ASTM D4591-22

Standard Test Method for Determining Temperatures and Heats of Transitions of Fluoropolymers by Differential Scanning Calorimetry

SIGNIFICANCE AND USE
4.1 DSC analysis may be used with fluoropolymers to achieve at least four different objectives as follows:  
4.1.1 To measure transition temperatures to aid in the identification of the various fluoropolymers, individually or in mixtures;  
4.1.2 To compare the relative levels of crystalline content of two or more specimens of a sample of a fluoropolymer relative to another sample by measuring the heat of fusion;
Note 2: Absolute values of crystalline content cannot be determined until values for heats of fusion of the completely crystalline polymers are available.  
4.1.3 The heat of crystallization of pure PTFE homopolymer is depending on the relative molecular weight of the specimen. Some PTFE resins are modified with small amounts of comonomers. These modifications have profound effects on crystallization behavior and shall be considered when evaluating the results.  
4.1.4 To characterize PTFE (DSC thermal curves determined on powders or products of PTFE that have never been melted convey appreciable information about details of morphology and molecular structure);4  
4.1.5 To supplement the test for standard specific gravity (SSG) described in Specifications D4894 and D4895 by using the heat of crystallization of pure PTFE homopolymer, depending on the relative molecular weight of the specimen. The scopes of these specifications, however, include PTFE resins modified with small amounts of comonomers, and many commercial PTFE resins are modified in this manner. These modifications can have profound effects on crystallization behavior. Published relationships4 between heat of crystallization and molecular weight refer to pure PTFE homopolymers and, therefore, cannot be applied to the modified resins.
SCOPE
1.1 This test method defines conditions for the use of differential scanning calorimetry (DSC) with fluoropolymers. It covers the use of DSC analyses with the fluoropolymers, PTFE, PVDF, PCTFE, and PVF and their copolymers PFA, MFA, FEP, ECTFE, EFEP, VDF/HFP, VDF/TFE/HFP, VDF/CTFE. The test method is applicable to the analysis of powders as well as samples taken from semi-finished or finished products. The nature of fluoropolymers is such that special procedures are needed for running DSC analysis and interpreting the results.  
1.2 The values stated in SI units as detailed in IEEE/ASTM SI-10 are to be regarded as the 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, health, and environmental practices and determine the applicability of regulatory limitations prior to use.
Note 1: There is currently no ISO standard that duplicates this test method. ISO 20568-1 and ISO 20568-2 cover similar testing and reference this test method for testing conditions.  
1.4 This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.

General Information

• Status: Published
• Publication Date: 14-Mar-2022
• ICS: 83.080.20 - Thermoplastic materials
• Technical Committee: D20 - Plastics
• Drafting Committee: D20.15 - Thermoplastic Materials

Standards Content (Sample)

This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
Designation: D4591 − 22
Standard Test Method for
Determining Temperatures and Heats of Transitions of
1
Fluoropolymers by Differential Scanning Calorimetry
This standard is issued under the fixed designation D4591; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
This standard has been approved for use by agencies of the U.S. Department of Defense.
1. Scope* D1600TerminologyforAbbreviatedTermsRelatingtoPlas-
tics
1.1 This test method defines conditions for the use of
D3418Test Method for Transition Temperatures and En-
differential scanning calorimetry (DSC) with fluoropolymers.
thalpies of Fusion and Crystallization of Polymers by
It covers the use of DSC analyses with the fluoropolymers,
Differential Scanning Calorimetry
PTFE, PVDF, PCTFE, and PVF and their copolymers PFA,
D4894 Specification for Polytetrafluoroethylene (PTFE)
MFA, FEP, ECTFE, EFEP, VDF/HFP, VDF/TFE/HFP, VDF/
Granular Molding and Ram Extrusion Materials
CTFE.Thetestmethodisapplicabletotheanalysisofpowders
D4895 Specification for Polytetrafluoroethylene (PTFE)
as well as samples taken from semi-finished or finished
Resin Produced From Dispersion
products. The nature of fluoropolymers is such that special
E473Terminology Relating to Thermal Analysis and Rhe-
procedures are needed for running DSC analysis and interpret-
ology
ing the results.
E793Test Method for Enthalpies of Fusion and Crystalliza-
1.2 The values stated in SI units as detailed in IEEE/ASTM
tion by Differential Scanning Calorimetry
SI-10 are to be regarded as the standard.
IEEE/ASTM SI-10Standard for Use of the International
1.3 This standard does not purport to address all of the
System of Units (SI) (the Modern Metric System)
3
safety concerns, if any, associated with its use. It is the 2.2 ISO Standards:
responsibility of the user of this standard to establish appro-
ISO 20568-1 Plastics—Fluoropolymer Dispersion and
priate safety, health, and environmental practices and deter- Molding and Extrusion Materials—Part 1: Designation
mine the applicability of regulatory limitations prior to use.
and Specification
ISO 20568-2 Plastics—Fluoropolymer Dispersion and
NOTE 1—There is currently no ISO standard that duplicates this test
Molding and Extrusion Materials—Part 2: Preparation of
method.ISO20568-1andISO20568-2coversimilartestingandreference
this test method for testing conditions. Test Specimen and Determination of Properties
1.4 This international standard was developed in accor-
3. Terminology
dance with internationally recognized principles on standard-
3.1 Definitions:
ization established in the Decision on Principles for the
3.1.1 differential scanning calorimetry (DSC)—a technique
Development of International Standards, Guides and Recom-
in which the difference in energy inputs into a substance and a
mendations issued by the World Trade Organization Technical
reference material is measured as a function of temperature,
Barriers to Trade (TBT) Committee.
while the substance and reference material are subjected to a
controlled increase or decrease in temperature.
2. Referenced Documents
2
3.1.2 Refer to Terminology E473 for general terminology
2.1 ASTM Standards:
used in this test method.
3.2 Abbreviated Terms:
1
3.2.1 Abbreviations used in this test method are in accor-
ThistestmethodisunderthejurisdictionofASTMCommitteeD20onPlastics
and is the direct responsibility of Subcommittee D20.15 on Thermoplastic Materi-
dance with Terminology D1600.
als.
3.2.2 PTFE—polytetrafluoroethylene.
Current edition approved March 15, 2022. Published March 2022. Originally
3.2.3 PFA—perfluoro(alkoxy alkane) resin.
approved in 1987. Last previous edition approved in 2017 as D4591-17. DOI:
3.2.4 FEP—perfluoro(ethylene-propene) copolymer.
10.1520/D4591-22.
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
3
Standards volume information, refer to the standard’s Document Summary page on Available fromAmerican National Standards Institute (ANSI), 25 W. 43rd St.,
the ASTM website. 4th Floor, New York, NY 10036, http://www.ansi.org.
*A Summary of Changes section appears at the end of this standard
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
1

