BS-EN-ISO-11357-1-1997.pdf

BRITISH STANDARD BS EN ISO 11357-1:1997 Plastics Differential scanning calorimetry (DSC) Part 1: General principles The European Standard EN ISO 11357-1:1997 has the status of a British Standard ICS 83.080.01 BS EN ISO 11357-1:1997 This British Standard, having been prepared under the direction of the Sector Board for Materials and Chemicals, was published under the authority of the Standards Board and comes into effect on 15 July 1997 © BSI 03-2000 ISBN 0 580 27579 5 National foreword This British Standard is the English language version of EN ISO 11357-1:1997. It is identical with ISO 11357-1:1997. The UK participation in its preparation was entrusted to Technical Committee PRI/21, Testing of plastics, which has the responsibility to: aid enquirers to understand the text; present to the responsible international/European committee any enquiries on the interpretation, or proposals for change, and keep the UK interests informed; monitor related international and European developments and promulgate them in the UK. A list of organizations represented on this committee can be obtained on request to its secretary. Cross-references Attention is drawn to the fact that CEN and CENELEC standards normally include an annex which lists normative references to international publications with their corresponding European publications. The British Standards which implement international or European publications referred to in this document may be found in the BSI Standards Catalogue under the section entitled “International Standards Correspondence Index”, or using the “Find” facility of the BSI Standards Electronic Catalogue. A British Standard does not purport to include all the necessary provisions of a contract. Users of British Standards are responsible for their correct application. Compliance with a British Standard does not of itself confer immunity from legal obligations. Summary of pages This document comprises a front cover, an inside front cover, pages i and ii, the EN ISO title page, page 2, the ISO title page, pages ii to iv, pages 1 to 8, an inside back cover and a back cover. This standard has been updated (see copyright date) and may have had amendments incorporated. This will be indicated in the amendment table on the inside front cover. Amendments issued since publication Amd. No.DateComments BS EN ISO 11357-1:1997 © BSI 02-2000i Contents Page National forewordInside front cover Foreword2 Forewordiii Text of ISO 11357-11 ii blank EUROPEAN STANDARD NORME EUROPÉENNE EUROPÄISCHE NORM EN ISO 11357-1 April 1997 ICS 83.080.01 Descriptors: See ISO document English version Plastics Differential scanning calorimetry (DSC) Part 1: General principles (ISO 11357-1:1997) Plastiques Analyse calorimétrique différentielle (DSC) Partie 1: Principes généraux (ISO 11357-1:1997) Kunststoffe Dynamische Differenz-Thermoanalyse (DSC) Teil 1: Allgemeine Grundlagen (ISO 11357-1:1997) This European Standard was approved by CEN on 1997-03-28. CEN 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 CEN member. The European Standards exist in three official versions (English, French, German). A version in any other language made by translation under the responsibility of a CEN member into its own language and notified to the Central Secretariat has the same status as the official versions. CEN members are the national standards bodies of Austria, Belgium, Czech Republic, Denmark, Finland, France, Germany, Greece, Iceland, Ireland, Italy, Luxembourg, Netherlands, Norway, Portugal, Spain, Sweden, Switzerland and United Kingdom. CEN European Committee for Standardization Comité Européen de Normalisation Europäisches Komitee für Normung Central Secretariat: rue de Stassart 36, B-1050 Brussels © 1997 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN ISO 11357-1:1997 E EN ISO 11357-1:1997 © BSI 02-2000 2 Foreword The text of the International Standard ISO 11357-1:1997 has been prepared by Technical Committee ISO/TC 61 “Plastics” in collaboration with Technical Committee CEN/TC 249 “Plastics”, the secretariat of which is held by IBN. This European Standard shall be given the status of a national standard, either by publication of an identical text or by endorsement, at the latest by October 1997, and conflicting national standards shall be withdrawn at the latest by October 1997. According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Czech Republic, Denmark, Finland, France, Germany, Greece, Iceland, Ireland, Italy, Luxembourg, Netherlands, Norway, Portugal, Spain, Sweden, Switzerland and the United Kingdom. Endorsement notice The text of the International