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 − 17

Standard Test Method for

Determining Temperatures and Heats of Transitions of
Fluoropolymers by Differential Scanning Calorimetry1
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* D1600 Terminology for Abbreviated Terms Relating to Plas-

1.1 This test method defines conditions for the use of tics
differential scanning calorimetry (DSC) with fluoropolymers. D3418 Test Method for Transition Temperatures and En-
It covers the use of DSC analyses with the fluoropolymers, thalpies of Fusion and Crystallization of Polymers by
PTFE, PVDF, PCTFE, and PVF and their copolymers PFA, Differential Scanning Calorimetry
MFA, FEP, ECTFE, EFEP, VDF/HFP, VDF/TFE/HFP, VDF/ D4894 Specification for Polytetrafluoroethylene (PTFE)
CTFE. The test method is applicable to the analysis of powders Granular Molding and Ram Extrusion Materials
as well as samples taken from semi-finished or finished D4895 Specification for Polytetrafluoroethylene (PTFE)
products. The nature of fluoropolymers is such that special Resin Produced From Dispersion
procedures are needed for running DSC analysis and interpret- E473 Terminology Relating to Thermal Analysis and Rhe-
ing the results. ology
E793 Test 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-10 Standard 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)
safety concerns, if any, associated with its use. It is the 2.2 ISO Standards:3
responsibility of the user of this standard to establish appro- ISO 12086-1 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
NOTE 1—There is currently no ISO standard that duplicates this test
ISO 12086-2 Plastics—Fluoropolymer Dispersion and
method. ISO 12086-1 and ISO 12086-2 cover similar testing and reference Molding and Extrusion Materials—Part 2: Preparation of
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-
ization established in the Decision on Principles for the 3.1 Definitions:
Development of International Standards, Guides and Recom- 3.1.1 differential scanning calorimetry (DSC)—a technique
mendations issued by the World Trade Organization Technical in which the difference in energy inputs into a substance and a
Barriers to Trade (TBT) Committee. reference material is measured as a function of temperature,
while the substance and reference material are subjected to a
2. Referenced Documents controlled increase or decrease in temperature.
2.1 ASTM Standards:2 3.1.2 Refer to Terminology E473 for general terminology
used in this test method.
3.2 Abbreviated Terms:
1
This test method is under the jurisdiction of ASTM Committee D20 on Plastics 3.2.1 Abbreviations used in this test method are in accor-
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 Dec. 1, 2017. Published January 2018. Originally
approved in 1987. Last previous edition approved in 2012 as D4591 - 07(2012). 3.2.3 PFA—perfluoro(alkoxy alkane) resin.
DOI: 10.1520/D4591-17. 3.2.4 FEP—perfluoro(ethylene-propene) copolymer.
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at [email protected]. For Annual Book of ASTM
3
Standards volume information, refer to the standard’s Document Summary page on Available from American 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

