Plastics - Differential Scanning Calorimetry (DSC) - : Draft International Standard Iso/Dis 11357-1

DRAFT INTERNATIONAL STANDARD ISO/DIS 11357-1
ISO/TC 61/SC 5 Secretariat: ANSI
Voting begins on: Voting terminates on:

2008-04-10 2008-09-10
INTERNATIONAL ORGANIZATION FOR STANDARDIZATION • МЕЖДУНАРОДНАЯ ОРГАНИЗАЦИЯ ПО СТАНДАРТИЗАЦИИ • ORGANISATION INTERNATIONALE DE NORMALISATION
Plastics — Differential scanning calorimetry (DSC) —

Part 1:
General principles
Plastiques — Analyse calorimétrique différentielle (DSC) —
Partie 1: Principes généraux
[Revision of first edition (ISO 11357-1:1997)]
ICS 83.080.01
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The CEN Secretary-General has advised the ISO Secretary-General that this ISO/DIS covers a subject
of interest to European standardization. In accordance with the ISO-lead mode of collaboration as
defined in the Vienna Agreement, consultation on this ISO/DIS has the same effect for CEN
members as would a CEN enquiry on a draft European Standard. Should this draft be accepted, a
final draft, established on the basis of comments received, will be submitted to a parallel two-month FDIS
vote in ISO and formal vote in CEN.
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ISO Central Secretariat work of editing and text composition will be undertaken at publication
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THIS DOCUMENT IS A DRAFT CIRCULATED FOR COMMENT AND APPROVAL. IT IS THEREFORE SUBJECT TO CHANGE AND MAY NOT BE
REFERRED TO AS AN INTERNATIONAL STANDARD UNTIL PUBLISHED AS SUCH.
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© International Organization for Standardization, 2008

ISO/DIS 11357-1
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ii © ISO 2008 – All rights reserved

ISO/DIS 11357-1
Contents Page
1 Scope ............................................................................................................................................. 1
2 Normative references .................................................................................................................... 1
3 Terms, definitions, symbols, units and abbreviated terms ......................................................... 2
3.1 Differential scanning calorimetry (DSC).................................................................................. 2
3.2 Calibration material .................................................................................................................. 2
3.3 Reference.................................................................................................................................. 2
3.4 Heat flow rate............................................................................................................................ 2
3.5 Change of heat, ∆Q................................................................................................................... 3
3.6 Specific heat capacity at constant pressure, cp ...................................................................... 3
3.7 Baseline .................................................................................................................................... 4
3.7.1 General................................................................................................................................. 4
3.7.2 Instrument baseline............................................................................................................. 4
3.7.3 Specimen baseline .............................................................................................................. 4
3.7.4 Virtual baseline.................................................................................................................... 5
3.8 Step ........................................................................................................................................... 5
3.8.1 General................................................................................................................................. 5
3.8.2 Step height........................................................................................................................... 5
3.9 Peak .......................................................................................................................................... 5
3.9.1 General................................................................................................................................. 5
3.9.2 Endothermic peak................................................................................................................ 5
3.9.3 Exothermic peak.................................................................................................................. 5
3.9.4 Peak area ............................................................................................................................. 5
3.9.5 Peak height .......................................................................................................................... 6
3.9.6 Peak width ........................................................................................................................... 6
3.10 Characteristic temperatures or times ...................................................................................... 6
4 Principle......................................................................................................................................... 8
4.1 General...................................................................................................................................... 8
4.2 Heat Flux DSC........................................................................................................................... 8
4.3 Power Compensation DSC....................................................................................................... 9
5 Apparatus and materials............................................................................................................... 9
5.1 Differential scanning calorimeter (DSC instrument) ............................................................... 9
5.2 Crucibles................................................................................................................................. 10
5.3 Balance ................................................................................................................................... 10
5.4 Calibration materials .............................................................................................................. 10
5.5 Purge gas................................................................................................................................ 10
6 Specimen ..................................................................................................................................... 11
7 Test conditions and specimen conditioning.............................................................................. 11
7.1 Test conditions....................................................................................................................... 11
7.2 Conditioning of specimens.................................................................................................... 11
8 Calibration ................................................................................................................................... 11
8.1 General.................................................................................................................................... 11
8.2 Calibration materials .............................................................................................................. 12
8.3 Temperature calibration......................................................................................................... 13
8.3.1 General............................................................................................................................... 13
8.3.2 Procedure .......................................................................................................................... 13
8.3.3 Accuracy of calibration ..................................................................................................... 14
8.4 Heat calibration ...................................................................................................................... 14
© ISO 2008 – All rights reserved iii

ISO/DIS 11357-1
8.4.1 General ...............................................................................................................................14

8.4.2 Procedure ...........................................................................................................................14
8.4.3 Accuracy of calibration ......................................................................................................15
8.5 Heat flow rate calibration ........................................................................................................15
8.5.1 General ...............................................................................................................................15
8.5.2 Procedure ...........................................................................................................................16
9 Procedure .....................................................................................................................................17
9.1 Setting up the apparatus.........................................................................................................17
9.1.1 Switching on.......................................................................................................................17
9.1.2 Purge gas............................................................................................................................17
9.1.3 Experimental conditions....................................................................................................17
9.1.4 Baseline determination ......................................................................................................18
9.2 Loading the specimen into the crucible.................................................................................18
9.2.1 General ...............................................................................................................................18
9.2.2 Selection of crucibles ........................................................................................................18
9.2.3 Weighing of specimen crucible .........................................................................................18
9.2.4 Loading of specimen..........................................................................................................18
9.2.5 Crucible requirements........................................................................................................18
9.2.6 Weighing the specimen......................................................................................................18
9.3 Insertion of crucibles into the instrument..............................................................................19
9.4 Performing measurements .....................................................................................................19
9.4.1 General ...............................................................................................................................19
9.4.2 Scanning mode...................................................................................................................19
9.4.3 Isothermal mode.................................................................................................................19
9.5 Removal of crucibles ..............................................................................................................20
9.5.1 Checking for loss of mass .................................................................................................20
9.5.2 Inspection of specimens after measurements..................................................................21
9.5.3 Checking of crucibles and specimen holder assembly....................................................21
10 Test report ....................................................................................................................................21
Annex A (normative) Extended, high precision temperature calibration [14] .........................................22
Annex B (normative) Extended, high precision heat calibration .............................................................25
Annex C (informative) Recommended calibration materials ...................................................................27
Annex D (informative) Interaction of calibration materials with different crucible materials.................30
Annex E (informative) General recommendations ...................................................................................32
Annex F (informative) Bibliography ..........................................................................................................33
iv © ISO 2008 – All rights reserved

ISO/DIS 11357-1
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 Interna-
tional Electrotechnical Commission (IEC) on all matters of electrotechnical standardization.
International Standards are drafted in accordance with the rules given in the ISO/IEC Directives, Part 2.
The main task of technical committees is to prepare International Standards. Draft International Standards
adopted by the technical committees are circulated to the member bodies for voting. Publication as an Interna-
tional Standard requires approval by at least 75 % of the member bodies casting a vote.
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.
ISO 11357-1 was prepared by Technical Committee ISO/TC 61, Plastics, Subcommittee SC 5, Physical-
chemical properties.
This second/third/... edition cancels and replaces the first/second/... edition (ISO 11357-1:1997), [clause(s) /
subclause(s) / table(s) / figure(s) / annex(es)] of which [has / have] been technically revised.
ISO 11357 consists of the following parts, under the general title Plastics — Differential scanning calorimetry
(DSC):
 Part 1: General principles
 Part 2: Determination of glass transition temperature
 Part 3: Determination of temperature and enthalpy of melting and crystallisation
 Part 4: Determination of specific heat capacity
 Part 5: Determination of characteristic reaction-curve temperatures and times, enthalpy of reaction and
degree of conversion
 Part 6: Oxidation induction time (isothermal OIT) or temperature (dynamic OIT)
 Part 7: Determination of crystallisation kinetics
Annexes C, D, E and F of this part of ISO 11357 are for information only. Deletion requested by France, ok?
© ISO 2008 – All rights reserved v

ISO/DIS 11357-1
Introduction
This International Standard describes the realization of several standardised thermoanalytical test methods
which can be used for quality assurance purposes, for routine checks of raw materials and finished products
or for determination of comparable data needed for data sheets or databases. The procedures mentioned in
this International Standard apply as long as special product standards or standards describing special atmos-
pheres for conditioning of specimens do not require alternate regulations.
For scientific investigations or resolution of special analytical problems all technical capabilities of instruments
beyond the regulations of this International Standard may be used.
The most important changes in this revision of ISO 11357-1 include:
• Indication of the preferred graphical representation of DSC diagrams in accordance with thermody-
namic requirements.
• An additional more precise method for temperature calibration providing an accuracy of ± 0,3 K for an
extended temperature range.
• An additional more precise procedure for enthalpy calibration providing an accuracy of ± 0,5 %.
• A procedure for heat flow rate calibration.
• Information on interactions between calibration substances and crucible materials.
vi © ISO 2008 – All rights reserved

DRAFT INTERNATIONAL STANDARD ISO/DIS 11357-1
Plastics — Differential scanning calorimetry (DSC) — Part 1:

General principles
WARNING — Use of this International Standard may involve hazardous materials, operations
and equipment. This International Standard does not purport to address all of the safety
problems associated with its use. It is the responsibility of the user of this standard to estab-
lish appropriate health and safety practices and to determine the applicability of the regula-
tory limitations prior to its use.
1 Scope
This International Standard specifies differential scanning calorimetry (DSC) methods for the thermal analysis
of polymers and polymer blends such as
− thermoplastics (polymers, moulding compounds and moulding products with or without filler(s), fibres or
reinforcing additives),
− thermosets (uncured or cured materials with or without filler(s), fibres or reinforcing additives),
− elastomers (with or without filler(s), fibres or reinforcing additives).
This International Standard is applicable for observing and quantifying various phenomena or properties of the
above mentioned materials such as
− physical transitions (glass transition, phase transitions like melting and crystallisation, polymorphic transi-
tions, etc.),
− chemical reactions (polymerisation, cross-linking and curing of elastomers and thermosets, etc.),
− oxidation stability,
− heat capacity.
Part 1 of this International Standard establishes general principles of differential scanning calorimetry such as
description of the principle and the apparatus, sampling, calibration and general aspects of the procedure and
test report common to all following parts.
Details on performing specific methods are given in subsequent parts of this International Standard (see fore-
word).
2 Normative references
The following normative documents contain provisions which, through reference in this text, constitute provi-
sions of this International Standard. For dated references, subsequent amendments to, or revisions of, any of
these publications do not apply. However, parties to agreements based on this International Standard are en-
couraged to investigate the possibility of applying the most recent editions of the normative documents indi-
cated below. For undated references, the latest edition of the normative document referred to applies includ-
ing any amendment. Members of ISO and IEC maintain registers of currently valid International Standards.
© ISO 2008 – All rights reserved 1

ISO/DIS 11357-1
The following referenced documents are indispensable for the application of this document. For dated refer-
ences, only the edition cited applies. For undated references, the latest edition of the referenced document
st
(including any amendments) applies. France requests exchange of 1 paragraph to text highlighted in yellow,
ok?
− ISO 291, Plastics - Standard atmospheres for conditioning and testing
− ISO 472, Plastics – Vocabulary
− ISO 80000-5, Quantities and units – Part 5: Thermodynamics
3 Terms, definitions, symbols, units and abbreviated terms