Standard ISO 11357-1:1997 was approved by CEN as a European Standard without any modification. EN ISO 11357-1:1997 ii © BSI 02-2000 Contents Page Forewordiii 1Scope1 2Normative reference1 3Definitions1 4Principle3 5Apparatus and materials3 6Test specimen3 7Test conditions and specimen conditioning3 8Calibration4 9Procedure5 10Test report6 Annex A (informative) Standard reference materials7 Annex B (informative) General recommendations8 Annex C (informative) BibliographyInside back cover Figure 1 Typical DSC curve2 Table A.1 Transition or melting temperatures and enthalpies of fusion for various reference materials7 Table A.2 Reference material for glass transition temperature7 Table A.3 Reference material for measurement of specific heat capacity7 Descriptors: Plastics, polymers, calorimetry, tests, thermal analysis, differential thermal analysis, generalities. EN ISO 11357-1:1997 © BSI 02-2000iii Foreword ISO (the International Organization for Standardization) is a worldwide federation of national standards bodies (ISO member bodies). The work of preparing International Standards is normally carried out through ISO technical committees. Each member body interested in a subject for which a technical committee has been established has the right to be represented on that committee. International organizations, governmental and non-governmental, in liaison with ISO, also take part in the work. ISO collaborates closely with the International Electrotechnical Commission (IEC) on all matters of electrotechnical standardization. Draft International Standards adopted by the technical committees are circulated to the member bodies for voting. Publication as an International Standard requires approval by at least 75 % of the member bodies casting a vote. International Standard ISO 11357 was prepared by Technical Committee ISO/TC 61, Plastics, Subcommittee SC 5, Physical-chemical properties. 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 crystallization; Part 4: Determination of specific heat capacity; Part 5: Determination of polymerization temperatures and/or times and polymerization kinetics; Part 6: Determination of oxidation induction time; Part 7: Determination of crystallization kinetics. Annex A, Annex B and Annex C of this part of ISO 11357 are for information only. iv blank EN ISO 11357-1:1997 © BSI 02-20001 WARNING The use of this International Standard may involve hazardous materials, operations and equipment. This 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 establish appropriate health and safety practices and to determine the applicability of regulatory limitations prior to use. 1 Scope This International Standard specifies a method for the thermal analysis of polymers such as thermoplastics and thermosetting plastics, including moulding materials and composite materials, using differential scanning calorimetry (DSC). Various determinations can be made on polymers by using differential scanning calorimetry. These determinations are dealt with in parts 2 to 7 of this standard (see the foreword). 2 Normative reference The following standard contains provisions which, through reference in this text, constitute provisions of this part of ISO 11357. At the time of publication, the edition indicated was valid. All standards are subject to revision, and parties to agreements based on this part of ISO 11357 are encouraged to investigate the possibility of applying the most recent edition of the standard indicated below. Members of IEC and ISO maintain registers of currently valid International Standards. ISO 291:, Plastics Standard atmospheres for conditioning and testing1). 3 Definitions For the purposes of this International Standard, the following definitions apply: 3.1 differential scanning calorimetry (DSC) a technique in which the difference between the heat flux (power) into a test specimen and that into a reference specimen is measured as a function of temperature and/or time while the test specimen and the reference specimen are subjected to a controlled temperature programme it is common practice to record, for each measurement, a curve in which temperature or time is plotted on the x-axis and heat flux difference is plotted on the y-axis 3.2 reference specimen a known specimen which is usually thermally inactive over the temperature and time range of interest NOTEGenerally an empty pan identical to the one containing the test specimen is used as the reference specimen. 