INTERNATIONAL ISO

STANDARD 11359-2

Second edition
2021-11

Plastics — Thermomechanical
analysis (TMA) —
Part 2:
Determination of coefficient of
linear thermal expansion and glass
transition temperature
Plastiques — Analyse thermomécanique (TMA) —
Partie 2: Détermination du coefficient de dilatation thermique
linéique et de la température de transition vitreuse

Reference number
ISO 11359-2:2021(E)

© ISO 2021
ISO 11359-2:2021(E)

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 ISO 11359-2:2021(E)

Contents Page

Foreword......................................................................................................................................................................................................................................... iv
1 Scope.................................................................................................................................................................................................................................. 1
2 Normative references...................................................................................................................................................................................... 1
3 Terms and definitions..................................................................................................................................................................................... 1
4 Principle......................................................................................................................................................................................................................... 2
5 Apparatus..................................................................................................................................................................................................................... 2
6 Test specimens........................................................................................................................................................................................................ 2
6.1 Preparation................................................................................................................................................................................................. 2
6.2 Conditioning.............................................................................................................................................................................................. 3
7 Procedure..................................................................................................................................................................................................................... 3
7.1 Calibration of apparatus................................................................................................................................................................. 3
7.2 Determination.......................................................................................................................................................................................... 3
8 Expression of results........................................................................................................................................................................................ 4
8.1 Method of calculation........................................................................................................................................................................ 4
8.1.1 Differential coefficient of linear thermal expansion, ........................................................................ 4
8.1.2 Mean coefficient of linear thermal expansion, ........................................................................................ 5
8.1.3 Glass transition temperature................................................................................................................................... 6
8.1.4 Representative temperature.................................................................................................................................... 7
8.2 Precision........................................................................................................................................................................................................ 7
9 Test report................................................................................................................................................................................................................... 7
Annex A (informative) Precision and reproducibility data for the determination of the
mean coefficient of linear thermal expansion using TMA....................................................................................... 9
Bibliography.............................................................................................................................................................................................................................. 10

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ISO 11359-2:2021(E)

Foreword
ISO (the International Organization for Standardization) is a worldwide federation of national standards
bodies (ISO member bodies). The work of preparing International Standards is normally carried out
through ISO technical committees. Each member body interested in a subject for which a technical
committee has been established has the right to be represented on that committee. International
organizations, governmental and non-governmental, in liaison with ISO, also take part in the work.
ISO collaborates closely with the International Electrotechnical Commission (IEC) on all matters of
electrotechnical standardization.
The procedures used to develop this document and those intended for its further maintenance are
described in the ISO/IEC Directives, Part 1. In particular, the different approval criteria needed for the
different types of ISO documents should be noted. This document was drafted in accordance with the
editorial rules of the ISO/IEC Directives, Part 2 (see www.iso.org/directives).
Attention is drawn to the possibility that some of the elements of this document may be the subject of
patent rights. ISO shall not be held responsible for identifying any or all such patent rights. Details of
any patent rights identified during the development of the document will be in the Introduction and/or
on the ISO list of patent declarations received (see www.iso.org/patents).
Any trade name used in this document is information given for the convenience of users and does not
constitute an endorsement.
For an explanation of the voluntary nature of standards, the meaning of ISO specific terms and
expressions related to conformity assessment, as well as information about ISO's adherence to
the World Trade Organization (WTO) principles in the Technical Barriers to Trade (TBT), see
www.iso.org/iso/foreword.html.
This document was prepared by Technical Committee ISO/TC 61, Plastics, Subcommittee SC 5, Physical-
chemical properties.
This second edition cancels and replaces the first edition (ISO 11359-2:1999), which has been technically
revised.
The main changes compared to the previous edition are as follows:
— the testing procedure has been revised with regard to test load and purge gas conditions;
— the evaluation of determination of the mean coefficient of thermal expansion with reference
specimen has been specified more precisely;
— the document has been editorial revised.
A list of all parts in the ISO 11359 series can be found on the ISO website.
Any feedback or questions on this document should be directed to the user’s national standards body. A
complete listing of these bodies can be found at www.iso.org/members.html.

