SIST EN 61006:2005
(Main)Electrical insulating materials - Methods of test for the determination of the glass transition temperature
Electrical insulating materials - Methods of test for the determination of the glass transition temperature
Specifies procedures for test methods for the determination of the glass transition temperature of solid electrical insulating materials. They are applicable to amorphous materials or to partially crystalline materials containing amorphous regions which are stable and do not undergo decomposition or sublimation in the glass transition region. Changes from the first edition are as follows: - the standard has been completely revised from an editorial point of view and adapted to the state of the art; - a figure to demonstrate the dynamic mechanical analysis has been introduced.
Elektroisolierstoffe - Prüfverfahren zur Bestimmung der Glasübergangstemperatur
Matériaux isolants électriques - Méthodes d'essai pour la détermination de la température de transition vitreuse
Spécifie les procédures des méthodes d'essai pour la détermination de la température de transition vitreuse des matériaux isolants électriques solides. Elles s'appliquent aux matériaux amorphes ou aux matériaux partiellement cristallins comportant des zones amorphes stables et ne subissant pas de décomposition ni de sublimation dans la zone de transition vitreuse. Les changements par rapport à la première édition sont les suivants: - la norme a été complètement révisée d'un point de vue éditorial et adaptée à l'état de la technique; - une figure démontrant l'analyse mécanique dynamique a été introduite.
Električni izolacijski materiali – Preskusne metode za ugotavljanje temperaturne prehodnosti stekla (Tg) (IEC 61006:2004)
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SIST EN 61006:2005SLOVENSKIjanuar 2005
STANDARD(istoveten EN 61006:2004)Električni izolacijski materiali – Preskusne metode za ugotavljanje temperaturne prehodnosti stekla (Tg) (IEC 61006:2004)Electrical insulating materials - Methods of test for the determination of the glass transition temperature (IEC 61006:2004)©
Standard je založil in izdal Slovenski inštitut za standardizacijo. Razmnoževanje ali kopiranje celote ali delov tega dokumenta ni dovoljenoReferenčna številkaSIST EN 61006:2005(en)ICS29.035.01
EUROPEAN STANDARD
EN 61006 NORME EUROPÉENNE EUROPÄISCHE NORM
April 2004 CENELEC European Committee for Electrotechnical Standardization Comité Européen de Normalisation Electrotechnique Europäisches Komitee für Elektrotechnische Normung
Central Secretariat: rue de Stassart 35, B - 1050 Brussels
© 2004 CENELEC - All rights of exploitation in any form and by any means reserved worldwide for CENELEC members.
Ref. No. EN 61006:2004 E
ICS 17.220.99; 29.035.01 Supersedes EN 61006:1993
English version
Electrical insulating materials –
Methods of test for the determination
of the glass transition temperature (IEC 61006:2004)
Matériaux isolants électriques –
Méthodes d'essai pour la détermination
de la température de transition vitreuse (CEI 61006:2004)
Elektroisolierstoffe –
Prüfverfahren zur Bestimmung
der Glasübergangstemperatur (IEC 61006:2004)
This European Standard was approved by CENELEC on 2004-03-01. CENELEC members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this European Standard the status of a national standard without any alteration.
Up-to-date lists and bibliographical references concerning such national standards may be obtained on application to the Central Secretariat or to any CENELEC member.
This European Standard exists in three official versions (English, French, German). A version in any other language made by translation under the responsibility of a CENELEC member into its own language and notified to the Central Secretariat has the same status as the official versions.
CENELEC members are the national electrotechnical committees of Austria, Belgium, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom.