3.3 standard reference 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 DSC apparatus, for the assessment of a measurement method or for assigning values to materials 3.4 heat flux; thermal power the amount of heat transferred per unit time (dQ/dt) NOTEThe total quantity of heat transferred Q corresponds to the time integral of the heat flux where Q is expressed in joules or in joules per unit mass (J·kg1 or J·g1). 3.5 change in enthalpy, %H the quantity of heat absorbed (%H positive) or released (%H negative) by a test specimen undergoing a chemical or physical change, and/or a temperature change, at constant pressure. %H is expressed in joules or in joules per unit mass (J·kg1 or J·g1): 3.6 specific heat capacity at constant pressure, cp the quantity of heat necessary to raise the temperature of unit mass of material by 1 °C at constant pressure, with all other intensive parameters constant: where 1) To be published. (Revision of ISO 291:1977) ·Qis the quantity of heat, expressed in joules, necessary to raise the temperature of material of mass m by ·T degrees Celsius at constant pressure; cpis expressed in joules per kilogram degree Celsius J/(kg·°C) or joules per gram degree Celsius J/(g·°C). EN ISO 11357-1:1997 2 © BSI 02-2000 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 3.7 baseline the part of the recorded curve outside, but adjacent to, the reaction or transition zone. In this part of the recorded curve, the heat flux difference is approximately constant 3.8 virtual baseline an imaginary line drawn through a reaction and/or transition zone assuming that the heat of reaction and/or transition is zero. It is commonly drawn by interpolating or extrapolating the recorded baseline. It is normally indicated on the DSC curve for convenience (see Figure 1) 3.9 peak The part of the DSC curve which departs from the baseline, reaches a maximum, and subsequently returns to the baseline. NOTEThe start of the peak corresponds to the start of the reaction or transition. 3.9.1 endothermic peak a peak in which the energy supplied to the test specimen is greater than the energy corresponding to the virtual baseline 3.9.2 exothermic peak a peak in which the energy supplied to the test specimen is less than the energy corresponding to the virtual baseline NOTEIn accordance with the accepted conventions of thermodynamics, the enthalpy change is negative when the reaction or transition is exothermic and positive when the reaction or transition is endothermic. The direction corresponding to exothermic or endothermic is normally indicated on the DSC curve. 3.9.3 peak height the distance between the virtual baseline and the point of maximum height of a peak. The height is expressed in milliwatts. The height is not proportional to the mass of the test specimen 3.10 characteristic temperatures the following are the characteristic temperature on a DSC curve: onset temperatureTi extrapolated onset temperatureTei peak temperatureTp extrapolated end temperatureTef end temperatureTf Figure 1 Typical DSC curve EN ISO 11357-1:1997 © BSI 02-20003 4 Principle The difference between the heat flux into a test specimen and that into a reference specimen is measured as a function of temperature and/or time, while the test specimen and the reference specimen are subjected to a controlled temperature programme under a specified atmosphere. NOTETwo types of DSC, power-compensation DSC and heat-flux DSC, may be carried out. They are distinguished by the design of instrumentation used for measurement, as follows: a) Power-compensation DSC: The difference between the heat flux into the test specimen and that into the reference specimen is measured as a function of temperature or time while varying the temperature of the specimens in accordance with a controlled programme, keeping the temperature of both specimens equal. b) Heat-flux DSC: The difference in heat flux derived from the temperature difference between a test specimen and a reference specimen is measured as a function of temperature or time while varying the temperature of the specimens in accordance with a controlled programme. In this type of measurement, the difference in temperature between the test specimen and reference specimen is proportional to the difference in heat flux. 5 Apparatus and materials 5.1 Differential scanning calorimeter, the main features of which are as follows: a) the capability to generate constant heating and cooling rates between 0,5 °C/min and 20 °C/min; b) the capability to maintain the test temperature constant to within ± 0,5 °C for at least 60 min; c) the capability to carry out step heating or any other heating mode; d) a gas-flow rate in the range 10 ml/min to 50 ml/min, controllable to ± 10 %; e) temperature signals with 0,1 °C resolution and noise below 0,5 °C; f