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INTERNATIONAL STANDARD ISO 11359-2:2021(E)

Plastics — Thermomechanical analysis (TMA) —

Part 2:
Determination of coefficient of linear thermal expansion
and glass transition temperature

1 Scope
This document specifies a test method, using thermodilatometry[1], for the determination of the
coefficient of linear thermal expansion of plastics in a solid state by thermomechanical analysis (TMA).
This document also specifies the determination of the glass transition temperature using TMA.
NOTE The coefficient of linear thermal expansion can be measured using various types of thermodilatometry
apparatus. This document concerns only TMA apparatus.

2 Normative references
The following documents are referred to in the text in such a way that some or all of their content
constitutes requirements of this document. For dated references, only the edition cited applies. For
undated references, the latest edition of the referenced document (including any amendments) applies.
ISO 291, Plastics — Standard atmospheres for conditioning and testing
ISO 472, Plastics — Vocabulary
ISO 11359-1, Plastics — Thermomechanical analysis (TMA) — Part 1: General principles

3 Terms and definitions

For the purposes of this document, the terms and definitions given in ISO 472, ISO 11359-1 and the
following apply.
ISO and IEC maintain terminological databases for use in standardization at the following addresses:
— ISO Online browsing platform: available at https://​w ww​.iso​.org/​obp
— IEC Electropedia: available at https://​w ww​.electropedia​.org/​
3.1
differential coefficient of linear thermal expansion
α
expansion, normalised to the reference length L0 at room temperature, for any of the three dimensions
at temperature T and at constant pressure p , given in reciprocal kelvins, by the following formula:

( dL ) p 1 ( dL / dt ) p 1
α= × = ×
( dT ) p L0 ( dT / dt ) p L0
where

L0 is the reference length at room temperature T0 , in the axis of measurement;

L is the length at temperature T , in the axis of measurement;

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ISO 11359-2:2021(E)

dL is the change in length over the time interval dt at constant pressure p ;

dT is the change in temperature over the time interval dt at constant pressure p

3.2
mean coefficient of linear thermal expansion
α
expansion, normalised to the reference length L0 at room temperature, for any of the three dimensions
in a specified temperature interval ΔT at constant pressure, given in reciprocal kelvins, by the following
formula:
∆L 1
α= ×
∆T L0
where

∆L is the change in length of the test specimen between two temperatures T1 and T2 ;

L0 is the reference length of the test specimen at room temperature in the axis of measurement;
∆T is the change in temperature, equal to T2 − T1

Note 1 to entry: The determination is made over a temperature interval ∆T between T1 and T2 . The
representative temperature Trep is given by

T1 + T2
Trep =
2

Note 2 to entry: By replacing the term “length” by “volume” in the formulae in 3.1 and 3.2, the coefficient of
volumetric thermal expansion can be obtained.

4 Principle
The change in a dimension of a test specimen is measured as a function of temperature using a TMA
apparatus to generate a TMA curve from which the coefficient of linear thermal expansion can be
calculated.

5 Apparatus
The components of the TMA apparatus used for this document shall be as specified in ISO 11359-1 and
shall also be capable of
a) operating in a compression mode or a tension mode or both, and
b) maintaining the specimen under a controlled atmosphere in accordance with ISO 291.
NOTE 1 Measurements on specimens of film or fibre are made in the tension mode.

NOTE 2 Typically, an atmosphere of dry air or an inert gas such as nitrogen is used.

6 Test specimens

6.1 Preparation
Test specimens shall be prepared in accordance with ISO 11359-1.
The standard test specimen is a rectangular specimen 5 mm to 10 mm in length and about 5 mm in
width. However, specimens of other dimensions may be used by agreement between the interested

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 ISO 11359-2:2021(E)

parties. The ends of the test specimen shall be parallel. If applicable, the orientation of the specimen
with respect to the direction of production shall be recorded, i.e. machine direction, transverse
direction or other.
Reference shall be given to the relevant material standards for the number of test specimens, but at
least three specimens shall be prepared and tested from each sample.