For the purposes of this International Standard, the terms, definitions, symbols, units and abbreviated terms of
ISO 472, ISO 80000-5 and the following apply:
3.1 Differential scanning calorimetry (DSC)
A technique in which the difference between the heat flow rate into the sample crucible containing the speci-
men and that into the reference crucible is derived as a function of temperature and/or time while the speci-
men and reference are subjected to the same controlled temperature program in a specified atmosphere us-
ing a symmetrical measuring system.
It is common practice to record, for each measurement, a curve in which temperature or time is plotted on the
abscissa and heat flow rate difference on the ordinate. The endothermic and / or exothermic direction shall be
indicated on the DSC curve.
NOTE According to the principles of thermodynamics, energy absorbed by a system is considered positive while en-
ergy released is negative. This approach implies that the endothermic direction points upwards in the ordinate and the
exothermic direction downwards (cf. Figs. 1 and 2). It also has the advantage that the direction of thermal effects in plots
of heat flow rate and specific heat are consistent.
3.2 Calibration material
A material for which one or more of the thermal properties are sufficiently homogeneous and well established
to be used for the calibration of a DSC apparatus or for assessment of a measurement method.
3.3 Reference
The crucible used on the reference side of the symmetric specimen holder assembly.
NOTE 1 Normally the reference crucible is empty.
NOTE 2 In special cases such as the measurement of highly filled or reinforced polymers or specimens having a heat
capacity comparable to that of the crucibles a suitable material can be used inside the reference crucible. This reference
material should be thermally inactive over the temperature and time range of interest and its heat capacity should be simi-
lar to that of the specimen. In the case of filled or reinforced products the pure filler or reinforcement can be used for ex-
ample.
3.4 Heat flow rate
Heat transferred per unit time (dQ / dt) expressed in watts (W) or milliwatts (mW).
NOTE The total quantity of heat transferred Q corresponds to the time integral of heat flow rate
dQ
Q= ∫ dt
dt (1)
2 © ISO 2008 – All rights reserved

ISO/DIS 11357-1
3.5 Change of heat, ∆Q
Quantity of heat absorbed (endothermic: ∆Q positive) or released (exothermic: ∆Q negative) within a specified
time ( t ) or temperature ( T ) range by a specimen undergoing a chemical or physical change and/or a tem-
perature change.
t2
dQ
∆Q = ∫
t1
dt
dt (2)
T2
60 dQ
or ∆Q =
β ∫
T1
dt
dT (3)
where ∆Q is expressed in joules (J) or as molar or specific quantity ∆ q in joules per amount of substance
(J . mol -1) or joules per unit mass (J . g-1)
dT
and β is the constant heating or cooling rate . -1
expressed in Kelvin per minute (K min )
dt
NOTE if measurements are done at constant pressure, ∆Q corresponds to the change of enthalpy ∆H .
3.6 Specific heat capacity at constant pressure, cp
Quantity of heat necessary to raise the temperature of a unit mass of material by 1 K at constant pressure
1 ∂ Q 
cp = ⋅   (4)
m  ∂ T p
1 60 dQ
or cp = ⋅ ⋅   (5)
m β  d t p
where ∂ Q is the quantity of heat, expressed in joules (J), necessary to raise the temperature of material of
mass m , expressed in amount of substance (mol) or mass (g), by ∂ T expressed in Kelvin (K) at
constant pressure and β is the constant heating rate, expressed in Kelvin per minute (K min )
. -1
and c p is expressed in joules per gram Kelvin (J . g-1 . K-1]
. -1 . -1
NOTE 1 c p may also be expressed in joules per mol Kelvin [J mol K ] where conversion from grams to moles is
performed (i.e. m then represents the quantity of material expressed in moles).
NOTE 2 When analysing polymers, care must be taken to ensure that the measured specific heat capacity does not
include any heat change due to a chemical reaction or a physical transition.

ISO/DIS 11357-1
2
endo
1
T
3
dQ/dt
4
t
Key
dQ/dt Hreat flow rate 1 Specimen baselines
T Temperature 2 Virtual baseline
T Time 3 Instrument baseline
endo Endothermal direction 4 Quasi-stationary range
Figure 1 — Schematic drawing of baselines
3.7 Baseline
3.7.1 General
Part of the recorded curve without any reactions or transitions. This can be an isothermal baseline when the
temperature is maintained constant or a dynamic baseline when the temperature is changed according to a
controlled temperature program.
The baselines described hereafter shall be used in the quasi-stationary range only, i.e. when the instrument
runs at stable conditions after starting and before ending the DSC run (cf. Figure 1).
3.7.2 Instrument baseline
Curve obtained using only empty crucibles of identical mass and material in the sample and reference posi-
tions of the DSC cell.
NOTE The instrument baseline is required for heat capacity measurements.
3.7.3 Specimen baseline
DSC curve obtained outside any reaction or transition zone(s) while the instrument is loaded with specimen in
its crucible and reference. In this part of the recorded curve, the heat flow rate difference depends solely on
the heat capacity of the specimen and the instrument baseline.

ISO/DIS 11357-1
NOTE The specimen baseline reflects the relatively low temperature dependence of the heat capacity of the speci-
men and is thus approximately constant, i.e. the baseline is approximately flat.
For heat capacity determinations in addition to the dynamic DSC curve isothermal start and end baselines are
required as well as an interpolated baseline between start and end isotherms (see Figure1).
3.7.4 Virtual baseline
An imaginary line drawn through a reaction and/or transition zone assuming the heat of reaction and/or transi-
tion to be zero. Assuming the heat capacity change with temperature to be linear, it is drawn by interpolating
or extrapolating the recorded specimen baseline using a straight line. The virtual baseline is normally indi-
cated on the DSC curve for convenience (see Figures 1 and 2).
The virtual baseline drawn from peak onset Ti to peak end Tf (peak baseline) allows the determination of the
peak area from which the heat of transition can be obtained. If there is no significant change of heat capacity
during the transition or reaction the baseline can be drawn simply by connecting peak onset and peak end
linearly. If significant heat capacity changes occur sigmoidal baselines can be used.
NOTE Extrapolated and interpolated virtual baselines can deviate from each other (see Figure 2).
3.8 Step
3.8.1 General
A maintained positive or negative change of the level of a DSC curve within a limited temperature range.
NOTE A step in the DSC curve is caused e.g. by glass transitions (see Figure 2).
3.8.2 Step height
Difference between height of extrapolated baselines after and before step at the time or temperature at which
the distance to either baserline is equal.
3.9 Peak
3.9.1 General
Part of the DSC curve which departs from a specimen baseline, reaches a maximum or minimum, and subse-
quently returns to a specimen baseline.
NOTE A peak in the DSC curve may indicate a chemical reaction or first order transition. The initial deviation of the
peak from the virtual baseline corresponds to the start of the reaction or transition.
3.9.2 Endothermic peak
A peak in which the heat flow rate into the specimen compartment is greater than that into the reference com-
partment. This corresponds to a transition which absorbs heat.
3.9.3 Exothermic peak
A peak in which the heat flow rate into the specimen compartment is less than that into the reference com-
partment. This corresponds to a transition which releases heat.
3.9.4 Peak area
Area enclosed by the peak and the virtual interpolated baseline.

ISO/DIS 11357-1
3.9.5 Peak height
Greatest distance in the ordinate direction between the virtual interpolated baseline and the DSC curve during
a peak.
NOTE The height which is expressed in Watts (W) or watts per gram (W/g), is not necessarily proportional to the
mass of the specimen.
3.9.6 Peak width
Distance between onset and end temperatures or times of a peak.
3.10 Characteristic temperatures or times
For all types of DSC instruments different types of temperatures are to be distinguished:
temperature of reference position
temperature of sample position
Preferably the reference position temperature shall be used for displaying thermograms. If the sample position
temperature is used then this shall be reported.
The following are the characteristic temperatures (T) and times (t) on a DSC curve, where distinct tempera-
tures shall be expressed in degree Celsius (°C), relative temperatures and temperature differences in Kelvin
(K) and time in seconds (sec) or minutes (min) (cf. Figure 2).

ISO/DIS 11357-1
endo T p,m
T f,m
T i,m
T ei,c T ef,c
T ef,g T f,g
T 1/2,g T ei,m T ef,m

T i,c T f,c
dQ/dt
T i,g T ei,g
T p,c
1
2
Key
dQ/dt Heat flow rate 1 Extrapolated baseline
T Temperature 2 Interpolated baseline
endo Endothermal direction
Characteristic temperatures:
The first index denotes the particular point of step or peak:
– Onset Ti , ti First detectable deviation of DSC curve from extrapolated start baseline,
– Extrapolated onset Tei , tei Intersection of virtual interpolated baseline and tangent at the point of inflection of the
peak onset or extrapolated start specimen baseline and tangent at the point of inflection
of the step of a DSC curve,
– Midpoint T1/2 Half height of a step of a DSC curve,
– Peak Tp , t p Greatest difference between DSC curve and virtual baseline,
– Extrapolated end Tef , tef Intersection of virtual interpolated baseline and tangent at the point of inflection of the
peak end or extrapolated end specimen baseline and tangent at the point of inflection of
the step of a DSC curve,
– End Tf, tf Last detectable deviation of DSC curve from extrapolated end baseline.
The second index indicates the type of transition:

g Glass transition
c Crystallisation
m Melting
Figure 2 — Typical DSC heating curve (schematic)
The DSC curve can also be shown using time (t) as abscissa instead of temperature (T).

ISO/DIS 11357-1
4 Principle
4.1 General
The difference between the heat flow rate into a specimen and that into a reference is measured as a function
of temperature and/or time while the specimen and the reference are subjected to the same controlled tem-
perature program under a specified atmosphere.
Depending on the design of instrumentation, two types of DSC are to be distinguished:
4.2 Heat Flux DSC
The sample and reference positions are subjected to the same controlled temperature program by a single
heater. A difference in temperature ( ∆T ) occurs between the sample and reference positions because of the
difference in heat capacity of the specimen and reference crucibles. From this temperature difference the dif-
ference in heat flow rate into the sample and reference positions is derived and is normally recorded against
the temperature of the reference ( Tref ) or time.
A schematic drawing of a heat flux DSC is shown in Figure 3.
1 2
6
3
∆T
T1 T2
4
5
Key
1 Sample position T1 Temperature of sample position (Tsample)
2 Reference position T2 Temperature of reference position (Tref)
3 Thermocouples
4 Single heater
5 Measurement circuit of Tsample, Tref and ? T
6 Surrounding oven
Figure 3 — Basic principle of Heat Flux DSC

ISO/DIS 11357-1
4.3 Power Compensation DSC
In Power Compensated DSC individual heaters are used for the sample and reference positions. The differ-
ence in electrical power required to maintain both the sample and reference positions at the same tempera-
ture is recorded against temperature or time, while each position is subjected to the same controlled tempera-
ture program.
For power compensated isoperibolic calorimeters the surrounding temperature (i.e. the temperature of the
heat sink) shall be kept constant.
A schematic drawing of a power compensation DSC is shown in Figure 4.
5
3
1 2
7
T1 T2
4
6
Key
1 Sample position T1 Temperature of sample position (Tsample)
2 Reference position T2 Temperature of reference position (Tref)
3 Thermometerss
4 Individual heaters
5 Measurement circuit of Tsample and Tref
6 Heat flux compensation circuoit
7 Surrounding heat sink
Figure 4 — Basic principle of Power Compensation DSC
5 Apparatus and materials
5.1 Differential scanning calorimeter (DSC instrument)
Differential scanning calorimeter meeting the following requirements:
a) Symmetric specimen holder assembly which has holders for specimen and reference crucibles;
b) Capability to generate constant heating and cooling rates suitable for intended measurements;
c) Capability to maintain the test temperature constant (to within ± 0,3 K or less for at least 60 min);
d) Capability to carry out step heating or step cooling;