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 D4591 − 17
3.2.5 ETFE—ethylene-tetrafluoroethylene copolymer. 5. Apparatus
3.2.6 PVDF—poly(vinylidene fluoride).
5.1 Differential Scanning Calorimeter, capable of heating
3.2.7 PCTFE—polymonochlorotrifluoroethylene.
and cooling rates of at least 10.0 °C/min and of recording
3.2.8 ECTFE—ethylene-monochlorotrifluoroethylene co-
automatically the differential heat flow between a specimen
polymer.
and a reference material as a function of time, both to the
3.2.9 EFEP—ethylene-perfluoroethylene-propene copoly-
required sensitivity and precision. For comparison purposes,
mer.
the same heating rate shall be used for all calibrations and test
3.2.10 VDF/HFP—vinylidene fluoride-hexafluoropropene
runs. Thermal curves are recorded using a computerized data
copolymer.
collection system or on a time-based recorder. The resulting
3.2.11 VDF/TFE—vinylidene fluoride-tetrafluoroethylene
curves are used for the measurement of peak areas either by
copolymer.
computer integration or an alternative area measuring proce-
3.2.12 VDF/TFE/HFP—vinylidene fluoride-
dure. The instrument should have a sensitivity for heat flow
tetrafluoroethylene-hexafluoropropene copolymer.
sufficient to provide a precision of 61 % when run using a
3.2.13 VDF/CTFE—vinylidene fluoride-
suitable standard for calibration, such as indium. The instru-
chlorotrifluoroethylene copolymer.
ment must have a precision of 61 % for either the computer-
3.2.14 PVF—poly(vinyl fluoride).
ized data collections or over a time-base range of 0.1 to 2.0
3.2.15 MFA—perfluoromethylvinylether-tetrafluoroethyl-
min/cm of chart.
ene copolymer.
3.2.16 SSG—standard specific gravity. NOTE 3—Most DSC systems report data with a temperature ordinate.
The temperature values are directly related to time based on the heating or
4. Significance and Use cooling rate. Integrated areas measured from the DSC curves will be
directly proportional to the differential caloric input.
4.1 DSC analysis may be used with fluoropolymers to NOTE 4—Noncomputerized area measurement shall be done with a
achieve at least four different objectives as follows: precision of 61 % or better.
4.1.1 To measure transition temperatures to aid in the 5.2 Specimen Holders and Covers, made from aluminum or
identification of the various fluoropolymers, individually or in other materials of high thermal conductivity that do not react
mixtures; with the specimen. It is preferable to use holders designed for
4.1.2 To compare the relative levels of crystalline content of the particular DSC instrument being used. For holders for
two or more specimens of a sample of a fluoropolymer relative which the cover has the shape of a small cup, the top should be
to another sample by measuring the heat of fusion; inserted with the open side of the cup up.
NOTE 2—Absolute values of crystalline content cannot be determined
until values for heats of fusion of the completely crystalline polymers are 5.3 Nitrogen, or other inert gas supply for purging purposes.
available. 5.4 Balance, with capacity greater than 15 mg, capable of
4.1.3 The heat of crystallization of pure PTFE homopoly- weighing to the nearest 0.01 mg.
mer is depending on the relative molecular weight of the
specimen. Some PTFE resins are modified with small amounts 6. Procedure
of comonomers. These modifications have profound effects on
6.1 General Requirements—In general, Test Method D3418
crystallization behavior and shall be considered when evaluat-
shall be used whenever possible. There are instances, however,
ing the results.
when following Test Method D3418 will not give the desired
4.1.4 To characterize PTFE (DSC thermal curves deter-
results, will not provide information needed for proper inter-
mined on powders or products of PTFE that have never been
pretation of the resultant thermal curve, or will require more
melted convey appreciable information about details of mor-
time for the analysis than need be spent for results having
phology and molecular structure);4
suitable precision. Examples of these instances include the
4.1.5 To supplement the test for standard specific gravity
following:
(SSG) described in Specifications D4894 and D4895 by using
the heat of crystallization of pure PTFE homopolymer, depend- 6.1.1 The requirement that scans be started at room
ing on the relative molecular weight of the specimen. The temperature, a provision usually not required with all fluoropo-
scopes of these specifications, however, include PTFE resins lymers;
modified with small amounts of comonomers, and many 6.1.2 At times the thermal curve that results from the
commercial PTFE resins are modified in this manner. These analysis provides information that cannot be interpreted in a
modifications can have profound effects on crystallization useful manner by Test Method D3418, but can be interpreted
behavior. Published relationships4 between heat of crystalliza- following the procedures of Section 7.
tion and molecular weight refer to pure PTFE homopolymers 6.2 Calibration—The procedures for calibration provided in
and, therefore, cannot be applied to the modified resins. Test Method E793 shall be used. The comments in Test Method
D3418 are helpful when reviewed. The calibration is carried
4
out by using an appropriate amount of at least two selected
Sperati, C. A., “Polytetrafluoroethylene: History of Its Development and Some
standards weighed to the nearest 0.01 mg. Select the standard
Recent Advances” (67 references), High Performance Polymers: Their Origin and
Development, Seymour and Kirshenbaume (eds), Marcel Deckker, New York, 1986, materials so that their range includes the first-order transition
p. 274. temperature(s) of the fluoropolymer being tested. It has been