---------------------- Page: 1 ----------------------
D4591 − 22
3.2.5 ETFE—ethylene-tetrafluoroethylene copolymer. 5. Apparatus
3.2.6 PVDF—
...

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. Because
it may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current version
of the standard as published by ASTM is to be considered the official document.
Designation: D4591 − 17 D4591 − 22
Standard Test Method for
Determining Temperatures and Heats of Transitions of
1
Fluoropolymers by Differential Scanning Calorimetry
This standard is issued under the fixed designation D4591; 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.
This standard has been approved for use by agencies of the U.S. Department of Defense.
1. Scope*
1.1 This test method defines conditions for the use of differential scanning calorimetry (DSC) with fluoropolymers. It covers the
use of DSC analyses with the fluoropolymers, PTFE, PVDF, PCTFE, and PVF and their copolymers PFA, MFA, FEP, ECTFE,
EFEP, VDF/HFP, VDF/TFE/HFP, VDF/CTFE. The test method is applicable to the analysis of powders as well as samples taken
from semi-finished or finished products. The nature of fluoropolymers is such that special procedures are needed for running DSC
analysis and interpreting the results.
1.2 The values stated in SI units as detailed in IEEE/ASTM SI-10 are to be regarded as the 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, health, and environmental practices and determine the applicability of
regulatory limitations prior to use.
NOTE 1—There is currently no ISO standard that duplicates this test method. ISO 12086-120568-1 and ISO 12086-220568-2 cover similar testing and
reference this test method for testing conditions.
1.4 This international standard was developed in accordance with internationally recognized principles on standardization
established in the Decision on Principles for the Development of International Standards, Guides and Recommendations issued
by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
2. Referenced Documents
2
2.1 ASTM Standards:
D1600 Terminology for Abbreviated Terms Relating to Plastics
D3418 Test Method for Transition Temperatures and Enthalpies of Fusion and Crystallization of Polymers by Differential
Scanning Calorimetry
D4894 Specification for Polytetrafluoroethylene (PTFE) Granular Molding and Ram Extrusion Materials
D4895 Specification for Polytetrafluoroethylene (PTFE) Resin Produced From Dispersion
E473 Terminology Relating to Thermal Analysis and Rheology
E793 Test Method for Enthalpies of Fusion and Crystallization by Differential Scanning Calorimetry
IEEE/ASTM SI-10 Standard for Use of the International System of Units (SI) (the Modern Metric System)
1
This test method is under the jurisdiction of ASTM Committee D20 on Plastics and is the direct responsibility of Subcommittee D20.15 on Thermoplastic Materials.
Current edition approved Dec. 1, 2017March 15, 2022. Published January 2018March 2022. Originally approved in 1987. Last previous edition approved in 20122017
as D4591 - 07D4591 - 17.(2012). DOI: 10.1520/D4591-17.10.1520/D4591-22.
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or 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.
*A Summary of Changes section appears at the end of this standard
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
1

---------------------- Page: 1 ----------------------
D4591 − 22
3
2.2 ISO Standards:
ISO 12086-120568-1 Plastics—Fluoropolymer Dispersion and Molding and Extrusion Materials—Part 1: Designation and
Specification
ISO 12086-220568-2 Plastics—Fluoropolymer Dispersion and Molding and Extrusion Materials—Part 2: Preparation of Test
Specimen and Determination of Properties
3. Terminology
3.1 Definitions:
3.1.1 differential scanning calorimetry (DSC)—a technique in which the difference in energy inputs into a substance and a
reference material is measured as a function of temperature, while the substance and reference material are subjected to a controlled
increase or decrease in temperature.
3.1.2 Refer to Terminology E473 for general terminology used in this test method.
3.2 Abbreviated Terms:
3.2.1 Abbreviations used in this test method are in accordance with Terminology D1600.
3.2.2 PTFE—polytetrafluoroethylene.
3.2.3 PFA—perfluoro(alkoxy alkane) resin.
3.2.4
...