ASTM D4457-02(2014)

Standard Test Method for Determination of Dichloromethane and 1,1,1-Trichloroethane in Paints and Coatings by Direct Injection into a Gas Chromatograph (Withdrawn 2019)

SIGNIFICANCE AND USE
4.1 Use of 1,1,1-trichloroethane and dichloromethane, which do not measurably contribute to the atmospheric oxidant level, is a way for industry to meet government or other regulations on volatile organic compounds. This test method is designed to determine the content of these halohydrocarbon solvents in paints and coatings. That content can subsequently be used in calculating the volatile organic compound content of a coating.
SCOPE
1.1 This test method covers the determination of total amount of dichloromethane or 1,1,1-trichloroethane, or both, in paints and coatings. It has been evaluated for cellulose nitrate, alkyd, vinyl, and styrene-butadiene systems. It has not yet been evaluated for other formulations, but is believed to be applicable. The established working range of this test method is from 31 to 65 % for 1,1,1-trichloroethane and 32 to 78 % for dichloromethane. There is no reason to believe it will not work outside of these ranges. The presence of 1-propanol in paints and coatings requires the use of a different internal standard. (See also Practice E260.)  
1.2 The values stated in inch-pound units are to be regarded as standard. The values given in parentheses are mathematical conversions to SI units that are provided for information only and are not considered standard.  
1.3 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. Specific hazard statements are given in Section 7.
WITHDRAWN RATIONALE
This test method covers the determination of total amount of dichloromethane or 1,1,1-trichloroethane, or both, in paints and coatings. It has been evaluated for cellulose nitrate, alkyd, vinyl, and styrene-butadiene systems. It has not yet been evaluated for other formulations, but is believed to be applicable. The established working range of this test method is from 31 to 65 % for 1,1,1-trichloroethane and 32 to 78 % for dichloromethane. There is no reason to believe it will not work outside of these ranges. The presence of 1-propanol in paints and coatings requires the use of a different internal standard. (See also Practice E260.)
Formerly under the jurisdiction of Committee D01 on Paint and Related Coatings, Materials, and Applications, this test method was withdrawn in December 2019 and replaced by D6886-2018 Standard Test Method for Determination of the Weight Percent Individual Volatile Organic Compounds in Waterborne Air-Dry Coatings by Gas Chromatography1 because D4457 employs an outdated packed chromatography column and is being balloted for withdrawal. The standard will be replaced by D6886, a more modern standard which calls for an open-tubular capillary column.

General Information

• Status: Withdrawn
• Publication Date: 30-Jun-2014
• ICS: 87.040 - Paints and varnishes
• Technical Committee: D01 - Paint and Related Coatings, Materials, and Applications
• Drafting Committee: D01.21 - Chemical Analysis of Paints and Paint Materials

Relations

• Replaces: ASTM D4457-02(2008) - Standard Test Method for Determination of Dichloromethane and 1,1,1-Trichloroethane in Paints and Coatings by Direct Injection into a Gas Chromatograph
• Effective Date: 01-Jul-2014
• Replaced By: ASTM D6886-18 - Standard Test Method for Determination of the Weight Percent Individual Volatile Organic Compounds in Waterborne Air-Dry Coatings by Gas Chromatography
• Effective Date: 23-Dec-2019
• Referred By: ASTM D6577-15(2019) - Standard Guide for Testing Industrial Protective Coatings
• Effective Date: 01-Jul-2014
• Referred By: ASTM D7270-07(2021) - Standard Guide for Environmental and Performance Verification of Factory-Applied Liquid Coatings
• Effective Date: 01-Jul-2014
• Referred By: ASTM D3960-05(2018) - Standard Practice for Determining Volatile Organic Compound (VOC) Content of Paints and Related Coatings
• Effective Date: 01-Jul-2014

Standards Content (Sample)

NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Contact ASTM International (www.astm.org) for the latest information
Designation: D4457 − 02 (Reapproved 2014)
Standard Test Method for
Determination of Dichloromethane and 1,1,1-Trichloroethane
in Paints and Coatings by Direct Injection into a Gas
Chromatograph
This standard is issued under the fixed designation D4457; 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.
1. Scope 3. Summary of Test Method
1.1 This test method covers the determination of total 3.1 Anhydrous 1-propanol (see 10.5) is added as an internal
amountofdichloromethaneor1,1,1-trichloroethane,orboth,in standard to suitable aliquot of the whole paint. The aliquot is
paints and coatings. It has been evaluated for cellulose nitrate, then diluted with dimethylformamide and injected onto a gas
alkyd,vinyl,andstyrene-butadienesystems.Ithasnotyetbeen chromatographic column containing a porous polymer packing
evaluated for other formulations, but is believed to be appli- that separates dichloromethane and 1,1,1-trichloroethane from
cable. The established working range of this test method is other volatile compounds.
from 31 to 65 % for 1,1,1-trichloroethane and 32 to 78 % for
4. Significance and Use
dichloromethane.There is no reason to believe it will not work
outside of these ranges. The presence of 1-propanol in paints
4.1 Use of 1,1,1-trichloroethane and dichloromethane,
and coatings requires the use of a different internal standard.
which do not measurably contribute to the atmospheric oxidant
(See also Practice E260.)
level, is a way for industry to meet government or other
regulations on volatile organic compounds. This test method is
1.2 The values stated in inch-pound units are to be regarded
designed to determine the content of these halohydrocarbon
as standard. The values given in parentheses are mathematical
solvents in paints and coatings. That content can subsequently
conversions to SI units that are provided for information only
beusedincalculatingthevolatileorganiccompoundcontentof
and are not considered standard.
a coating.
1.3 This standard does not purport to address all of the
safety concerns, if any, associated with its use. It is the
5. Apparatus
responsibility of the user of this standard to establish appro-
5.1 Chromatograph, any gas-liquid chromatographic instru-
priate safety and health practices and determine the applica-
ment equipped with a thermal conductivity detector and
bility of regulatory limitations prior to use. Specific hazard
capable of being temperature programmed (see Table 1).
statements are given in Section 7.
Optionally, a flame ionization detector may be used if the
2. Referenced Documents sample is diluted so that no more than 1000 ppm each of
dichloromethane and 1,1,1-trichloroethane is present in the
2.1 ASTM Standards:
injected specimen.
E180 Practice for Determining the Precision of ASTM
Methods for Analysis and Testing of Industrial and Spe- 5.2 Recorder, a recording potentiometer with a full-scale
cialty Chemicals (Withdrawn 2009) deflection of 10 mV, a full-scale response time of 2 s or less,
E260 Practice for Packed Column Gas Chromatography and a maximum noise of 60.03 % of full scale.
5.3 Pre-Column, 40 in. (100 mm) long by ⁄8 in. (3.2 mm)
outside diameter stainless steel, packed with glass wool, fitted
This test method is under the jurisdiction of ASTM Committee D01 on Paint
on the entrance end of the column to retain any nonvolatile
and Related Coatings, Materials, andApplications and is the direct responsibility of
Subcommittee D01.21 on Chemical Analysis of Paints and Paint Materials. materials and minimize sludge buildup in the column.
Current edition approved July 1, 2014. Published July 2014. Originally approved
5.4 Column, 4 ft (1.22 m) long by ⁄8 in. (3.2 mm) outside
in 1985. Last previous edition approved in 2008 as D4457 – 02 (2008). DOI:
10.1520/D4457-02R14. diameter stainless steel, packed with 80/100 mesh (150 to
2 4
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
180 µm) porous polymer packing material, or other suitable
contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website.
3 4
The last approved version of this historical standard is referenced on Porapak R, a registered trademark ofWatersAssociates, Inc., Milford, MA, has
www.astm.org. been found satisfactory for this purpose.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D4457 − 02 (Reapproved 2014)
material.
D4457 − 02 (2014)
TABLE 1 Typical Instrument Conditions
8. Preparation of Apparatus
Detector thermal conductivity
8.1 Column Conditioning—The packed column is installed
Column 4 ft (1.22 m) by ⁄8 in. (3.2 mm) outside
diameter packed with 80–100 mesh
in the gas chromatographic unit leaving the exit end discon-
porous polymer packing
nected from the detector. This will prevent any contamination
Temperature, °C
of the detector with the column bleed. Set the helium flow rate
Injection port 200
Detector block 250 1
at 30 mL/min if a ⁄8 in. (3.2 mm) outside diameter column is
Column
used. Purge the column 5 to 10 min before heating. Heat the
Initial 100
Final 230 (for 8 min) column from room temperature to 200°C at 5°C/min and hold
°C/min 8
this temperature for at least 12 h (overnight).At the end of this
Carrier gas helium
period of time, heat the column to 240°C at a 5°C/min rate and
Flow rate, mL/min 30
Specimen size, µL 1
hold this temperature for several hours. The maximum tem-
perature for this packing is 250°C. Cool the column to 100°C
and reheat to 240°C at 5°C/min to observe the column bleed.
5.5 Liquid Charging Devices,suchasmicrosyringesof5-µL
Optimum conditioning of this column may take several cycles
or 10-µL capacity, cleaned with acetone or other suitable
of the heating program before a good recorder baseline is
solvent. Visually inspect for plugs or cracks before and after
achieved. Conditioning of any column other than that sug-
each injection.
gested (5.4) should be in accordance with the manufacturer’s
5.6 Vials, 25-mL to minimize head space, capable of being recommendations.
septum sealed.
8.2 Install the column in the chromatograph and use the
information in Table 1 as a guide to establish the conditions
6. Reagents and Materials
required to give the desired separation. Allow sufficient time
6.1 Purity of Reagents—Reagent grade chemicals shall be
for the instrument to reach equilibrium as indicated by a stable
used in all tests, unless otherwise specified (as in 6.7). Unless
recorder baseline.Adjust the carrier-gas flow to a constant rate.
otherwise indicated, it is intended that all reagents shall
Before each calibration and series of determinations (or daily),
conform to the specifications of the Committee on Analytical
condition the column at 200°C for 1 h with carrier-gas flow.
Reagents of the American Chemical Society, where such
specifications are available. Other grades may be used pro-
9. Calibration
vided it is first ascertained that the reagent is of sufficient high
purity to permit its use without lessening the accuracy of the
9.1 Preparation of Standards—All standards, as well as
determination.
samples and blanks, should be at a constant temperature. The
given order of ingredient addition should be observed to
6.2 Carrier Gas, helium of 99.995 % or higher purity. High
minimize loss of volatile ingredients.
purity nitrogen may also be used.
9.1.1 Weighingto1.0mg,add16.0gofdimethylformamide
6.3 Dimethylformamide (DMF), reagent grade.
to a vial capable of being septum sealed. Add 2.0 g of
6.4 1-Propanol, gas chromatography spectrophotometric
1,1,1-trichloroethane, 2.0 g of 1-propanol (see 10.5) and 2.0 g
quality (see 10.5).
of dichloromethane. Seal the vial with a crimp-on or septum
6.5 1,1,1-Trichloroethane (see 6.7).
seal.
6.6 Dichloromethane (see 6.7).
9.2 Determine the retention time of each component by
6.7 Halogenated Hydrocarbon Stabilizers—All commercial injecting small amounts either separately or in known mix-
grades of these halogenated hydrocarbons contain stabilizers. tures. The components should elute close to the typical
Eitherobtainthesamesolventusedinthecoatingforuseasthe retention times given in Table 1 and the chromatograms sh
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