ISO/DIS 11357-1
NOTE 1 Normally this is achieved by a suitable combination of linear heating or cooling and constant temperature re-
gimes.
e) Capability to maintain a constant purge gas flow rate controllable to within ± 10% over a range of flow
. -1 . -1
rates (e.g. 10 ml min to 100 ml min );
NOTE 2 The actual gas flow rate may depend on the design of the instrument used.
f) Temperature range in line with experimental requirements;
g) Heat flow rate range of ± 100 mW or higher;
h) Recording device capable of automatically recording the measured curve of heat flow rate against tem-
perature and time;
i) Measurement of temperature signals with a resolution of ± 0,1 K and an accuracy of ± 0,5 K or better;
j) Measurement of time with a resolution of ± 0,5 s and an accuracy ± 1 s or better;
k) Measurement of heat flow rate with a resolution of ± 0,5 µW and an accuracy of ± 2 µW or better.
5.2 Crucibles
Crucibles for the specimen and reference shall be of same type, made of the same material and have similar
mass. Crucibles shall be physically and chemically inert to the specimen and the purge gas atmosphere under
the measurement conditions (see Annexes C and D).
NOTE If required, small deviationsof crubiles can be arithmetically corrected considering the specific het capacity of
the crucible material.
Crucibles shall preferably be made of a material with high thermal conductivity, e.g. aluminium. Preferably
ventilated crucibles shall be used to avoid changes of pressure during the measurement and to allow for gas
exchange with the surrounding atmosphere. However, for special purposes crucibles closed with lids or her-
metically sealed crucibles may be required so that they can withstand the overpressure arising during the
measurement.
When using special high-pressure or glass crucibles their relatively big mass and poor thermal conductivity
shall be taken into account. Recalibration of the instrument may be required.
NOTE When using high-pressure or hermetically closed crucibles measurements are not necessarily performed at
constant pressure. Hence the constant pressure requirement for measuring enthalpies or c p may not be fulfilled.
5.3 Balance
Balance capable of determining the specimen mass with a resolution of ± 0,01 mg and an accuracy of ± 0,1
mg or better.
5.4 Calibration materials
Calibration materials should cover the temperature range of interest and should preferably be chosen from the
list of recommended calibration materials (see Annex C).
5.5 Purge gas
Purge gas, preferably a dry and inert gas (e.g. Nitrogen, purity 99.99% or better), shall be used to avoid oxida-
tive or hydrolytic degradation during testing.

ISO/DIS 11357-1
For the investigation of chemical reactions, including oxidation, special reaction gases may be required for
purging the instrument.
NOTE If a gas generator is used to supply gas for purging and environmental control during testing, rather than using
pressurised gas bottle purge, it is recommended to install suitable drying and filtering systems.
6 Specimen
The specimen shall be in the liquid or solid state. Solid state specimens may be in any form fitting the crucible
(e.g. powder, pellets, granules, fibres) or may be cut from bigger test pieces to a suitable size. The specimen
shall be representative of the sample being examined and shall be prepared and handled with care. Special
attention is drawn to the fact that any contamination of the specimen shall be avoided. If the specimen is taken
from test pieces by cutting, care shall be taken to prevent heating, polymer orientation or any other effect that
may alter the specimen properties. Operations such as grinding that could cause heating or reorientation and
could therefore change the thermal history of the specimen shall be avoided. The method of sampling and
specimen preparation shall be stated in the test report.
During closing the bottom of the crucible shall not be deformed. Good thermal contact between the specimen
and crucible and between the crucible and holder has to be ensured.
Typical specimen masses are between 2 mg and 40 mg.
NOTE Incorrect specimen preparation can change the thermal history and can affect the properties of the polymers
examined. For further information refer to annex E.
7 Test conditions and specimen conditioning
7.1 Test conditions
The instrument shall be maintained and operated in an atmosphere suitable for the intended test.
If not excluded by special requirements of testing procedures, all calibration and test measurements shall be
performed using closed, ventilated crucibles, preferably made of aluminium, to improve reproducibility.
NOTE It is recommended to protect the instrument from air draughts, exposure to direct sunlight and severe changes
in temperature, pressure or line voltage.
7.2 Conditioning of specimens
The specimen shall be conditioned prior to the measurement as specified in the relevant material standard or
by a method agreed between the parties involved.
Unless otherwise specified, specimens shall be dried to constant mass before performing measurements.
Care shall be taken to choose suitable drying conditions to prevent physical changes such as crystallinity or
ageing of the specimens.
NOTE Depending on the material and its thermal history the methods of preparation and conditioning of the sample
and specimen may be crucial to the values and consistency of results and their significance.
8 Calibration
8.1 General
Before taking into operation a new instrument, after replacing or modifying essential components or after
cleaning the measuring cell by heating to elevated temperatures the calorimeter shall be calibrated at least

ISO/DIS 11357-1
with respect to temperature and heat. An additional heat flow rate calibration may be required for heat capac-
ity measurements. Recalibration of the instrument shall be done regularly where the calibration intervals shall
be established, e.g. within quality assurance systems.
NOTE 1 In many cases the calibration procedures will be inbuilt into the instrument control software and thus at least
partly automated.
NOTE 2 Recalibration of the instrument should be performed each time the test conditions are significantly changed.
More frequent checks may be carried out as required.
The calibration may be affected by
− the type and stability of calorimeter used,
− the heating and cooling rates,
− the type of cooling system used,
− the type and flow rate of the purge gas used,
− the type and size of crucibles used and their position in the specimen holder,
− the location of the specimen in the crucible,
− the mass and particle size of specimen,
− the thermal contact between specimen and specimen holder.
Therefore, the conditions of the actual determination should be defined as precisely as possible and the cali-
bration carried out meeting these conditions as close as possible. Computer aided DSC instruments may
automatically correct the effects of some of these sources of error.
The calibration must be done with the same type and material of crucibles and the same purge gas and same
flow rate as those to be used for subsequent measurements.
Calibration specimens shall be heated only slightly above their transition temperatures to prevent reactions
between calibration materials and crucibles.
NOTE 3 Immediately after the measurement the specimens should be cooled quickly until re-transition to the initial
phase has occurred.
NOTE 4 For most practical measurements, it will be sufficient to use the calibration procedures specified in clauses 8.2
to 8.5. For more accurate calibrations the procedures specified in Annexes A and B may be used.
8.2 Calibration materials
Preferably, certified calibration materials shall be used. The true temperature Tcal , the true transition heat
∆Qcal and true specific heat c cal
p , which are used for the DSC calibration, shall be those appearing on the
calibration certificates.
If certified values are not available, data given in the tables C.1, C.2a and C.2b can then be used. Additional
calibration materials may be used provided their thermal properties are sufficiently defined. The calibration
materials must not interact with the crucibles or purge gas used (see annex D).
NOTE 1 For suitable additional calibration materials the recommendations of ICTAC [10], GEFTA [11], NIST [12] or
others may be referred to.

ISO/DIS 11357-1
NOTE 2 Certified calibration materials can be obtained via National Metrological Institutes (e.g. LGC, PTB, NIST, LNE,
NMIJ …), machine manufacturers or other qualified sources.
For each calibration a fresh calibration specimen shall be used. Possibly existing coatings of oxide on the sur-
face of the calibration specimen must be removed, e.g. by freshly cutting the specimen. The position of the
specimen in the crucible should be kept the same to improve on the repeatability of the results.
NOTE 3 To avoid misleading results or damage of the specimen holder preferably those combinations of calibration
and crucible materials should be used which are expected to show no influence on the melting temperature (see Annex D).
Combinations in which the calibration material is expected to dissolve the crucible material should be avoided.
8.3 Temperature calibration
8.3.1 General
This is the establishment of the relationship between the temperature Tmeas indicated by the instrument and
the true temperature Tcal of the transition of the calibration material. The relation Tcal =Tmeas +∆Tcorr is valid,
where ∆Tcorr is the temperature correction.
When using calibration materials other than those listed in Annex C, only first order transitions, e.g. melting of
pure substances, shall be used.
NOTE True transition temperatures can be obtained from calibration material certificates, other qualified sources or
the literature.
With the calibration materials listed in Annex C temperature calibration shall be carried out in heating mode
only. Therefore, correctly calibrated instruments that give consistent results in heating mode may not neces-
sarily give consistent results in cooling mode because of supercooling of the transition in question. The sym-
metry of the temperature scale in heating and cooling mode can be checked with substances which do not
supercool, e.g. liquid crystals.
8.3.2 Procedure
The following procedure describes the minimum requirements for temperature calibration.
At least two calibration materials covering the temperature range required are weighed into crucibles, prefera-
bly made of aluminium with an oxidised surface.
After having been melted and re-crystallised each specimen shall be subjected to a heating run during which
the melting peak is recorded. Cooling and heating runs shall be performed at the same rate to be used for
subsequent measurements.
For each peak the extrapolated peak onset temperature Tei ,m (cf. clause 3.10, Figure 2) is determined using
the interpolated virtual baseline between peak onset and peak end.
For each calibration material i the temperature correction ∆Tcorr is obtained by subtracting the extrapolated
i
i i
peak onset Tei ,m from the true transition temperature Tcal .
∆Tcorr
i
= Tcal
i
− Teii , m . (6)
The temperature scale of the instrument shall be corrected by linear interpolation of the temperature correc-
tion within the temperature range covered by the calibration materials used according to

ISO/DIS 11357-1
[ ] T − Tcal
1
∆Tcorr (T ) = ∆Tcorr
1
+ ∆Tcorr
2
− ∆Tcorr
1
⋅ (7)
2
Tcal − Tcal
1
where ∆Tcorr , ∆Tcorr are the temperature corrections for the two calibration materials
1 2
1 2
Tcal , Tcal are the transition temperatures of the two calibration materials.
In order to keep errors caused by deviation from linearity of the temperature correction versus temperature
small it is recommended to keep the temperature range covered by the two calibration materials as small as
possible. If bigger temperature ranges are required more than two calibration materials should be used.
NOTE 2 If more than two calibration materials are used a polynomial interpolation can also be applied
NOTE 3 The temperature correction may be performed automatically by some instruments.
This calibration procedure is dependent on heating rate and has to be performed for each heating rate.
8.3.3 Accuracy of calibration
The accuracy of this temperature calibration procedure is expected to be better than ± 0,8 K provided the
temperature difference between the calibration materials does not exceed 50 K and there is no deviation from
linearity of ∆Tcorr versus T . For bigger temperature diifference and significant deviation from linearity lower
accuracy will result [13,14].
For a more precise method of temperature calibration taking into account the effect of heating rate refer to
annex A.
8.4 Heat calibration
8.4.1 General
This procedure establishes the relationship between the heat ∆Qm measured by the instrument
 t2

 ∆Qm = dQ dt  , which is proportional to the area between the DSC curve and virtual baseline, and the true
 ∫ dt 
 t1
heat ∆Qtr absorbed or released by the specimen as a result of a transition. The relation ∆Qtr = K Q (T ) ⋅ ∆Q m
is valid where K Q (T ) is a temperature dependent calibration factor.
For calibration materials ∆Qtr is equal to ∆Qcal .
8.4.2 Procedure
The following procedure describes the minimum requirements for heat calibration.
For heat calibration the same measurements as used for temperature calibration can be used.
The heating run of one material, preferably indium, is chosen.
A linear virtual baseline (cf. clause 3.7.4, Fig. 1) is drawn and the specific heat of melting is obtained from the
area between the DSC curve and the virtual baseline according to Equation (8):

ISO/DIS 11357-1
1 1 d (∆Q )
T f ,m
m β T∫i ,m dt
∆q m = ⋅ dT (8)
where ∆q m : specific heat change ∆Q m / m ,

m: mass of calibration specimen,
β: heating rate,
d (∆Q )
: difference of heat flow rate between DSC curve and virtual baseline,
dt
T: temperature of specimen.
The heat calibration factor K Q is obtained through division of the true specific heat of transition of the calibra-
tion material ∆q tcal by the measured specific transition heat ∆q m :
K Q = ∆ q cal ∆q m (9)
8.4.3 Accuracy of calibration
The accuracy of this method is expected to be not better than ± 2,5 % for Indium. Due to the dependence of
the calibration factor on mass and thermal conductivity of the sample, on heating rate, peak shape and tem-
perature this may rise up to ± 10 % and even beyond [13, 14].
For an extended, more precise method of heat calibration refer to Annex B.
8.5 Heat flow rate calibration
8.5.1 General
This procedure establishes the relationship between the heat flow rate ( dQ / dt ) m measured by the instrument
and the true heat flow rate ( dQ / dt ) tr absorbed by the specimen due to its heat capacity c p , the heating rate
β and its mass m :
(dQ / dt ) tr = c p ⋅ β ⋅ m . (10)
The relation (dQ / dt )tr = K (dQ / dt ) (T ) ⋅ (dQ / dt )m is valid where K (dQ / dt ) (T ) is a temperature dependent
calibration factor.
The heat flow rate calibration shall be carried out for measurements of specific heat and changes of specific
heat at Tg.
For calibration materials (dQ / dt )tr is equal to (dQ / dt )cal .