6.2 Conditioning
Reference to the relevant material standards shall be given for the conditioning of specimens before
measurement.
In order to eliminate any thermal-memory effects in the specimen, each specimen may be heated from
the minimum measurement temperature (at least 50 °C below Tg ) to the maximum temperature (at
least 50 °C above Tg ), and held at this latter temperature for at least 5 min. Subsequently, the specimen
may be cooled to the minimum temperature at the same rate as that to be used for actual measurements.
NOTE 1 Heating the test specimen to temperatures of 50 °C above Tg can result in changes in molecular
orientation and/or blend morphology, thereby changing the coefficient of linear thermal expansion in certain
directions.

NOTE 2 If thermal-memory effects are observed despite preheating for 5 min at maximum temperature, the
preheating time can be extended as long as no decomposition occurs.

7 Procedure

7.1 Calibration of apparatus

The apparatus shall be calibrated in accordance with ISO 11359-1. After cleaning the surfaces of the
specimen, probe and sample holder, the specimen shall be placed on the sample holder with the probe
as close as possible.

7.2 Determination
The unloaded probe shall be set on the upper surface of the specimen. A load shall be applied that is
big enough to achieve a reliable transfer of the load to the specimen, but at the same time low enough
to prevent a detectable compression of the specimen. Preferably, loads in the range between 1 mN and
50 mN should be used. Provided the effect on the measured value is small, other loads may be used.
When specimens made of film, fibre or soft material are tested, the determination shall be carried out
in tension mode with both ends of the specimen gripped.
A constant gas flow shall be maintained around the specimen, preferably of dry inert gas or dry air,
within a flow rate range of 0 ml/min to 100 ml/min. However, other atmospheres may be used by
agreement between the interested parties.
The temperature of the specimen shall be increased at a constant rate of not more than 5 K/min.
The TMA curve for the test specimen shall be recorded, i.e. the change in length with increasing
temperature.
NOTE 1 In order to check for anisotropy effects, specimens can be taken in different directions from the
sample to be investigated.

Under the same conditions, the change in length of a reference specimen having a known mean coefficient
of linear thermal expansion and about the same length as the test specimen may be measured.
NOTE 2 This is not necessary when the apparatus used measures the difference in length between the test
specimen and a reference specimen directly.

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ISO 11359-2:2021(E)

8 Expression of results

8.1 Method of calculation

8.1.1 Differential coefficient of linear thermal expansion, α

The differential coefficient of linear thermal expansion α , in reciprocal kelvins (K−1), at temperature T
shall be obtained from the TMA curve using Formula (1)(see Figure 1):
dL 1
α= × (1)
dT L0
where

L0 is the length of the specimen, in micrometres, at room temperature;

L is the length of the specimen, in micrometres, at temperature T;
T is the temperature, in kelvins.
The value of α shall be calculated to the nearest 10−7 K−1 for each specimen. The mean of these individual
values shall be calculated and rounded to the nearest 10−6 K−1.
In the case of a test specimen exhibiting a glass transition, the differential coefficient of thermal
expansion shall be calculated before and after the glass transition.

Key
L length of the specimen
T temperature
T1, T2 selected temperatures for determination of the differential coefficient of linear thermal expansion
1 slope dL/dT at temperature T1
2 slope dL/dT at temperature T2

Figure 1 — Determination of differential coefficient of linear thermal expansion, α

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 ISO 11359-2:2021(E)

8.1.2 Mean coefficient of linear thermal expansion, α

8.1.2.1 Method A: Determination without reference specimen

The mean coefficient of linear thermal expansion, α , in reciprocal kelvins (K−1), between two
temperatures T1 and T2 shall be obtained from the TMA curve using Formula (2) (see Figure 2):
∆L 1
α= × (2)
∆T L0
where

L0 is the length of the specimen, in micrometres, at room temperature;

∆L is the difference in length, in micrometres;

∆T ( = T2 − T1 ) is the temperature difference, in kelvins.