2
 D4591 − 17
found that only one standard is needed to validate the instru- Table 1. Use a dwell time long enough to remove (or
ment between calibrations. normalize) any homogenous crystal nucleation effects of the
6.3 A standard specimen mass shall be in the range of 9 to polymer before starting the cooling. For PVDF a dwell time of
10 mg weighed to an accuracy of 0.01 mg. For routine analysis, ten minutes at 210°C is required. DSC analysis used to
a nonstandard specimen size may be used in cases where determine the presence of other components in the specimens
equivalence to the standard mass has been established for should usually be started at room temperature.
particular properties. A specimen mass different from the NOTE 7—Residual homogeneous crystal nuclei can affect the values of
standard shall be reported. Tm, Tc, and heats of transition.

NOTE 5—Thermal curves from such analyses not using the standard 7. Calculation
specimen mass range may not compare with curves obtained using the
standard mass range. Due to the sensitivity of the peak, Tm, to the 7.1 Determining Transition Temperatures—As illustrated in
specimen size, the results may be outside the expected precision and bias. both Fig. 1 and in Test Method D3418, the temperature of a
6.4 Place the test specimen in the DSC sample pan, cover melting peak on a DSC thermal curve shall be designated Tm 1,
with pan cover, and crimp. Place the pan with specimen in the Tm 2, etc., numbered in order of increasing temperature. The
DSC sample holder or cell at the heating cycle starting temperature at which a tangent to the curve intercepts an
temperature. extension of the base line on the low-temperature side shall be
designated T f, and the temperature at which a tangent to the
6.5 Heating and cooling rates of 10°C/min shall be standard curve intercepts an extension of the base line on the high-
(except as noted in Table 1). Other heating rates may be useful temperature side shall be designated Te.
for some routine analyses. Any rates different from the stan-
dard must be reported and thermal curves from such analyses NOTE 8—Fluoropolymers can have various crystal forms or undergo
must not be used in comparison with curves obtained using the reorganization. Therefore, the resulting DSC curve can have two or more
peaks or peaks with pronounced shoulders. The Tm 1 value of one sample
standard rate. with one peak may be the same as the Tm2 value of another sample with
NOTE 6—Other heating rates will change the observed melting and two peaks.
cooling temperature values. 7.1.1 Fig. 1 was selected to show two endothermic peaks
6.6 Before starting the scan at the controlled rate, heat the during a melting cycle, and the peaks are identified on the
specimen at the highest rate possible with the instrument being figure. Determination of the temperatures for crystallization is
used to the temperature shown in Table 1 for the fluoropolymer carried out in a comparable manner, as shown both in Fig. 2
being tested. The time required to reach thermal equilibrium at and in Figure 1 of Test Method D3418.
the starting temperature will depend on the particular instru- 7.2 Determining Heats of Transition—Calculation of heats
ment being used. If heats of crystallization are being of fusion or crystallization shall be done in accordance with
determined, stop the heating at the end temperature given in Test Method D3418. Instrumental determination of heats of
transition requires temperature ranges to determine heat con-
tent. Due to instrument start-up effects that can last up to 1 or
TABLE 1 Recommended Temperature Limits for DSC 2 min, the integration range should be 10 to 20°C above the
Measurements for Various FluoropolymersA, B
starting and below the final temperature. A smaller integration
Heating Curve Dwell Cooling Curve
Fluoropolymer
Rate, Typical range would be Tf − 20 or 30°C and Te + 10 or 20°C. The
Start, End, Time, Start, End, °C/min Values,C °C
°C °C min °C °C calculated heat value should not be sensitive to small changes
(homopolymers) (5°C in the integration range).
PTFE 270 380 5 380 270 10 315–360
PCTFE 130 250 250 195 10
NOTE 9—Multiple crystal forms and the complicated morphology of
195 130 0.2 200–225
PVDF 25 210 10 210 25 10 155–180
(copolymers)
PFA 200 350 350 200 10 280–330
MFA 200 350 350 200 10 260–290
FEP 200 320 320 200 10 240–290
ETFE 140 320 320 140 10 210–270
ECTFE 200 300 300 200 10 230–250
VDF/HFP 25 210 10 210 25 10 130–165
VDF/CTFE 25 210 10 210 25 10 90–170
VDF/TFE 25 200 10 200 25 10 100–150
VDF/TFE/HFP 25 150 10 150 25 10 <130
VDF/TFE/HFP 25 210 10 210 25 10 >130
A
Report peaks (and shoulders) from lowest to highest (for example, Tm 1 < Tm 2 <
Tm 3 ... ).
B
The integration range should be 10 to 20°C above the starting and below the final
temperature. A smaller integration range would be Tf − 20 or 30°C and Te + 10 or
20°C. The calculated heat value should not be sensitive to small changes (5°C in
the integration range).
C
Typical values cited represent an expected range of peak values for this test.
These values shall not be used for specifications. Copolymer peak values (and
intensities) will vary with comonomer ratios and may not be within the cited ranges.
FIG. 1 Heating Curve