ISO/DIS 11357-1
Tend
Tst
endo
∆ (dQ dt )
s
dQ/dt
(dQ dt )iso , end

s
(dQ dt )iso,end
0 5
(dQ dt )
s
∆(dQ dt )
iso, st
4 0
(dQ dt )0iso, st
2
3
t st tend
t
Key
1 Calibration specimen run T Temperature
2 Empty run dQ/dt Heat flow rate
3 Quasi-stationary range endo Endothermal direction
4 Isothermal starting lines t Time
5 Isothermal end lines
Figure 5 — DSC curves for heat flow rate calibration
8.5.2 Procedure
Heat flow rate calibration can be done with corundum (synthetic sapphire) or another material of well defined
heat capacity in the temperature range of interest. The heat capacity of sapphire is given in Annex C.
The mass of the calibration specimen shall be chosen such that the heat capacity of the specimen matches
the heat capacity of the calibration specimen as close as possible. Crucibles to be used shall be of same type
and material and shall have masses as similar as possible for empty runs and specimen measurements.
− Calibration specimen and empty crucible shall be subjected to the same temperature program, respectively,
which is divided in three segments (cf. Figure 5):isothermal starting lines for specimen measurement
s 0
( dQ / dt ) iso , st and empty run ( dQ / dt ) iso, st ,

ISO/DIS 11357-1
− dynamic segment (heating rate preferably 10 K/min, duration preferably between 10 min and 30 min) for
specimen measurement (dQ / dt ) and empty run (dQ / dt ) ,
s 0
− isothermal ending lines for specimen measurement ( dQ / dt ) iso

s 0
,end and empty run ( dQ / dt ) iso, end .
Isothermal segments shall be long enough to reach stationary conditions (generally after 2 min to 5 min).
In the quasi-stationary range of the dynamic segment, the corresponding heat flow rate values of calibration
specimen measurement and empty run are evaluated according to Equation (11) and are monitored against
temperature to obtain the calibration function K (dQ / dt ) (T ) :
(11)
p (T ) ⋅ β ⋅ mcal + cp (T ) ⋅ β ⋅ (ms − mr )
ccal cr
K (T ) =


dQ/ dt    dQ
s
 dQ
s
    dQ
0
 dQ
0

 s  s   −    0  0   −  
 dQ  dQ  iso, end  iso, st   dQ  dQ  iso,end  iso, st 
⋅ (t − tst ) −   −   + ⋅ (t − tst )
dt dt dt dt
  −   +
 dt   dt iso,st tend − tst   dt   dt iso, st tend − tst
  
     
    
where c cal cr
p , c p : heat capacity of calibration and crucible material, respectively,
β: heating rate,
mcal , m s , mr : mass of calibration specimen, specimen crucible and reference crucible, respectively.
According to Figure 5 Equation (11) can be rewritten as:
p (T ) ⋅ β ⋅ mcal + c p (T ) ⋅ β ⋅ (ms − mr )
c cal cr
K(dQ/ dt (T ) = (12)
∆(dQ/ dt) − ∆(dQ/ dt)
s 0
9 Procedure
9.1 Setting up the apparatus
9.1.1 Switching on
The instrument shall be switched on at least one hour prior to any calibration or testing to allow the apparatus
to reach stationary conditions.
9.1.2 Purge gas
If not excluded by special requirements measurements shall be performed purging the instrument with inert
gas (e.g. N2, He, Ar). The instrument shall be calibrated with the same purge gas that is to be used for meas-
urements.
9.1.3 Experimental conditions
The experimental conditions (e.g. heating rate, specimen mass) to be used depend on the thermal effect to be
investigated and will be described in the appropriate parts of this standard. Other experimental parameters
can be used if prescribed in relevant material or product standards or specifications or agreed between the
parties involved.

ISO/DIS 11357-1
9.1.4 Baseline determination
Empty crucibles of the same nominal mass are placed in the specimen and reference position of the specimen
holder assembly The experimental conditions are adjusted to those which will be used for the actual meas-
urement. The recorded DSC curve (i.e. the instrument baseline) should be close to a straight line over the re-
quired temperature range.
NOTE 1 If significant baseline curvature is observed the specimen holder should be checked for contamination.
When a reasonable straight line cannot be obtained, the DSC curve is recorded after confirming its repeatabil-
ity.
NOTE 2 In case of computer controlled instruments, a remaining curvature can be corrected for by subtracting the in-
strumental baseline from the actual DSC curve.
9.2 Loading the specimen into the crucible
9.2.1 General
Sample material and crucibles must not be handled with bare hands. Either tweezers or gloves shall be used.
9.2.2 Selection of crucibles
Clean crucibles of appropriate volume and material for the intended measurements are selected.
Two identical crucibles are used usually including lids, one for the specimen and one (normally empty) as the
reference.
9.2.3 Weighing of specimen crucible
The specimen crucible is weighed together with its lid to the nearest 0,01 mg.
9.2.4 Loading of specimen
The specimen is loaded into the specimen crucible. The specimen mass depends on the thermal effect to be
investigated and is referenced in the relevant parts of this standard in more detail.
NOTE In case of transitions and reactions of filled or reinforced materials the specimen mass should refer to the
polymer fraction which contributes to such thermal effects only.
If necessary the sample to be investigated should be homogenised to obtain a representative specimen.
9.2.5 Crucible requirements
If not excluded by the special type of test, closed ventilated crucibles shall be used to obtain quantitative re-
sults and to allow for sufficient contact of purge gas. The crucibles must not be deformed during loading and
closing to ensure good thermal contact between the specimen and the instrument.
9.2.6 Weighing the specimen
The crucible containing the specimen is weighed to obtain the mass of the specimen by subtracting the weight
of the empty crucible determined in 9.2.3.
NOTE Preferably the specimen to be tested should not contain volatiles, which should be eliminated by appropriate
conditioning. However, it should be taken into account that conditioning may change the specimen through inducing
chemical reactions, removing volatiles, ageing or changing the morphology or crystallinity. If volatiles are an important part
of the specimen to be investigated, gas and pressure tight crucibles or a pressure-DSC instrument should be used.

ISO/DIS 11357-1
9.3 Insertion of crucibles into the instrument
Preferably loading of specimen and reference crucible should be done at or slightly above room temperature
(max. 50°C) to prevent condensation of moisture on or within the crucibles. Unless crucibles are loaded by an
automatic specimen changer, tweezers or any other suitable tool shall be used to insert the crucibles in the
specimen holder checking for good thermal contact between crucibles and specimen holder assembly. The
use of bare hands shall be strictly avoided. After having loaded the crucibles, the cover of the specimen holder
assembly shall be closed, if applicable.
9.4 Performing measurements
9.4.1 General
NOTE Due to transients on starting, reliable data cannot be obtained near to the starting temperature or time. The
transient effects are arger for higher heating or cooling rates.
9.4.2 Scanning mode
9.4.2.1 Preparing the instrument
The instrument is programmed and the experimental parameters are set to carry out the required thermal cy-
cle(s). Two types of program can be used: continuous or stepwise heating or cooling.
9.4.2.2 Starting the measurement
The intended temperature program is started and the heat flow rate data are recorded and stored for evalua-
tion of results.
NOTE Since DSC measurements on polymers are greatly affected by the thermal history and morphology of the
specimen it is recommended to carry out the heating run twice. The first run reflects the as-received state and is per-
formed up to the melt or glass transition where the material reaches thermal equilibrium. The second run is done after hav-
ing cooled the specimen at a defined rate to erase prior thermal history and thus allows for comparison of material proper-
ties. The intermediate cooling run reveals information about nucleation and crystallisation of the material (see annex E for
further information).
9.4.2.3 Unloading the specimen
After having finished the measurement the specimen holder assembly is brought back to loading temperature
and the crucible containing the specimen is taken out.
9.4.2.4 Processing of data
The recorded data shall be processed according to the instrument manufacturer's instructions and the thermal
effects under investigation.
9.4.3 Isothermal mode
9.4.3.1 General
Depending on the type of instrument used, two different isothermal procedures are available with the speci-
men being introduced at room temperature or at a specified arbitrary temperature.

ISO/DIS 11357-1
9.4.3.2 Specimen introduced at room temperature
9.4.3.2.1 Loading the instrument
The crucibles containing the specimen and serving as reference are loaded into the specimen holder at or
slightly above room temperature (max. 50°C) and the instrument is brought to the specified measurement
temperature as fast as possible.
9.4.3.2.2 Starting the measurement
Maintaining the temperature at this value, the DSC curve is recorded as a function of time. The DSC run is
continued with the test conditions unchanged up to at least 5 min after the endo- or exothermic reaction or
transition has finished and a stable baseline is obtained. The heat flow rate data are recorded and stored for
evaluation of results.
9.4.3.2.3 Unloading the instrument
The instrument is brought back to the loading temperature and the specimen crucible removed.
9.4.3.2.4 Data processing
9.4.3.3 Specimen introduced at arbitrary measurement temperature
9.4.3.3.1 Preparing the instrument
The instrument is set to the specified measurement temperature and allowed to reach steady-state conditions.
9.4.3.3.2 Loading the specimen and starting the measurement
The crucible containing the specimen and the refernce crucible are inserted into the specimen holder at this
temperature and the instrument is immediately started to record the DSC curve as a function of time. To re-
duce uncontrolled temporary temperature change of the specimen holder assembly, the time for which the
measuring system is open should be kept as short as possible. The DSC run is continued with the test condi-
tions unchanged up to at least 5 min after the endo- or exothermic reaction or transition has finished and a
stable baseline is obtained again. The heat flow rate data are recorded and stored for evaluation of results.
9.4.3.3.3 Unloading the specimen
The instrument is brought back to normal loading temperature and the specimen removed.
9.4.3.3.4 Data processing
9.5 Removal of crucibles
9.5.1 Checking for loss of mass
The crucible containing the specimen shall be reweighed after the test. If any loss of mass is observed this
could have created an extra thermal effect or disturbed the instrument baseline.