EN 61006:2004 - 2 -
Foreword The text of document 15E/222/FDIS, future edition 2 of IEC 61006, prepared by SC 15E, Methods of test, of IEC TC 15, Insulating materials, was submitted to the IEC-CENELEC parallel vote and was approved by CENELEC as EN 61006 on 2004-03-01. This European Standard supersedes EN 61006:1993 Changes from EN 61006:1993 are as follows: – the standard has been completely revised from an editorial point of view and adapted to the state of the art; – a figure to demonstrate the dynamic mechanical analysis has been introduced. The following dates were fixed: – latest date by which the EN has to be implemented
at national level by publication of an identical
national standard or by endorsement
(dop)
2004-12-01 – latest date by which the national standards conflicting
with the EN have to be withdrawn
(dow)
2007-03-01 __________ Endorsement notice The text of the International Standard IEC 61006:2004 was approved by CENELEC as a European Standard without any modification. __________
NORME INTERNATIONALECEIIEC INTERNATIONAL STANDARD 61006Deuxième éditionSecond edition2004-01 Matériaux isolants électriques – Méthodes d'essai pour la détermination de la température de transition vitreuse
Electrical insulating materials – Methods of test for the determination of the glass transition temperature Pour prix, voir catalogue en vigueur For price, see current catalogue IEC 2004
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Copyright - all rights reserved Aucune partie de cette publication ne peut être reproduite ni utilisée sous quelque forme que ce soit et par aucun procédé, électronique ou mécanique, y compris la photocopie et les microfilms, sans l'accord écrit de l'éditeur. No part of this publication may be reproduced or utilized in any form or by any means, electronic or mechanical, including photocopying and microfilm, without permission in writing from the publisher. International Electrotechnical Commission,
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Web: www.iec.ch CODE PRIX PRICE CODE T Commission Electrotechnique InternationaleInternational Electrotechnical Commission
61006 IEC:2004 – 3 –
CONTENTS FOREWORD.7
1 Scope.11 2 Terms and definitions.11 3 Significance of a method.15 4 Test methods.15 5 Method A: By differential scanning calorimetry (DSC) or differential thermal analysis (DTA).17 5.1 General.17 5.2 Interferences.17 5.3 Apparatus.17 5.4 Calibration.19 5.5 Precautions.19 5.6 Test specimens.19 5.7 Procedure.21 5.8 Test report.21 6 Method B: By thermomechanical analysis (TMA).23 6.1 General.23 6.2 Apparatus.23 6.3 Calibration.25 6.4 Precautions.27 6.5 Test specimens.27 6.6 Procedure.27 6.7 Calculations.29 6.8 Test report.29 7 Method C: By dynamic mechanical analysis (DMA).29 7.1 General.29 7.2 Interferences.31 7.3 Methods and apparatus.31 7.3.1 Apparatus.31 7.3.2 Methods.31 7.3.3 Composition of the apparatus.31 7.4 Calibration.33 7.4.1 Temperature.33 7.4.2 Other parameters.33 7.5 Precautions.33 7.6 Test specimens.33 7.7 Procedure.33 7.8 Calculations.35 7.9 Test report.37
Annex A (informative)
Graphical evaluation.45
Bibliography.47
61006 IEC:2004 – 5 –
Figure 1 – Differential scanning calometry (DSC):
characteristic transition points associated with glass transition.39 Figure 2 – Thermomechanical analysis (TMA) (Expansion mode):
determination of glass transition temperature Tg.39 Figure 3 – Thermomechanical analysis (TMA) (Penetration mode):
determination of the glass transition temperature Tg.41 Figure 4 – Thermomechanical analysis (TMA) (Expansion mode): determination of the glass transition temperature (second run).41 Figure 5 – Typical mechanical dissipation factor profile.43 Figure 6 – Dynamic mechanical analysis (DMA):
determination of the glass transition temperature Tg.43
61006 IEC:2004 – 7 –
INTERNATIONAL ELECTROTECHNICAL COMMISSION ___________
ELECTRICAL INSULATING MATERIALS – METHODS OF TEST FOR THE DETERMINATION OF THE GLASS TRANSITION TEMPERATURE
FOREWORD 1) The International Electrotechnical Commission (IEC) is a worldwide organization for standardization comprising all national electrotechnical committees (IEC National Committees). The object of IEC is to promote international co-operation on all questions concerning standardization in the electrical and electronic fields. To this end and in addition to other activities, IEC publishes International Standards, Technical Specifications, Technical Reports, Publicly Available Specifications (PAS) and Guides (hereafter referred to as “IEC Publication(s)”). Their preparation is entrusted to technical committees; any IEC National Committee interested in the subject dealt with may participate in this preparatory work. International, governmental and non-governmental organizations liaising with the IEC also participate in this preparation. IEC collaborates closely with the International Organization for Standardization (ISO) in accordance with conditions determined by agreement between the two organizations. 2) The formal decisions or agreements of IEC on technical matters express, as nearly as possible, an international consensus of opinion on the relevant subjects since each technical committee has representation from all interested IEC National Committees.