Two temperatures shall be selected and the difference in temperature ∆T shall be calculated.
The corresponding change in length ∆L shall be determined from the TMA curve.
The value of the mean coefficient of linear thermal expansion, α , shall be calculated to the nearest 10−7
K−1 for each specimen. The mean of these individual values shall be calculated and rounded to the
nearest 10−6 K−1.
Calculation of the corresponding representative temperature is specified in 8.1.4.
In the case of a test specimen exhibiting a glass transition, the coefficient of linear thermal expansion
shall be calculated before and after the glass transition.

Key
L length of the specimen
T temperature
T1, T2 limits of the temperature range ΔT used for determination of the mean coefficient of linear thermal
expansion
1 change of length ΔL between temperatures T1 and T2
2 change of temperature ΔT between temperatures T1 and T2

Figure 2 — Determination of mean coefficient of linear thermal expansion α

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ISO 11359-2:2021(E)

8.1.2.2 Method B: Determination with reference specimen

For this method, the length of the test specimen and the reference specimen L0 shall be the same. The
mean coefficient of linear thermal expansion α , in reciprocal kelvins (K−1), between two temperatures
T1 and T2 shall be obtained using Formula (3):
∆LSpm − ∆LRef
α= + α Ref (3)
L0 × (T2 − T1 )
where

α is the mean coefficient of linear thermal expansion of the test specimen, in reciprocal kelvins
(K−1)

L0 is the length of the test specimen and reference specimen, in micrometres, at room temperature

T1 is the lower end of the temperature range, in degrees Celsius, used to measure the mean
coefficient of linear thermal expansion

T2 is the higher end of the temperature range, in degrees Celsius, used to measure the mean
coefficient of linear thermal expansion

∆LSpm is the difference in test specimen length, in micrometres, between T1 and T2 , i.e. the meas-
ured value of [(length at T2 ) − (length at T1 )]

∆LRef is the difference in reference specimen length, in micrometres, between T1 and T2 ,, i.e. the
measured value of [(length at T2 ) − (length at T1 )]

α Ref is the value of the mean coefficient of linear thermal expansion of the reference specimen,
in reciprocal kelvins, between T1 and T2

The value of the mean coefficient of linear thermal expansion α shall be calculated to the nearest
10−7 K−1 for each specimen. The mean of these individual values shall be calculated and rounded to the
nearest 10−6 K−1.
Calculation of the corresponding representative temperature is specified in 8.1.4.
In the case of a test specimen exhibiting a glass transition, the coefficient shall be calculated before and
after the glass transition.
NOTE 1 Any material with known constant and reproducible coefficients of linear thermal expansion can be
used for the reference specimen. Suitable examples include aluminium, gold, silica, sapphire, etc.

NOTE 2 Some instruments can measure the difference in length between the test specimen and the reference
specimen ∆LSpm − ∆LRef directly.

8.1.3 Glass transition temperature

The glass transition temperature shall be determined as the point of intersection of the tangents to the
TMA curve before and after the transition (see Figure 3).
NOTE The extrapolated glass transition onset temperature Teig and the extrapolated glass transition end
temperature Tefg can be determined from a differential TMA (DTMA) curve as the points of intersection of the
tangent at the point of inflection with the extrapolated baseline before the glass transition and the extrapolated
baseline after the glass transition, respectively. The width of the transition region is given by Tefg − Teig .

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 ISO 11359-2:2021(E)

Key
L length of the specimen
T temperature
dL/dT slope of the TMA curve
1 differential TMA (DTMA) curve (corresponding to the right ordinate axis dL/dT)
2 TMA curve (corresponding to the left ordinate axis L)
3 glass transition temperature Tg
4 extrapolated glass transition onset temperature Teig
5 extrapolated glass transition end temperature Tefg

Figure 3 — Determination of glass transition temperature

8.1.4 Representative temperature

The corresponding representative temperatures (see 3.2) for the determination of the mean coefficients
of thermal expansion specified in 8.1.2.1 and 8.1.2.2 shall be calculated to the nearest ±0,1 °C for each
specimen. Calculate the mean of these individual values and round to the nearest whole number.