ISO/DIS 11357-1
9.5.2 Inspection of specimens after measurements
If an unexpected chemical change is suspected, the specimen crucible should be opened and the specimen
should be inspected carefully. Damaged crucibles shall not be used for further measurements.´
NOTE Crucibles should not normally be reused. Their re-use is not recommended. However, in exceptional circum-
stances where it has been unambiguously demonstrated that there are no interactions of the specimens with the crucibles,
that no residual contamination is left on removal of the specimen, and that the crucibles are not damaged then crucibles
may be re-used. Their re-use must be reported in the test report.
9.5.3 Checking of crucibles and specimen holder assembly
The specimen crucible shall be examined to check for any dislocation, deformation or overflow and the meas-
urement repeated if this had occurred.
If the specimen holder has been contaminated from specimen overflow or condensed volatiles it shall be
cleaned in accordance with the manufacturer's instructions and recalibrated.
10 Test report
The test report shall include the following information:
a) a reference to this International Standard,
b) type and complete identification of specimen,
c) type (heat flux or power compensated), manufacturer and model of DSC instrument used,
d) material, type and masses of crucibles used,
e) type, purity and flow rate of purge gas used,
f) type of calibration procedure (simplified or extended), and details of the calibration materials used, includ-
ing source, mass and other properties important for calibration,
g) details of sampling, preparation of specimen and conditioning procedures, if applicable,
h) shape and dimensions of specimen, if applicable,
i) mass of specimen,
j) thermal histories of sample and specimen,
k) temperature program parameters, including time and temperature of isothermal steps and rate of dynamic
steps,
l) change of mass of specimen over duration of test, if any,
m) test results including DSC curves,
n) date of test,
o) any additional information or operating details not specified in this International Standard which may be
important for assessment of the results.

ISO/DIS 11357-1
Annex A
(normative)
Extended, high precision temperature calibration [14]
The extended temperature calibration shall be used if one ore more of the following are required:
 Higher precision than ± 0,8 K per temperature range of 50 K.
 Include effect of heating rate in calibration procedure.
 Include influence of specimen mass in calibration procedure.
Two specimens of each of at least 3 different calibration materials covering the temperature range required
with approximate masses m of approximatrely 3 mg and 10 mg shall be weighed into crucibles, preferably
made of aluminium with an oxidised surface.
For each heating and cooling rate, β = 1 K/min, 5 K/min, 10 K/min and 20 K/min, the specimen shall be
melted and re-crystallised and then subjected to a heating run at the same rate during which the melting peak
is recorded.
For each peak the extrapolated peak onset temperature Tei ,m (cf. 3.10, Figure 2) is determined using the in-
terpolated virtual baseline between peak onset and peak end.
For each calibration material and each mass the extrapolated peak onset temperatures are plotted against the
heating rate and are linearly extrapolated to the heating rate β = 0 K/min (cf. Figure A.1).
The temperature correction ∆Tcorr (Tcal , m ) is obtained by subtracting the extrapolated peak onset Tei ,m (β =0 )
thus determined from the true transition temperature Tcal (cf. Figure A.1):
∆Tcorr (Tcal , m ) = Tcal − Tei ,m (β = 0 ) . (A.1)
The temperature correction terms determined by this procedure are recorded against extrapolated peak onset
temperatures Tei ,m (β = 0 ) and thus yield the temperature dependence of the temperature calibration
(cf. Figure A.2):
∆Tcorr (T , m) = f [Tcal − Tei,m (Tcal , m, β = 0)]. (A.2)
NOTE The temperature correction with respect to heating rate and./or temperature may be done automatically by
some instruments.
If bigger temperature ranges are required more than three calibration materials should be used.
The accuracy of this temperature calibration procedure is expected to be better than ± 0,3 K over a tempera-
ture range from 25 °C to 330 °C[15].

ISO/DIS 11357-1
235,0
T / °C
234,0
3 mg
233,0
10 mg
T2 ei,m(ß=0)
Tcal
T1ei,m(ß=0) T 1corr T2corr

232,0
Tcal
231,0
0 5 10 15 20
. -1
ß / K min
Key
T Temperature
ß Heating rate
Tcal True transition temperature of calibration material tin
1 2
T ei,m(ß=0), T ei,m(ß=0) Peak onset temperatures extrapolated to zero heating rate for 3 mg and 10 mg specimen mass,
respectively
1 2
?T corr, ?T corr Temperature correction for 3 mg and 10 mg specimen mass, respectively
Figure A.1 — Determination of temperature correction from extrapolated peak onset temperatures
versus heating rate using tin as calibration material

ISO/DIS 11357-1
1,5
1,0
? Tcorr / K
0,5
3 mg
0,0 10 mg
-0,5
-1,0
-1,5
0 50 100 150 200 250
Tei, m (ß=0) / °C
Key
? Tcorr Temperature correction depending on calibration materials and specimen mass
Tei, m (ß=0) Peak onset temperature of different calibration materials extrapolated to zero heating rate
Figure A.2 — Temperature calibration function obtained with gallium, indium and tin

ISO/DIS 11357-1
Annex B
(normative)
Extended, high precision heat calibration
The extended heat calibration shall be used if one or more of the following are required:
 Higher precision than ± 2 %.
 Include effect of heating rate in calibration procedure.
 Include influence of specimen mass in calibration procedure.
For each of the peaks obtained according to annex A a linear virtual baseline (cf. 3.7.4, Figure 1) is drawn and
the heat of melting is obtained from the area between the DSC curve and the virtual baseline according to eq.
(8) (cf. 8.4).
1,02
3 mg / 1 K/min
3 mg / 5 K/min
1,01
3 mg / 10 K/min
KQ 3 mg / 20 K/min
10 mg / 1 K/min
1,00
10 mg / 5 K/min
10 mg / 10 K/min
10 mg / 20 K/min
0,99
0,98
0 50 100 150 200 250
T / °C
Key
KQ Heat calibration factor depending on calibration material, specimen mass and heating rate
T Temperature
Calibration curve for specimen mass of 3 mg and heating rate of 1 K/min
Calibration curve for specimen mass of 10 mg and heating rate of 1 K/min
Figure B.1 — Heat calibration function determined with gallium, indium and tin

ISO/DIS 11357-1
The individual heat calibration factors K Q are obtained through division of the true specific heats of transition
∆q cal by the measured specific heats of transition ∆qm of the respective calibration materials:
K Q (Tcal , m, β )=∆q cal ∆q m (Tcal , m, β ) . (B.1)
where Tcal : True transition temperature of calibration material.
The heat calibration factors are plotted against temperature to obtain the heat calibration function
K Q (T , m, β ) = f [∆q cal ∆q m (Tcal , m, β )] (B.2)
(cf. Fig. B.1). If the dependencies on heating rate and/or mass are not negligible these have to be determined
separately.
The accuracy of this method is expected to be better than ± 0.5 % [5].

ISO/DIS 11357-1
Annex C
(informative)
Recommended calibration materials
Table C.1 — Temperature, heat and type of transition for various recommended calibration materials
[3,5]
Material Transition Transition Type of transition Remarks

temperature heat
°C J.g-1
Cyclopentane -155,77 69,60 solid - solid Measure in hermetically sealed crucible

only. Weigh in as a liquid, reweigh to de-
Cyclopentane -135,09 4,91 solid - solid termine the mass.
Cyclopentane -93,43 8,63 solid - liquid
Water 0,00 – solid - liquid Not suitable for heat calibration.
Gallium 29,76 79,88 solid - liquid Melt reacts with Al.

Allow for strong supercooling.
Indium 156,60 28,62 solid - liquid
Tin 231,93 60,40 solid - liquid Melt reacts with Al.
Bismuth (271,40) 53,84 solid - liquid Melt reacts with Al. Not suitable for tem-
perature calibration.
Lead 327,46 – solid - liquid Not suitable for heat calibration.
Zinc 419,53 – solid - liquid Not suitable for heat calibration.
Lithium sulfate 578,28 228,1 solid - solid Anhydrate hygroscopic; weigh in as

Li2SO4•H2O. Dehydration starting from
110°C with brisk movement of the parti-
cles in the crucible; high water vapor
pressure (do not use hermetically sealed
crucibles). Reweigh after measurement
for mass determination.
Aluminium 660,32 398,1 solid - liquid Melt reacts strongly with Pt.
Calibration materials that have, or potentially have reacted with crucible material shall not be reused.

ISO/DIS 11357-1
Table C.2a — Recommended materials for heat flow rate calibration [4,5]
Material Temperature Heat capacity Uncertainty Remarks

range cp(T) [4]
K J.g-1.K-1 %
Corundum (α - Al2O3) 70 - 300 7 0,4 – 0,1 No limitation on crucible material

(synthetic sapphire) ∑a
i =0
i ⋅T i below its melting temperature.
290 – 2.250 7 0,1 –0,2

∑ b ⋅T
i =0
i
i
Copper (Cu) 20 – 97,5 6 0,1 Oxygen-free, high conductivity

∑ c ⋅T
i =0
i
i
quality. No limitation on crucible
material below its melting tem-
perature.
97,5 - 320 4 0,1

∑ d i ⋅T i
i =0
where T is temperature in Kelvin.
Table C.2b — Coefficients of the fitting polynomials in Tab. C.2a for heat capacity of the heat flow rate
calibration materials [4,5]
i a b c d
0 3,63245 . 10-2 -5,81126 . 10-1 1,43745 . 10-2 -1,63570 . 10-1

. -3 . -3 . -3 . -3
1 -1,11472 10 8,25981 10 -1,21086 10 7,07745 10
. -6 . -5 . -5 . -5
2 -5,38683 10 -1,76767 10 -1,23305 10 -3,78932 10
. -7 . -8 . -6 . -8
3 5,96137 10 2,17663 10 4,20514 10 9,60753 10
. -9 . -11 . -8 . -11
4 -4,92923 10 -1,60541 10 -8,49738 10 -9,36151 10
. -11 . -15 . -10
5 1,83001 10 7,01732 10 6,71459 10
6 -3,36754 . 10-14 -1,67621 . 10-18 -1,94071 . 10-12
7 2,50251 . 10-17 1,68486 . 10-22

ISO/DIS 11357-1
Table C.3— Specific heat capacity of corundum in the temperature region from 290 K to 550 K
(calculated using data of Tab C.2a and C.2b)
Temperature Heat capacity cp(T)

. -1. -1
K Jg K
290 0,7583
300 0,7794
310 0,7995
320 0,8186
330 0,8368
340 0,8541
350 0,8706
360 0,8863
370 0,9012
380 0,9154
390 0,9290
400 0,9419
410 0,9541
420 0,9658
430 0,9769
440 0,9875
450 0,9976
460 1,0072
470 1,0164
480 1,0251
490 1,0335
500 1,0414
510 1,0490
520 1,0563
530 1,0632
540 1,0699
550 1,0762

ISO/DIS 11357-1
Annex D
(informative)
Interaction of calibration materials with different crucible materials
Table D.3 — Interaction of calibration and crucible materials [3]
Calibration material
Crucible material Cyclo- Water Gallium Indium Tin Lead Zinc Lithium Alumin-
pentane sulphate ium
Corundum, Al2O3 o o + + + + + + +
Boron nitride, BN o o + + + + + + +
Graphite, C o o + + + + + + +
Silicate glass + + + + + + ? + -
Quartz glass, SiO2 + + + + + + + + -
Aluminium, Al + • - + - + - + x
Aluminium, oxidized + + + + + + + + x
Silver, Ag + + - - - - - ? -
Gold, Au + + • • - - - + -
Nickel, Ni + + • • • • • ? -
Iron, Fe + • • + • + - ? -
Stainless steel + + • + • + - ? -
Platinum, Pt + + • • - - - + -
Molybdenum, Mo + + • ? • ? • ? ?
Tantalum, Ta + + ? + ? ? ? + -
Tungsten, W o o • ? ? • + ? •
Key: +: No solubility and no influence on melting temperature to be expected

-: Melt dissolves crucible material, greater change in melting temperature
•: Partial dissolution processes are possible with negligible change in melting temperature
x: Crucible melts
?: Interaction unknown
o: Hermetic sealing of crucible may be difficult

ISO/DIS 11357-1
The calibration materials recommended in Table C.1 may form mixed phases with some of the crucible mate-
rials normally used for DSC. In these cases there is a risk of molten calibration specimen dissolving part of the
crucible material which may result in an unpredictable change of melting temperature and/or damage of the
specimen holder. Table D.1 shows combinations in which interactions may occur which can be inferred from
the respective phase diagrams.
It is strongly recommended that those combinations in Table D.1 marked with - should not be used, because
dissolution of the crucible can not only invalidate the calibration but also damage the specimen holder assem-
bly. The combination marked with + should preferably be used for calibration. A • marks systems in which no
significant falsification of the temperature is to be expected, although, in these cases, certain caution is advis-
able with respect to the consequences of a partial dissolution of the crucible material.
As can be seen from Table D.1, there is at least one crucible material suitable for each of the recommended
calibration materials. If necessary, the crucible used must be coated with a protective layer for calibration pur-
poses. Aluminium oxide is ideally suited for this purpose; in the case of the aluminium crucibles normally used,
this protective oxide layer can be produced in sufficient thickness by heating to 570 °C in air atmosphere.