3) IEC Publications have the form of recommendations for international use and are accepted by IEC National Committees in that sense. While all reasonable efforts are made to ensure that the technical content of IEC Publications is accurate, IEC cannot be held responsible for the way in which they are used or for any misinterpretation by any end user. 4) In order to promote international uniformity, IEC National Committees undertake to apply IEC Publications transparently to the maximum extent possible in their national and regional publications. Any divergence between any IEC Publication and the corresponding national or regional publication shall be clearly indicated in the latter. 5) IEC provides no marking procedure to indicate its approval and cannot be rendered responsible for any equipment declared to be in conformity with an IEC Publication. 6) All users should ensure that they have the latest edition of this publication. 7) No liability shall attach to IEC or its directors, employees, servants or agents including individual experts and members of its technical committees and IEC National Committees for any personal injury, property damage or other damage of any nature whatsoever, whether direct or indirect, or for costs (including legal fees) and expenses arising out of the publication, use of, or reliance upon, this IEC Publication or any other IEC Publications.
8) Attention is drawn to the Normative references cited in this publication. Use of the referenced publications is indispensable for the correct application of this publication. 9) Attention is drawn to the possibility that some of the elements of this IEC Publication may be the subject of patent rights. IEC shall not be held responsible for identifying any or all such patent rights. International Standard IEC 61006 has been prepared by subcommittee 15E: Methods of test, of IEC technical committee 15: Insulating materials. This second edition cancels and replaces the first edition, published in 1991, and constitutes an editorial revision.
Changes from the first edition are as follows: − the standard has been completely revised from an editorial point of view and adapted to the state of the art; − a figure to demonstrate the dynamic mechanical analysis has been introduced.
61006 IEC:2004 – 9 –
The text of this standard is based on the following documents: FDIS Report on voting 15E/222/FDIS 15E/226/RVD
Full information on the voting for the approval of this standard can be found in the report on voting indicated in the above table. This publication has been drafted in accordance with the ISO/IEC Directives, Part 2. The committee has decided that the contents of this publication will remain unchanged until 2010. At this date, the publication will be
• reconfirmed; • withdrawn; • replaced by a revised edition, or • amended.
61006 IEC:2004 – 11 –
ELECTRICAL INSULATING MATERIALS – METHODS OF TEST FOR THE DETERMINATION OF THE GLASS TRANSITION TEMPERATURE
1 Scope
This International Standard specifies procedures for test methods for the determination of the glass transition temperature of solid electrical insulating materials. They are applicable to amorphous materials or to partially crystalline materials containing amorphous regions which are stable and do not undergo decomposition or sublimation in the glass transition region. 2 Terms and definitions
For the purposes of this document, the following terms and definitions apply. 2.1 glass transition
physical change in an amorphous material or in amorphous regions of a partially crystalline material from (or to) a viscous or rubbery condition to (or from) a hard one NOTE The glass transition generally occurs over a relatively narrow temperature region and is similar to the solidification of a liquid to a glass state; it is not a first order transition. Not only do hardness and brittleness undergo rapid changes in this temperature region, but other properties such as thermal expansion and heat capacity also change rapidly. This phenomenon is also referred to as a second order transition, rubber transition or rubbery transition. Where more than one amorphous transition occurs in a material, the one associated with changes in the segmental motions of the molecular backbone or accompanied by the largest change in properties is usually considered to be the glass transition. Blends of amorphous materials may have more than one glass transition, each associated with a separate component of the blend.
2.2 glass transition temperature Tg midpoint of a temperature range over which the glass transition takes place NOTE 1 The glass transition temperature can be determined readily only by observing the temperature range in which a significant change takes place in some specific electrical, mechanical, thermal, or other physical property. Moreover, the observed temperature can vary significantly depending on the property chosen for observation and on details of the experimental technique (e.g., heating rate, frequency of test). Therefore, the observed Tg should be considered only an approximate value, valid only for that particular technique and test conditions. NOTE 2 For the purpose of test method C (see Clause 7), the temperature of the peak of the mechanical dissipation factor curve accompanying the glass transition is taken to be the glass transition temperature. 2.3 differential scanning calorimetry DSC technique in which the difference in heat flow energy inputs into a tested material and a reference material is measured as a function of temperature while the tested material and the reference material are subjected to a controlled temperature programme NOTE The record is the differential scanning calorimetric or DSC curve.
61006 IEC:2004 – 13 –
2.4 differential thermal analysis
DTA technique in which the temperature difference between a tested material and a reference material is measured as a function of temperature while the common environment of the tested material and the reference material is subjected to a controlled temperature programme NOTE 1 The record is the differential thermal analysis or DTA curve. NOTE 2 There are four characteristic transition points associated with a glass transition (see Figure 1). −
Extrapolated onset temperature (Tf) in °C – The point of intersection of the tangent drawn at the point of greatest slope on the transition curve with the extrapolated baseline prior to the transition.
−
Extrapolated endset temperature (Te) in °C – The point of intersection of the tangent drawn at the point of greatest slope on the transition curve with the extrapolated baseline following the transition.
