ASTM D3465-21

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Designation: D3465 − 14 D3465 − 21
Standard Test Method Guide for
Purity of Monomeric Plasticizers by Gas Chromatography
This standard is issued under the fixed designation D3465; 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*
1.1 This gas chromatographic test method covers a procedure for extending the range of purity determination of monomeric
plasticizers beyond that now determined by other methods. Due to the need to volatilize the plasticizer, only monomeric
plasticizers having definitive boiling points and a molecular weight less than 1000 Daltons, such as dioctyl phthalate, are applicable
to this test method.
1.2 The values in SI units are to be regarded as standard.
1.3 The text of this test method references notes and footnotes that provide explanatory material. These notes and footnotes
(excluding those in tables and figures) are not to be considered as requirements of this test method.
1.4 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 precautionary statements are given in Section 9
NOTE 1—There is no known ISO equivalent to this standard.
2. Referenced Documents
2.1 ASTM Standards:
D883 Terminology Relating to Plastics
D1600 Terminology for Abbreviated Terms Relating to Plastics
D2124 Test Method for Analysis of Components in Poly(Vinyl Chloride) Compounds Using an Infrared Spectrophotometric
Technique (Withdrawn 2020)
E177 Practice for Use of the Terms Precision and Bias in ASTM Test Methods
E260 Practice for Packed Column Gas Chromatography
E355 Practice for Gas Chromatography Terms and Relationships
E594 Practice for Testing Flame Ionization Detectors Used in Gas or Supercritical Fluid Chromatography
E1510 Practice for Installing Fused Silica Open Tubular Capillary Columns in Gas Chromatographs
IEEE/ASTM SI-10 Practice for Use of the International System of Units (SI), the Modernized Metric System
This test method guide is under the jurisdiction of ASTM Committee D20 on Plastics and is the direct responsibility of Subcommittee D20.70 on Analytical Methods
(Section D20.70.02).
Current edition approved March 1, 2014July 1, 2021. Published March 2014July 2021. Originally approved in 1975. Last previous edition approved in 20072014 as
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D3465 - 00(2007)D3465 - 14. . DOI: 10.1520/D3465-14.10.1520/D3465-21.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM Standards
volume information, refer to the standard’s Document Summary page on the ASTM website.
The last approved version of this historical standard is referenced on www.astm.org.
*A Summary of Changes section appears at the end of this standard
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D3465 − 21
3. Terminology
3.1 Definitions:
3.1.1 General—Definitions are in accordance with Terminology D883 and Terminology D1600 unless otherwise indicated.
3.1.2 All gas chromatography terms and relationships used in this test method are consistent with, or refer to, Practice E355.
4. Summary of Test Method
4.1 A test portion of the plasticizer to be analyzed is injected onto a gas chromatographic column and separated into its
components, which are sensed by the detector and quantified by an electronic data acquisition system (computer) or an integrator.
The purity is based on the total area response of the principal peak(s). All other components are impurities.
5. Significance and Use
5.1 Infrared techniques frequently cannot detect low-level materials. Gas chromatographic methods possess higher sensitivity, and
are used to extend limits of detection.
5.2 It is expected that this test method will be suitable for specifications, manufacturing control, and research and development.
An area percent method of determining concentration of the components shall be used if the area percent of the plasticizer is
99.0 % or higher. However, if the area percent of the plasticizer is less than 99.0 % or if any question were to arise about the data,
an internal standard shall be used.
5.3 Impurities potentially found in monomeric plasticizers include alcohols, dibasic acids, and monoesters.
6. Interferences
6.1 Gas chromatography (GC) retention times are dependent on several variables, and it is possible to have two or more
components with identical retention times. The analyst shall take the necessary steps to ensure that adequate separation of the
plasticizer components is achieved. It is possible that analysis by gas chromatography/mass spectrometry will identify the presence
of overlapping components.
7. Apparatus
7.1 Gas Chromatograph, equipped with a flame ionization or thermal conductivity detector and capable of operating in the range
from 250 to 350°C.
7.1.1 Capillary or Packed Gas Chromatographic Column, capable of operating in the range from 250 to 350°C that provides
adequate separation and definition of components. Examples are as follows:
7.1.2 Packed Columns, stainless steel, 1.83 m (6 ft) long, with an outside diameter of 6.4 mm ( ⁄4 in.) and filled with Chromosorb
W or WAW, 60 to 80 mesh, as the solid support.