ISO/DIS 11357-1
Annex E
(informative)
General recommendations
This test method is suitable for comparative measurements on polymeric materials. However, the results ob-
tained may be influenced by systematic errors such as incorrect calibration, baseline correction, specimen
conditioning and preparation, etc. It is strongly recommended to establish polymeric reference materials (simi-
lar to those materials routinely analysed) for comparative analysis in parallel with the materials being tested.
This allows for comparison of data obtained from different laboratories, instruments, test dates, specimen
conditioning and preparation procedures, etc.
Except for special cases in which the decomposition of polymers is the subject of investigation, it is not rec-
ommended to continue measurements beyond the decomposition temperature of the sample polymer. This
decomposition may lead to contamination of the specimen holder assembly from materials in open or venti-
lated crucibles or to explosion from those in hermetically sealed crucibles. At worst the specimen holder as-
sembly may be destroyed. In addition to this, very high temperatures or large temperature scanning ranges
could cause alteration in the linearity of the calibration settings resulting in erroneous data.
The interpretation of a DSC curve having several thermal effects such as glass transition steps or first order
transition peaks is fairly straightforward when these effects are clearly separated. Quite often DSC curves will
show steps and/or peaks that cannot be separated easily. These types of curves are a result of several reac-
tions and/or transitions which overlap or occur simultaneously. In these cases, the only thermal properties that
can be determined without using sophisticated curve separation procedures are overall heat, onset tempera-
ture and extrapolated onset temperature of the first reaction or transition (keeping in mind that most often
these onset temperatures are poorly defined in the case of polymers having an extremely broad melting range
of up to 150 K), extrapolated end temperature and end temperature of the last reaction or transition, and sev-
eral peak temperatures. It is not always possible to identify all of these individual reactions and/or transitions
by DSC alone. In some cases, it may be helpful to adjust the heating and/or cooling rates to enhance the
separation of these phenomena. However, care should be exercised as the heating and cooling rates can
have significant effect on the characteristic temperature(s) observed in the subsequent heating rate.
For some polymers the DSC curve can have several peaks during the first heating run while there is only one
peak during the second heating run. Normally a cooling run performed at the same rate (i.e. 10 or 20 K/min)
used for heating precedes the second heating scan. The information obtained in the first heating run may be
indicative of the thermal history that the polymer has been subjected to (such as processing and specimen
conditioning and preparation). Therefore, it is advisable when analysing polymers to carry out three DSC runs:
first heating, subsequent cooling and finally second heating, preferably with the same rate. Using this proce-
dure in conjunction with a record of the initial mass of the specimen in the crucible and the masses of the
specimen in the crucible before and after the second heating scan can aid identification of the various peaks
observed. To obtain information on the thermal properties of the sample material without being influenced by
its thermal history, the results of the cooling and second heating scan should be used. With respect to the
solid - liquid phase transition this means that the cooling run indicates nucleation and the temperature or kinet-
ics of crystallisation while the second heating reflects the material-specific melting properties of polymers. Of
course, the glass transition characteristics can be estimated as well without being perturbed by thermal history.
In case of gas evolution (decomposition, solvent evaporation, etc.) during heating a specimen, the pressure
generated inside can deform a hermetically sealed crucible. This results in disturbances of the heat transfer
between the specimen and the measuring system. To avoid such deformations, a punched (perforated) lid or
a special pressure-tight crucible can be used.
To investigate chemical reactions induced by exposure to visible or UV light special photo-DSC instruments
are available.

ISO/DIS 11357-1
Annex F
(informative)
Bibliography
[1] ICTA (J.O. Hill, Ed.), For better thermal analysis and calorimetry, Edition III (1991)
[2] Preston-Thomas, H., The International Temperature Scale of 1990 (ITS-90), Metrologia 27 (1990) 3
[3] Cammenga, H.K., et al., Thermochim. Acta 219 (1993) 333
[4] Sarge, S.M., et al., Thermochim. Acta 247 (1994) 129
[5] Sarge, S.M., et al., J. Therm. Anal. 49 (1997) 1125.
[6] Wunderlich, B., Thermal analysis, Academic Press (1990) London
[7] Mathot, V.F.B., (Ed.), Calorimetry and thermal analysis of polymers, Hanser/Gardner (1994) Cincinnati,
Ohio
[8] Höhne, G.W.H., et al., Differential scanning calorimetry: An introduction for practitioners, Springer
(1996) Berlin
[9] Turi, E.A.. (Ed.), Thermal characterization of polymeric materials, Academic Press (1997), New York
[10] International Confederation for Thermal Analysis and Calorimetry (ICTAC)

Contact address: Prof Michael E. Brown
Chemistry Dept
Rhodes University
Grahamstown
6140 South Africa
http://www.ictac.org
[11] Gesellschaft für Thermische Analyse e.V. (GEFTA)

Contact address: Prof. Dr. Volker Krämer
Kristallographisches Institut der Universität
Hebelstr. 25
D-79104 Freiburg
Germany
http://www.gefta.uni-freiburg.de
[12] National Institute of Standards and Technology (NIST)

Contact address: NIST,
100 Bureau Drive, Stop 1070,
Gaithersburg, MD 20899-1070
USA
http://www.nist.gov
[13] Callanan, J.E., et al., NBS Spec. Publ. 260-99 (1985)
[14] Schubnell, M., T. Therm Anal. Cal., 61 (2000) 91
[15] Höhne, G.W.H., et. al., Thermochim. Acta 160 (1990) 25

EXPLANATORY REPORT
ISO/DIS 11357-1
RAPPORT EXPLICATIF
ISO/TC 61 / SC 5 Secretariat ANSI/ASTM
This form should be sent to the ISO Central Ce formulaire doit être envoyé au Secrétariat central de l'ISO en
Secretariat, together with the English and French même temps que les versions anglaise et française du projet de comité,
versions of the committee draft, by the secretariat of par le secrétariat du comité technique ou du sous-comité concerné.
the technical committee or subcommittee concerned.
The accompanying document is submitted for Le document ci-joint est soumis, pour diffusion comme DIS, au vote
circulation to member body vote as a DIS, following comité membre, suite au consensus des membres (P) du comité
consensus obtained from the P-members of the obtenu.
committee.
on 19 September 2007
at the meeting of TC 61 / SC 5 see resolution No. 1 in document N1129Rev1
à la réunion du voir résolution no dans le
by postal ballot initiated on
par un vote par correspondance démarré le
Number Countries
P-members in favour: 11 Germany, India, Italy, Japan, Malaysia,
Membres (P) approuvant le projet: Netherlands, Republic of Korea, Switzerland,
Thailand, United Kingdom, USA
P-members voting against: 0

Membres (P) désapprouvant:
P-members abstaining:
Membres (P) s'abstenant:
P-members who did not vote:

Membres (P) n'ayant pas voté:
Remarks/Remarques
See resolution of comments from CD2 ballot attached.
I hereby confirm that this draft meets the requirements of part 2 of the ISO/IEC Directives
Je confirme que ce projet satisfait aux prescriptions de la partie 2 des Directives ISO/CEI
Date Name and signature of the secretary
Nom et signature du secrétaire
2008-02-05 Todd J. Sandler
FORM 8 A (ISO) FORMULAIRE 8 A (ISO) Page 1 of/de 1