−
Midpoint temperature (Tm) in °C – The point on the thermal curve corresponding to half the heat flow difference between the extrapolated onset and extrapolated endset.
−
Inflection temperature (Ti) in °C – The point on the thermal curve corresponding to the peak of the first derivative (with respect to temperature) of the parent thermal curve. This point corresponds to the inflection point of the parent thermal curve.
Two additional transition points are sometimes identified and are defined. −
Temperature of first deviation (To) in °C – The point of first detectable deviation from the extrapolated baseline prior to the transition.
−
Temperature of return-to-baseline (Tr) in °C – The point of last deviation from the extrapolated baseline beyond transition.
For the purpose of this standard Tm will be taken as the glass transition temperature Tg which usually corresponds more closely to the transition determined by the dilatometric and other methods.
NOTE 3 Other temperatures than those previously defined can be used for specification purposes as established by individual contract. 2.5 thermodilatometry
technique in which a dimension of a test specimen under negligible load is measured as a function of temperature whilst the substance is subjected to a controlled temperature programme 2.6 thermomechanical analysis
TMA
technique in which a deformation of a test specimen under non-oscillatory load is measured as a function of temperature whilst the test specimen is subjected to a controlled temperature programme 2.7 dynamic mechanical analysis
DMA technique in which either the storage elastic or loss modulus, or both, of a substance under oscillatory load or deformation is measured as a function of temperature, frequency or time, or combination thereof 2.8 complex storage modulus
complex quantity equal to the ratio of mechanical stress to mechanical strain under sinusoidal conditions
61006 IEC:2004 – 15 –
2.9 elastic (storage) modulus
the mathematically real part of the complex storage modulus. A quantitative measurement of elastic properties defined as the ratio of the stress in-phase with oscillating strain to the magnitude of the strain 2.10 loss modulus
the mathematically imaginary part of the complex storage modulus. A quantitative measure of energy dissipation defined as the ratio of stress 90° out of phase with oscillating strain to the magnitude of the strain
2.11 mechanical dissipation factor
the ratio of the loss modulus to the storage elastic modulus
NOTE If, for instance, a material is subjected to forced, sinusoidally oscillating, linear strain ε of constant amplitude, then the mechanical stress σ in the material is determined by σ = Ε
ε = (Ε′ + i Ε′′) ε
where Ε is the complex storage modulus;
Ε′ is the storage modulus (in this case the elastic modulus);
Ε′′ is the loss modulus;
i is the square root of negative one.
The mechanical dissipation factor is equal to Ε′′/Ε′. 3 Significance of a method The glass transition temperature is highly dependent on the thermal history of the material structure to be tested.
For amorphous and semi-crystalline materials the determination of the glass transition temperature may provide important information about their thermal history, processing conditions, stability, progress of chemical reactions, and mechanical and electrical behaviour. The glass transition temperature may be used, for example, as an indication of the degree of cure of thermoset materials. The glass transition temperature of thermoset materials normally increases with increasing cure. Its determination is useful for quality assurance, specification compliance and research. 4 Test methods This standard describes three methods for the determination of the glass transition temperature. They are based on commercially available instruments, capable to operate in a typical temperature range of –100 °C to +500 °C. One method may be more effective in the delineation of the transition than the others depending on the specific material composition, structure and physical state, etc.
Selection of the method should therefore be made according to practical criteria.
NOTE The glass transition takes place over a temperature range and is known to be affected by time dependent phenomena, such as the rate of heating (cooling). For these reasons only data gathered at the same heating rate should be compared.
61006 IEC:2004 – 17 –
Care should be taken in comparing the glass transition temperature reported by one technique with that of another.
5 Method A: By differential scanning calorimetry (DSC) or differential thermal analysis (DTA)
5.1 General
a) Differential scanning calorimetry or differential thermal analysis provides a rapid method for determining changes in heat capacity in a material.
b) The glass transition is indicated by an endothermic shift in the differential heat flow resulting from a change of the heat capacity of the material. 5.2 Interferences
An increase or decrease in heating rate from those specified may alter the results.
The presence of additives and/or impurities will affect the transition, particularly if an impurity tends to form solid solutions, or to be miscible in the post-transition phase. If particle size has an effect upon the transition temperature determined, the samples to be compared should be of approximately the same particle size. The loss of volatile components (e.g., water) during the measuring process may affect the results.
