detector 270°
8.1 Purity of Reagents—Reagent grade chemicals shall be
Initial 35° for 12 min
Rate 1 30° per minute to 100°, hold 10 min
used in all tests. Unless otherwise indicated, it is intended that
Rate 2 30° per minute to 240°, hold 2 min
all reagents shall conform to the specifications of the Commit-
A
If the fiber desorption is carried out longer than 5 or 6 s, the acetone peaks
tee onAnalytical Reagents of theAmerican Chemical Society,
exhibittailing.A5to6–sdesorptiontimetransfers98to99 %oftheanalytestothe
where such specifications are available. Other grades may be
capillary column. The fiber may be cleaned by inserting it into the GC inlet for 15
s after analytes of interest have eluted. used, provided it is first ascertained that the reagent is of
sufficiently high purity to permit its use without lessening the
accuracy of the determination.
6.2.2 Inlet Liner, 0.75-mm should be placed in the injection
4 8.2 Carrier Gas, Helium of 99.995 % or higher purity.
port.
8.3 Acetone -d6, 99.9 % isotopic purity.
6.2.3 Integrator—Any electronic integrator that can accu-
8.4 Methyl Acetate -d3, 99.9 % isotopic purity (see Note 2).
rately quantify a gas chromatographic peak area is acceptable.
8.5 Parachlorobenzotrifluoride, technical grade, 99+ % (see
6.3 Gas Chromatograph, Mass Selective (MS) Detection—
Note 3).
Any capillary gas chromatograph equipped with a mass selec-
8.6 Metachlorobenzotrifluoride, 97 %, (see Note 4).
tive detector may be used. The detector must be capable of
8.7 Dedicated Syringes, 250-µL syringes, and Disposal
measuring in the selected ion monitoring (SIM) mode at dwell
Syringes, 1.0 mL.
times of 100 milliseconds or less.
8.8 Septum Vials, 22 or 40 mL, with fluorocarbon-faced
6.3.1 For MS instrument conditions, see Table 2.
silicone septa.
6.3.2 Inlet liner, 0.75-mm, should be placed in the injection
port.
NOTE 2—Methyl acetate-d3 was prepared by the acid-catalyzed reac-
6.3.3 The instrument should have a software data system to tion of methanol with acetic-d3 acid, 99.9 % isotopic purity.
NOTE 3—Parachlorobenzotrifluoride contained 0.5 % of the meta iso-
allow extraction and integration of the SIM ions.
mer and 0.1 % of the ortho isomer.
NOTE 4—The metachlorobenzotrifluoride standard was chromato-
7. Column and Fiber Conditioning
graphically analyzed on a 60–meter 100 % polyethylene glycol column
7.1 Either or both capillary columns should be conditioned
(see 6.2) and exhibited only a single peak.
according to the manufacturer’s recommendation. The col-
umns may then be used indefinitely without further condition- 9. Preparation of Standards
ing.
9.1 Place6-mLdioctylphthalateintoa22or40-mLvialand
7.2 TheSPMEfibershouldbeconditionedandusedaccord-
seal with a septum cap.
ing to the manufacturer’s recommendation.
4 5
The sole source of supply of the manual holder and fibers known to the Reagent Chemicals American Chemical Society, Specifications, American
committee at this time is Supelco Company, Supelco Pa
...
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