8.2 Precision
An interlaboratory testing for method A has been performed in the USA, and the results show precision
ranging from ±2,6 % to ±12 %. An interlaboratory testing for method B has been performed in Japan,
and the results show a coefficient of variation ranging from 0,99 % to 14,37 %. (See Annex A for details.)

9 Test report
The test report shall include the following:
a) a reference to this document, including its year of publication, i.e. ISO 11359-2:2021;
b) all details necessary for complete identification of the material or product tested (lot number, etc.);
c) the type of test specimen used, its dimensions, the method of preparation and its orientation with
reference to the sheet or article it was taken from;
d) details of the conditioning of the test specimen, if applicable;
e) the type of TMA equipment used;
f) the shape and dimensions of the probe;

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ISO 11359-2:2021(E)

g) the materials used for calibration purposes and the values obtained;
h) the experimental conditions used for the determination, i.e. the rate of heating, the test atmosphere,
the rate of gas flow (if any), the temperature range over which the mean coefficient of linear thermal
expansion was measured and the representative temperature;
i) details of the reference specimen used;
j) the results of the test, i.e., the value of the coefficient of linear thermal expansion α for each
specimen, the mean of α and the standard deviation, the value of the mean coefficient of linear
thermal expansion α for each specimen, the mean of α and the standard deviation, the glass
transition temperature and the TMA curves obtained;
k) details of any operation not specified in this document and/or agreed upon between the parties
concerned;
l) the date(s) of testing.

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 ISO 11359-2:2021(E)

Annex A
(informative)

Precision and reproducibility data for the determination of the

mean coefficient of linear thermal expansion using TMA

Precision data calculated from round-robin determinations of the mean coefficient of linear thermal
expansion using method A are presented in Table A.1. Eight laboratories in the USA participated, using
six different models of instrument, specimens 8 mm long and a 100 °C temperature range.

Table A.1 — Precision data using method A (USA)

Mean coefficient of linear thermal expansion a Precision Maximum deviation
K−1 % %
α ≥ 20 × 10−6 ±2,6 3,7
20 × 10−6 > α ≥ 5 × 10−6 ±5,1 7,8
5 × 10−6 > α ≥ 1 × 10−6 ±12 61
NOTE See ASTM E 831-93.

Reproducibility data calculated from round-robin determinations of the mean coefficients of linear
thermal expansion of different materials using method B are presented in Table A.2. Five laboratories
participated in Japan.

Table A.2 — Reproducibility data for different materials using method B (Japan)
Mean coefficient of linear Coefficient of vari-
Material Standard deviation
thermal expansion ation
α sR sR / α
K−1 K−1 %
Polyethylene (30 °C to 60 °C) 147,4 × 10−6 6,11 × 10−6 4,14
Polyethyleneoxide (30 °C to 120 °C) 106,5 × 10−6 3,63 × 10−6 3,41
Polyimide (30 °C to 200 °C) 17,5 × 10−6 2,51 × 10−6 14,37
Polyimide film (30 °C to 200 °C) 25,4 × 10−6 1,58 × 10−6 6,21
Aluminium (30 °C to 120 °C) 25,1 × 10−6 0,25 × 10−6 0,99
Aluminium (30 °C to 240 °C) 25,8 × 10−6 0,37 × 10−6 1,44

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ISO 11359-2:2021(E)

Bibliography

[1] ICTAC nomenclature of thermal analysis (IUPAC Recommendations 2014)

[2] ASTM E 831-93, Standard Test Method for Linear Thermal Expansion of Solid Materials by
Thermomechanical Analysis

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ISO 11359-2:2021(E)

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