In some cases the material of the test specimens may react with air during the temperature cycle, causing an incorrect transition to be measured. Where it has been shown that this effect is present, provision shall be made for running the test under vacuum or an inert gas blanket. Since some materials degrade near the transition region, care should be used to distinguish between degradation and transition.
Since milligram quantities of material are used, it is essential to ensure that test materials are homogeneous, representative and of similar mass and shape.
5.3 Apparatus
A differential scanning calorimeter (DSC) is used or a differential thermal analyzer (DTA) capable of heating (cooling) at rates up to at least (20 ± 1) K/min, and of automatically recording differential heat flow or differential temperature between the tested material and a reference material, to the required sensitivity and precision. NOTE DSC is the main used one. Aluminium or other metal pans of high thermal conductivity are used as test specimen holders.
For ease of operation an inert reference material with a heat capacity approximately equi-valent to the test specimen may be used (e.g. aluminium oxide).
Nitrogen of 99,9 % purity or other inert gas supply is used for blanketing the test specimen. If oxidative reactions are excluded, air can also be used. The pressure of the selected gas shall be constant.
61006 IEC:2004 – 19 –
The dew-point of the selected gas shall be below the lowest operating temperature.
5.4 Calibration
Following the instrument manufacturer's procedure calibrate the temperature axis of the instrument by using one or more of the standard reference materials given below. Reference materials shall have a minimum purity of 99,9 % and shall be selected according to the temperature range of interest. Calibration against these materials shall employ the same heating rate, purge gas and purge gas flow rate to be used for the test specimens.
For many test measurements, the following melting-point reference materials may be used:
Reference material Melting point (°C)
Mercury –38,9
[1]1
Gallium +29,8
Indium +156,6
[1]
Tin +232,0
[1]
Lead +327,5
[1]
Zinc
+419,6
[1] NOTE The extrapolated onset (see 2.4) should be used as the melting-point temperature, as reported above, in differential scanning calorimetry, and the melting endothermic peak should be used as the melting-point temperature in differential thermal analysis in cases where the temperature sensor is located inside the test specimen.
5.5 Precautions
This standard may involve the use of hazardous materials, operations and equipment. It is the responsibility of whoever uses this standard to establish appropriate safety practices and to determine the applicability of regulatory limitations prior to use.
5.6 Test specimens
• Powdered or granular test specimens – Avoid grinding if a preliminary thermal cycle as outlined in 5.7. is not performed. Grinding or similar techniques for size reduction often introduce thermal effects because of friction or orientation, or both, and thereby change the thermal history of the test specimen.
• Moulded or pelleted test specimens – Cut the test specimens with a microtome, razor blade, hypodermic punch, paper punch or cork borer (size No. 2 or 3) to appropriate size, in thickness or diameter and length that will best fit the test specimen holder and will approximate the desired mass in the subsequent procedure.
• Film or sheet test specimens – For films thicker than 0,04 mm. For thinner films, cut slivers to fit in the test specimen holder or punch disks, if circular test specimen pans are used.
• Liquid test specimens – Catalyzed liquid thermosetting resin can be directly cured in the test pan.
NOTE Any mechanical or thermal pre-treatment should be reported.
___________ 1 Figures in square brackets refer to the bibliography.
61006 IEC:2004 – 21 –
5.7 Procedure
a) Use a test specimen of appropriate mass for the material to be tested. In most cases 10 mg to 20 mg is satisfactory. An amount of reference material with a heat capacity closely matched to that of the test specimen shall be used.
b) Initiate flow of purge gas according to 5.3. Perform and record an initial thermal cycle up to a temperature high enough to erase previous thermal history, testing at a rate of (20 ± 1) K/min.
c) Hold temperature until a steady state is achieved (usually 5 min to 10 min).
d) Quench cool at a minimum rate of 20 K/min to well below the transition temperature of interest, usually 50 K below.
e) Hold temperature until a steady state is achieved (usually 5 min to 10 min).
f) Reheat at a maximum rate of 20 K/min and record the heating curve until all desired transitions have been completed.
Heating rates shall be reported.
NOTE The recommended reheating rate is 10 K/min in accordance with ISO/FDIS 11403-2 [2]. Increasing the heating rate produces greater base line shifts thereby improving detectability. In the case of DSC, the signal is directly proportional to the heating rate for heat capacity measurements.
g) Measure the mid-point temperature Tm (°C) and record it as Tg.
h) Determination should be made on a minimum of three test specimens and Tg reported as the mean of the determinations.
5.8 Test report
The report shall include the following. − Complete identification and description of the material tested, including source and manufacturer's code.
− Description of instrument used for the test.
− Form of test specimen, method of preparation and any
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