7.1.2.1 Liquid Phase—The liquid phase sensitivity changes the utility in detecting various impurities. Examples of detectability
of alcohol impurities are illustrated as follows:
7.1.2.2 A coating of 5 to 15 % of SE-30 silicone gumstock results in reasonably symmetrical peaks and accurate quantitative
measurements between 0.1 and 1 % alcoholic impurities.
7.1.2.3 A coating of 15 % Igepal CO-990 results in separations of similar types of esters such as diisooctyl phthalate and di
(2-ethylhexyl) phthalate at the 1 % level.
Trademark of Imerys Minerals California, Inc.
Trademark of Rhodia Operations.
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7.1.2.4 A coating of 20 % Ozonite is also effective for alcohols in the 0.1 to 1 % concentration level.
7.1.3 Capillary Columns, fused silica high-temperature capillary column with a 100 % poly(dimethylsiloxane) stationary phase;
length: 15 to 30 m; inside diameter: 0.25 to 0.5 mm; film thickness: 0.1 to 0.25 μm.
7.2 Integrator or Electronic Data Acquisition System.
7.3 Gas Chromatographic Syringe or Autosampler, 0.1 to 10.0 μL capacity.
7.4 Pressure Regulators, for all required gas cylinders.
7.5 Flowmeter, or other means of measuring gas flow rates.
8. Reagents and Materials
8.1 Helium, chromatographic grade.
8.2 Hydrogen, chromatographic grade.
8.3 Nitrogen, chromatographic grade.
8.4 Purified Air.
9. Hazards
9.1 Hydrogen is flammable. Ensure that all leaks are eliminated.
10. Preparation of the Gas Chromatograph
10.1 Temperature Settings—This test method requires injection port and detector temperatures of 260 to 350°C. For a plasticizer
with a nominal boiling point of 410°C, the following conditions are suggested:
Injection port 260 to 350°C
Detector 300 to 350°C
10.2 Program the temperature of the column suitable to best separate the components (see 7.1 for columns). Typical settings are
as follows:
10°C/min from 60 to 280°C and hold.
10°C/min from 100 to 300°C and hold for 10 min.
10.3 Sample Size—Select a sample size that provides an adequate chromatographic efficiency (that is, do not overload the column).
A typical sample size is 1 μL.
10.4 Carrier Gas—Helium, flow rate 30 to 60 cm /min.
11. Procedure
11.1 The method of injecting the sample onto the column and analyzing for the components is given in detail in Practice E260,
(specifically, Sections 10 and 14).
Trademark of Alltech Associates.
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11.2 The method for analyzing the components shall be consistent with Fig. 1 of Practice E355.
12. Report
12.1 Report the following information:
12.1.1 Proportion of the total area related to the principal component(s) as the purity of the plasticizer, percent,
12.1.2 Retention times of impurities, relating them to corresponding retention times of known substances,
12.1.3 Proportion of total area related to the impurities in percent,
12.1.4 Column description,
12.1.5 Gas chromatograph conditions, and
12.1.6 Internal standard when used for calibration.
13. Precision and Bias
13.1 Precision—A round robin is in progress. Table 1 is based on a single laboratory test using two different capillary columns
on one gas chromatograph.
13.1.1 S is the within-laboratory standard deviation of the average; r = 2.8 S (see 13.1.3 for application of r.)
r R
13.1.2 S is the between-laboratory standard deviation of the average; R = 2.8 S (see 13.1.4 for application of R).
R R
13.1.3 Repeatability—In comparing two test results for the same material, obtained by the same operator using the same
equipment on the same day, judge those test results as not equivalent if they differ by more than the r value for the material and
condition.
13.1.4 Reproducibility—By comparing two test results for the same material, obtained by different equipment on different days,
judge those test results as not equivalent if they differ by more than the R value for the material and condition. (This applies
between different laboratories or between different equipment within the same laboratory.)
13.1.5 Any judgment in accordance with 13.1.2 and 13.1.3 will have an approximate 95 % (0.95) probability of being correct.
13.2 Bias—There are no recognized standards on which to base an estimate of bias for this test method.
14. Keywords
14.1 adipate; benzoate; gas chromatography; monomeric; phthalate; plasticizers; poly(vinyl chloride); PVC; trimellitate
SUMMARY OF CHANGES
Committee D20 has identified the location of selected changes to this standard since the last issue
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(D3465 - 00(2007) ) that may impact the use of this standard. (March 1, 2014)
(1) Changed subcommittee section from D20.70.03 to D20.70.02.
(2) Removed “(FL)” in 5.1.
(3) Removed permissive language.
(4) Updated trademark information in Footnotes 3-5.
(5) Changed “quantity” to “sample size” in 10.3.
(6) Added new keywords to Section 14.
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ASTM I
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