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 D4591 − 17
higher-temperature peak by the height of a peak at a lower
temperature. Since this characteristic is reported as a ratio, the
heights can be measured in any convenient units. This mea-
surement is illustrated as CD/AB in Fig. 1.
NOTE 10—Great care must be taken to control the prior thermal history
of the specimen before testing due to the sensitivity of this parameter on
peak height obtained with polymorphic polymers.
7.3.2 A value for width at half-height of an endothermic
peak is defined as a value (in degrees Celsius) that represents
the width of a peak at a point one-half the distance between the
base line and the maximum of the peak that is being charac-
terized. Peak width at half-height is illustrated by the value of
the line, EG, in Fig. 1.

8. Report
8.1 The report for specimens analyzed in accordance with
the objective of 4.1.4 may include values for ratio of peak
FIG. 2 Cooling Curve
heights and for width at half-height of the endothermic peak(s).

9. Precision and Bias

VDF based copolymers can make it difficult to determine heats of
transition on this polymer. 9.1 Precision:
9.1.1 Repeatability—See Test Method D3418.
7.3 Calculation of Results of Determinations made in ac-
9.1.2 Reproducibility—See Test Method D3418.
cordance with the objectives of 4.1 may include transition
peaks or shoulders and transition heats. Additional determina- 9.2 Bias—See Test Method D3418.
tions may use the steps listed in 7.3.1 and 7.3.2.
7.3.1 The ratio of peak heights may be useful in character- 10. Keywords
izing materials that show two or more distinct peaks or 10.1 differential scanning calorimetry; DSC; fluoropoly-
shoulders. This ratio is determined by dividing the height of a mer(s); heats of fusion; melting point; thermal analysis

SUMMARY OF CHANGES

Committee D20 has identified the location of selected changes to this standard since the last issue
(D4591–07(2012)) that may impact the use of this standard. (December 1, 2017)

(1) Added new 4.1.3. (4) Changed Typical Values of VDF/HFP from “130-165” to
(2) Deleted “and” “Intergrating DSC Curve Thermal Curves “90-170” in Table 1.
with” in Title of Table 1. (5) Added “or undergo reorganization” in NOTE 8.
(3) Changed Typical Values of PVDF from “160-175” to
“155-180” in Table 1.

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