Version 2001-07
Template for comments and secretariat observations Date: 2008-02-05 Document: ISO/CD 11357-1.2, Plastics —
Differential scanning calorimetry (DSC) — Part
1: General principles
1 2 (3) 4 5 (6) (7)
MB1 Clause No./ Paragraph/ Type Comment (justification for change) by the MB Proposed change by the MB Secretariat observations
Subclause No./ Figure/Table/ of on each comment submitted
Annex Note com-
(e.g. 3.1) (e.g. Table 1) ment2
FR 3.1 Note Ed Change “(cf. Fig. 2)” to “(cf. Figs. 1 and 2) Accepted.
FR 3.1 Note Ed Reduce the point size of the type used in this note Accepted.
FR 3.6 Note 1 Ed Add a bracket after “material expressed in moles” Accepted.
FR 3.6 Figure 1 Ed The line appearing in the label of ordinates "heat flow rate" Change the dotted line to a full one on the left Accepted.
is a dotted line, whereas a full line represents the heat flow ordinates label "heat flow rate"
rate on the graph (the dotted line represents the
temperature).
FR 3.10 Figure 2 Ed The abscissa label is unreadable Clarification required.
No unreadable label found.
FR 5.5 Note Ed Reduce the point size of the type used in this note Accepted.
FR 8.3.2 Line 7 Ed Change “cf. clause 3.12” to “cf. clause 3.10” Accepted.
FR 8.4.2 Line 4 Ed Change “cf. clause 3.9.4” to “cf. clause 3.7.4” Accepted.
FR 8.4.2 Equation (9) Ed Delete the dot after (9) Accepted.
FR Annex A Paragraph 4 Ed Change “cf. clause 3.12” to “cf. clause 3.10” Accepted.
FR Annex B Paragraph 2 Ed Change “cf. clause 3.9.4” to “cf. clause 3.7.4” Accepted.
TH 3.6 NOTE ed “Cp” should read “Cp”. Accepted.
TH 8.3.3 Para 2 ed “efect” should read “effect”. No typing error found.
1 MB = Member body (enter the ISO 3166 two-letter country code, e.g. CN for China; comments from the ISO/CS editing unit are identified by **)
2 Type of comment: ge = general te = technical ed = editorial
NOTE Columns 1, 2, 4, 5 are compulsory.
page 1 of 15
ISO electronic balloting commenting template/version 2001-10
1 2 (3) 4 5 (6) (7)
Annex Note com-
UK Various Various Edit The term “sample” is used. Ensure as uses of the term “sample” are correct – Accepted.
change to “specimen” where appropriate, e.g. 3.1. Various instances of 'sample'
have been changed to
'specimen'.
However, terms 'sample' and
'specimen' are used based on
DSC convention and
definitions given in IS 472
which implies that not all
instances of sample can be
removed, e.g. in 3.1 use of the
term 'sample' is due to DSC
practice.
UK Foreword Para3 Gen Re “This second ..” State how it has been revised As mentioned earlier this is
described in the introduction.
UK Intro Para2 Gram Grammatical Change to “… capabilities of instruments…” Accepted.
nd
UK 1 2 bullet Gram Clarity Change to “…cured materials with or …” Accepted.
UK 3.1 Sentence 1 Gram Clarity Change to “ … into the specimen crucible and that Not accepted.
into the …” Present wording required to
point out difference between
meaning of 'sample' and
'specimen':
UK 3.1 Note Gram Grammatical Change “point” to “points” Accepted.
page 2 of 15
1 2 (3) 4 5 (6) (7)
Annex Note com-
UK 3.3 Para1 Edit Currently the text is this clause is not a definition. Change 1. Ensure that the text is a definition. Move 1. Accepted.
to a definition. equipment description to relevant clause e.g. 5.2 Term 'specimen holder
or change to Note in 3.3 if considered necessary assembly' was kept due to
here. DSC convention.
Proposed revised text:
“The crucible used on the reference side of
the symmetric specimen heater assembly.”
2. Move the following text to 5.2 (but already 2. Acccepted.
there is other wording): Text removed from 3.3 and
“The specimen and reference crucibles shall included in 5.2 which has
have similar mass, be of same type and made been revised.
of the same material.” A note has been added to 5.2
dealing with deviation of
crucible weight.
3. The reason for the following text is unknown: 3. Accepted.
“Specimen and reference crucibles shall have
a significantly higher heat capacity than the
specimen.”
Often the user has no choice. Delete the text.
4. Add to the existing Note at its beginning: 4. Accepted.
“Normally the reference crucible is empty.” For the sake of clarity a
separate note was added.
UK 3.3 Line 1 Edit The term specimen holder assembly is vague. Change to “specimen heater assembly” Not accepted.
Term 'specimen holder
assembly' is common use in
DSC convention.
page 3 of 15
1 2 (3) 4 5 (6) (7)
Annex Note com-
st
UK 3.3 Note Gram Gram (1 and last sentences) Change to “… such as the measurements …. of Accepted.
specimens …”
Change “In the case of filled …”
UK 3.4 Line 1 Edit Should be “watts” not “watts” – see Ensure correct lower case for units throughout Accepted.
http://www.bipm.org/en/si/si_brochure/chapter2/2- standard (here 9.5, and elsewhere probably) Units changed to lower case.
2/table3.html which specifies lower case for all units
3.4 Line 1 Tech For consistency of units only watts should be stated, Delete “or milliwatts (mw)” Discussion.
otherwise there is potential confusion in the equations. Unit milliwatts most commonly
used in DSC diagrams.
UK 3.5 Para 1 Tech Clarity Change to “(endothermic: ∆Q positive)” and Accepted.
“(exothermic: ∆Q negative)”
UK 3.5 Para 1 Edit Add symbols Change to “… specified time (t) of temperature (T) Accepted.
range …”
UK 3.5 Para 2 Tech Re “where ∆Q …” One symbol is used here to represent Can a subscript be used to identify which (mass or Discussion.
two different quantities, leading to potential confusion. molar) quantity is specified? In my view the intention is
very clear. It may create more
confusion than clarity if all
scientific details are included.
UK 3.5 Para 2 Tech Re “and β…” give units Add “Kelvin per second” - for consistent units BUT Accepted.
see next comment (3.6) Conversion factor of 60
added.
UK 3.6 Para 2 Tech RE: definition of units for heating rate. For the units of Revise accordingly. Option to state in Note that Accepted.
equation 5 to be consistent where the heat flow rate is although units for equation 5 are necessarily in K/s,
they are often expressed in K/min. Conversion factor of 60
given in watts, then the heating rate must be given in K/s.
If K/min are used then there is a factor of 60 error. added.
UK 3.6 Various Edit Use of differential symbols Check correct use of δ ∂ and d symbols Not accepted.
δ not found; ∂ used for partial
and d for full derivatives.
page 4 of 15
1 2 (3) 4 5 (6) (7)
Annex Note com-
UK Figure 1 Various Edit 1. Symbol for heat flow rate wrong (left y axis). Amend as appropriate. 1. Accepted.
2. “Specimen baseline” would be better labelled All text should be outside diagram in legend. 2. Not accepted.
“Specimen curve” Refers to part of specimen
3. The specimen curve appears to tail-off a bit early curve outside transitions
within the quasi-stationary range – extend linearly only.
to end of quasi-stationary range. 3. Accepted.
Figure revised to extend
specimen curve. Also the
wrongly assigned quasi-
stationary range was
corrected. Similarly
required changes of Fig.5
in 8.5.2 were done, too.
UK 3.7.3 Line 1 Gram Grammatical Change to “”… outside any reaction or …” and Accepted.
Change to “ … with the specimen in its crucible and
the reference ..”
UK 3.7.3 Note Gram The note is ambiguous / incorrect. If the temperature Change to “… is approximately flat.” Accepted.
dependence of heat capacity is low and is thus
approximately constant, i.e does not change much with
temperature, then the baseline should be approximately
flat. A straight baseline can still have a large gradient
implying a high heat capacity variation with temperature.
UK 3.7.4 P1, line 3 Edit Consistency in terminology Change “sample” to “specimen” Accepted.
Change to “… using a straight line.” (i.e. delete “in”)
UK 3.7.4 Note Edit Figure 2 does not show, or clearly show, that the Delete “(see Fig.2)” or amend figure so it does Accepted.
extrapolated and interpolated virtual baselines can deviate show deviation. Fig. 2 modified.
from each other.
page 5 of 15
1 2 (3) 4 5 (6) (7)
Annex Note com-
UK 3.9.2 and 3.9.3 Line 1 Tech Consistency of terminology Change “compartment” to “crucible” – twice in each Discussion.
clause. What we measure is the
energy exchanged with the
specimen and reference
compartment. If we assume
100% transfer into the
crucible, i.e. ideal thermal
contact, this would be correct,
but can we?
UK 3.10 Line 3 and Edit Consistency of terminology Change “sample” to “specimen”. Also check font Not accepted.
Note size. Occurrence of 'sample' in 3.10
complies with DSC
convention.
3.10 formatted in accordance
with template.
UK 3.10 Para 2 Edit/ Lost text from previous version (CD1) – thought to be Change to Accepted.
accidental. No loss of text or label in my
tech “The following are characteristic temperatures (T)
and times (t) on a DSC curve, where distinct copy. However, text changes
temperatures shall be expressed in degree Celsius done per request.
(°C), relative temperatures and temperature
differences in Kelvin (K) and time in seconds (s) of
minutes (min) (cf Fig 2).”
Also x-axis label partially lost in my print out.
UK 3.10 Legend to Fig Tech The definitions of extrapolated onset and extrapolated end Change titles to “Interpolated or extrapolated onset” Not accepted.
2 both refer to “interpolated” or “extrapolated” baselines. This and “Interpolated or extrapolated end” The onset and end
is inconsistent. temperatures are
extrapolated even if an
interpolated baseline is used.
In that respect the description
seems correct.
page 6 of 15
1 2 (3) 4 5 (6) (7)
Annex Note com-
UK 3.10 Legend to Fig Tech The height of a step has not been defined and therefore Clarify / defined “step height”. Accepted.
2 this description is ambiguous. Definition of step height
added.
UK 4.2 Line 4 Gram Grammatical and consistency of terminology. Change to “”… in heat flow into the sample …” Also Accepted.
check use of “sample” cf “specimen” in this clause, Some instances of sample
for consistency. kept due to DSC convention.
UK 5.1 a) Edit The term “specimen holder assembly” is not sufficiently Change to “specimen heater assembly” Not accepted.
descriptive (i.e. the holder holds). Term 'specimen holder
assembly' kept due to DSC
convention.
UK 5.1 Note 1 Gram Grammatical Change to “… combination of linear heating or Accepted.
cooling and constant temperature regimes.”
UK 5.2 Para 1 Gram Grammatical Move “under the measurement conditions” to after Accepted.
“atmosphere”
UK 5.2 Note Tech Grammatical Change to “… are not necessarily performed at Accepted.
constant pressure. Hence the constant pressure
requirement for measuring enthalpies or Cp may not
be fulfilled.”
UK 6 Para 1 Gram Grammatical Change “may” to “shall” – three times Partly accepted.
First instance changed, the
other three need to be kept.
UK 6 Para 1, line 2 Gram Grammatical Change “… to a suitable size.” Accepted.
UK 6 Para 2 Gram Grammatical Change to “… between the specimen and crucible Accepted.
and between the crucible and holder …”
UK 7.1 Para 2 Gram Grammatical Change to “… shall be performed using …” Accepted.
UK 7.1 Note Gram Grammatical Change to “…sunlight and severe …” Accepted.
page 7 of 15
1 2 (3) 4 5 (6) (7)
Annex Note com-
UK 7.2 Note Tech Technical Change to “ … crucial to the values and Accepted.
consistency of results …”
UK 8.1 End of Para 1 Tech Many instruments have automated calibration procedures Add Note after first paragraph: Accepted.
that are not necessarily transparent to the operator. It may
not be possible for the operator to knowingly comply with “NOTE 1: In many cases the calibration procedures Text revised.
will be inbuilt into the instrument control software
the procedures specified. In order to, at least,
acknowledge this a new Note is proposed. and thus at least partly automated.”
Revised subsequent Note numbering.
UK 8.1 Para 1 Gram Grammatical Change to “ … regularly where the calibration …” Accepted.
UK 8.1 Para 4 Edit Re “For power compensated …” This paragraph is more Move to 5.1 Accepted.
appropriate in clause 5.1 But moved to 4.3.
UK 8.1 Para 5 Gram Grammatical Change to “ … after the measurement the Accepted.
specimens …” Last sentence moved into
Note.
UK 8.2 Para 1 Tech mixed use of tr and cal subscripts/superscripts to denote Revise to provide consistency (here and elsewhere) Accepted.
calibrant value. All relevant instances of index
'tr' changed to 'cal'.
UK 8.2 Para 1, line 2 Tech Correct term Change to “”… true specific heat capacity cpcal …” Accepted.
UK 8.2 Note 2 Gram Clarity Change to “… Institutes (e.g. LG, PTB, NIST, LNE Accepted.
and NMJ), machine …”
UK 8.3.1 Para 2 Gram Grammatical Change to “ … shall be used.” Accepted.
UK 8.3.1 Last para Gram Grammatical Change to “”… instruments that give consistent Accepted.
results in heating mode may not necessarily give
consistent results in …”
UK 8.3.2 Para 2 Gram Grammatical Change to “”Cooling and heating runs shall be Accepted.
performed at the same rate to be used for
subsequent measurements.”
page 8 of 15
1 2 (3) 4 5 (6) (7)
Annex Note com-
UK 8.3.2 Para 4 & 5 Tech Inconsistent specification (semantics). How can an Resolve inconsistency of terms (see comments on Not accepted.
“extrapolated “ value be obtained by “interpolation” legend to Fig 2) Here we are talking about two
different things:
1. Peak onset temperatures
are extrapolated using an
interpolated virtual baseline
(see Fig. 2)
2. Measured temperature
corrections are interpolated
within the temperature
range covered by the
calibration materials.
UK 8.3.2 Para 5 Gram Unnecessary text Delete “thus determined”. Also put “i” in italics. Accepted.
UK 8.3.2 Para 6 Gram. Grammatical Change to “… interpolation of the temperature …” Accepted.
UK 8.3.2 Para 6 Gram Unnecessary text: superfluous Delete respectively in both definitions. Accepted.
UK 8.3.2 Note 3 Gram Grammatical Change to “The temperature correction may be Accepted.
performed automatically …”
UK 8.3.2 Last para Tech Is it too demanding that the calibration is performed each Consider changing to “”… and has to be performed Accepted.
time the heating rate is changed? for each heating rate.”
UK 8.3.3 Para 1 Gram Grammatical Change “temperature distance” to “temperature Accepted.
difference” / “temperature differences”
UK 8.3.3 Para 1 Gram Grammatical Change to “ For a more precise method of Accepted.
temperature calibration taking into account the
effect ….”
UK 8.4.1 and 8.5.1 Line 1 Gram Grammatical Change to “This procedure establishes …” Accepted.
page 9 of 15
1 2 (3) 4 5 (6) (7)
Annex Note com-
UK 8.4.1 and Various Edit Consistency of subscripts: both “m” and “meas” are used Use only one symbol per definition for each term – Accepted.
elsewhere (8.1, to specify the same item in this document. Similarly “tr” is revise for consistency. Wherever applicable, only
Annex A, …) used here, in 8.2 and “cal” in Annex A. indices 'm' and 'cal' are used,
respectively.
UK 8.4.1 Last sentence Tech The relation is only assumed. Change to “… is assumed where K Q….” Not accepted.
Not understood what is wrong
in expressing the difference
between true and measured
value by a temperature
dependent calibration factor.
UK 8.4.2 Para 4 Tech Equation 8 has mass as a divisor and thus the quantity is a Change to “… and the specific heat of melting is Accepted.
specific quantity. obtained from the area between the DSC curve and
the virtual …”
UK 8.4.2 Equation 8 Tech Tref is not the integral variable – surely T is. Delete the subscript “ref” from equation 8, and Accepted.
change the definition to “T – temperature”
UK 8.5.1 Para 2 Tech The relation is only assumed. Change to “… is assumed where K(dQ/dt) ….” Not accepted.
Not understood what is wrong
in expressing the difference
between true and measured
value by a temperature
dependent calibration factor.
UK 8.5.1 Last para Tech The term “specific heat difference at Tg” is not Delete, or clarify what is meant. Not clear.
understood. Is 'change of specific heat'
better?
UK 9.1.1 Line 1 Tech Completeness Change to “…prior to any calibration or testing …” Accepted.
UK 9.1.2 Line 2 Gram Grammatical Change to “ The instrument shall be …” Accepted.
UK 9.1.4 Line 2 Gram Superfluous text Delete “respectively”. Accepted.
page 10 of 15
1 2 (3) 4 5 (6) (7)
Annex Note com-
UK 9.1.4 Note 2 Gram Grammatical Change to “… computer controlled instruments, a Accepted.

remaining curvature can be corrected for by …”
UK 9.2.2 Para 2 Gram Grammatical Change to “ ... as the reference.” Accepted.
UK 9.4.1 Note Gram Grammatical Change to “… effects are larger for …” Accepted.
UK 9.4.2.2 Note, line4 Tech Appropriate description Change to “… to erase prior thermal history …” Accepted.
UK 9.4.3.2.2 Line 3 Gram Grammatical Change to “… baseline is obtained. The …” Accepted.
UK 9.4.3.3.2 Para 1 Tech No mention is made of loading the reference crucible. Add text to include the reference crucible. Accepted.,
Although not really required
as typically the reference
crucible is just left in its
position.
UK 9.5.1 Para 1 Gram Grammatical Change to “ … the instrument baseline.” Accepted.
UK 9.5.2 Note Gram Grammatical Change to “Their re-use …” Accepted.
UK 10 d) Tech Completeness Change to “ … and masses of crucibles used.” Accepted.
UK 10 f) Gram Grammatical Change to “ … extended) and details of the Accepted.
calibration materials used including …”
UK 8.3.3 General Tech In table C1 of Annex C there are few temperature Revise to provide clarity and consistent Comment not clear.
intervals between adjacent calibrants of less than 50K. information. Annex C does not require
On what basis therefore has the precision of ± 0,8 K for using adjacent calibration
a temperature range between calibrants of less than 50 materials but is just a list of
K been determined, and more significantly how can that recommendations.
be achieved by users of this standard.
As clearly mentioned in the
text all accuracy values have
been taken from published
literature. For details please
refer to the bibliography.
page 11 of 15
1 2 (3) 4 5 (6) (7)
Annex Note com-
UK Annex A Para 1 Tech ΡΕ : Higher precision than ± 0,8 K per temperature Change to: Not accepted.
range of 50 K is required.
The extended temperature calibration shall be used Publications referred to clearly
The precision statement should be independent of how if one ore more of the following are required: show that the precision
it is achieved. depends on the range of
 Higher precision than ± 0,8 K. adjacent calibration materials.
See comment on 8.3.3. For what reason shall this
 effect of heating rate in calibration procedure. important constraint not be
 influence of specimen mass in calibration mentioned?
procedure.
UK Annex A Para 2 Gram Grammatical Change to “Two specimens of each of at least 3 Accepted.
different …”
Change to “…with masses m of approximately 3 mg
and 10 mg …
UK Annex A Para 3 Gram Poor grammar Change to “ Accepted.
For each heating and cooling rate, β = 1 K/min,
5 K/min, 10 K/min and 20 K/min, the specimen
shall be melted and re-crystallised and then
subjected to a heating run at the same rate
during which the melting peak is recorded.
page 12 of 15
1 2 (3) 4 5 (6) (7)
Annex Note com-
UK Annex A Para 4 Tech Inconsistent specification (semantics). How can an Resolve inconsistency of terms (see comments on Not accepted.
“extrapolated “ value be obtained by “interpolation” legend to Fig 2) Here we are talking about two
different things:
1. Peak onset temperatures
are extrapolated using an
interpolated virtual baseline
(see Fig. 2)
2. Measured temperature
corrections are interpolated
within the temperature
range covered by the
calibration materials.
UK Annex A Eqn A.2 Tech Tech error Change “Ttcal” to “Tcal” Accepted.
(or use “tr” subscript for consistency” – see
comment 8.4.1)
UK Annex A Note Gram Grammatical Change to “NOTE The temperature correction with Accepted.
respect to heating rate and./or temperature may be
done …”
UK Annex A Para after Gram What is mean’t by “bigger”? Bigger than 50K? The Clarify text Not clear.
Note example, Fig A.2, gives temperature intervals of approx This is just general
130K and 70K between calibrants. information. Clearly, the
bigger the temperature range
the poorer the accuracy.
Giving any limit values is not
appropriate nor would it help
the user but would be rather
misleading.
Proposal?
page 13 of 15
1 2 (3) 4 5 (6) (7)
Annex Note com-
UK Annex B Para 1 Gram Grammatical The extended heat calibration shall be used if Accepted.
one or more of the following are required: Text revised.
 Higher precision than ± 2 %.
 effect of heating rate in calibration procedure.
 influence of specimen mass in calibration
procedure.
UK Annex A & B Equations Edit Editorial Extra spaces in equations A.1, B.1 and B.2 Accepted.
UK Annex C Table C.3, Edit Editorial Change to “… 290 K to 550 K …” Accepted.
title
UK Annex D Para 3 Gram Grammatical Change to “… crucible can invalidate the calibration Text not foiund in paragraph 3
and damage the …” of Annex D.
UK Annex E Para 1, line 4 Gram Grammatical Change to “”… comparative analysis in parallel ..” Accepted.
UK Annex E Para 3, line 4 Gram Grammatical Change to “ … transitions which overlap …” Accepted.
UK Annex E Para 3, line7 Gram Grammatical Change to “… defined in the case of …” Accepted.
UK Annex E Para 3, last Gram Grammatical Change to “… significant effect on the characteristic Accepted.
line …”
UK Annex E Para 4 Gram Grammatical Change to “For some polymers the DSC curve can Accepted.
have several peaks during …”
UK Annex E Para 4, line Gram Grammatical Change to “… without being influenced by its Accepted.
10 thermal …”
UK Annex E Para 4, line Gram Grammatical Change to “ … and the temperature of kinetics …” Accepted.
12
page 14 of 15
1 2 (3) 4 5 (6) (7)
Annex Note com-
JP 8.4, 8.5 Formula (9), te It is desirable to add the following note at the To add Note as follows: Not accepted.
(12) end of “8. Calibration.” NOTE The above two calibration factors, K(Q)(T) I do not really understand the
in Eq. (9) and K(dQ/dt)(T) in Eq. (12), are comment as it seems to
essentially the same as each other. Therefore, contradict itself. If K(Q)(T) and
they can be replaced each other. K(dQ/dt)(T) is K(dQ/dt)(T) were the same it
more desirable, because of the high accuracy and made no sense to discuss
high temperature resolution, though it needs higher what is more desirable.
skillfulness than K(Q)(T).
In fact, it can be shown by
Reference Y. Takahashi, Thermochim. Acta, 88, experience and has been
199 (1985) deduced by Sarge et. al. that
due to experimental effects
there is a difference between
calibration factors determined
by heat of fusion K(Q)(T) and
heat flow rate K(dQ/dt)(T)
even if we left out procedural
errors which in practice have
a significant additional
influence.
Ref. S.M. Sarge et. al.,
Thermochim. Acta, 247, 129
(1994)
page 15 of 15

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DRAFT INTERNATIONAL STANDARD ISO/DIS 11357-1

ISO/TC 61/SC 5 Secretariat: ANSI

Voting begins on: Voting terminates on:

Plastics — Differential scanning calorimetry (DSC) —

Plastiques — Analyse calorimétrique différentielle (DSC) —

Partie 1: Principes généraux

[Revision of first edition (ISO 11357-1:1997)]

ISO/CEN PARALLEL ENQUIRY

© International Organization for Standardization, 2008

Adobe is a trademark of Adobe Systems Incorporated.

ISO copyright office

Reproduction may be subject to royalty payments or a licensing agreement.

Violators may be prosecuted.

ii © ISO 2008 – All rights reserved

© ISO 2008 – All rights reserved iii

8.4.1 General ...............................................................................................................................14

iv © ISO 2008 – All rights reserved

 Part 1: General principles

 Part 2: Determination of glass transition temperature

 Part 3: Determination of temperature and enthalpy of melting and crystallisation

 Part 4: Determination of specific heat capacity

 Part 6: Oxidation induction time (isothermal OIT) or temperature (dynamic OIT)

 Part 7: Determination of crystallisation kinetics

© ISO 2008 – All rights reserved v

The most important changes in this revision of ISO 11357-1 include:

• A procedure for heat flow rate calibration.

• Information on interactions between calibration substances and crucible materials.

vi © ISO 2008 – All rights reserved

Plastics — Differential scanning calorimetry (DSC) — Part 1:

− elastomers (with or without filler(s), fibres or reinforcing additives).

© ISO 2008 – All rights reserved 1

− ISO 291, Plastics - Standard atmospheres for conditioning and testing

− ISO 472, Plastics – Vocabulary

− ISO 80000-5, Quantities and units – Part 5: Thermodynamics

3 Terms, definitions, symbols, units and abbreviated terms

3.1 Differential scanning calorimetry (DSC)

3.2 Calibration material

NOTE 1 Normally the reference crucible is empty.

3.4 Heat flow rate

2 © ISO 2008 – All rights reserved

3.5 Change of heat, ∆Q

3.6 Specific heat capacity at constant pressure, cp

and c p is expressed in joules per gram Kelvin (J . g-1 . K-1]

© ISO 2008 – All rights reserved 3

Figure 1 — Schematic drawing of baselines

3.7.2 Instrument baseline

NOTE The instrument baseline is required for heat capacity measurements.

3.7.3 Specimen baseline

4 © ISO 2008 – All rights reserved

3.7.4 Virtual baseline

3.8.2 Step height

3.9.2 Endothermic peak

3.9.3 Exothermic peak

3.9.4 Peak area

Area enclosed by the peak and the virtual interpolated baseline.

© ISO 2008 – All rights reserved 5

3.9.5 Peak height

3.9.6 Peak width

Distance between onset and end temperatures or times of a peak.

3.10 Characteristic temperatures or times

temperature of reference position

temperature of sample position

6 © ISO 2008 – All rights reserved