DIN EN ISO 11357-4-2014 Plastics - Differential scanning calorimetry (DSC) - Part 4 Determination of specific heat capacity (ISO 11357-4 2014) German version EN ISO 11357-4 2014《塑料.pdf

1、October 2014Translation by DIN-Sprachendienst.English price group 11No part of this translation may be reproduced without prior permission ofDIN Deutsches Institut fr Normung e. V., Berlin. Beuth Verlag GmbH, 10772 Berlin, Germany,has the exclusive right of sale for German Standards (DIN-Normen).ICS

2、 83.080.01!%;s(“2248005www.din.deDDIN EN ISO 11357-4Plastics Differential scanning calorimetry (DSC) Part 4: Determination of specific heat capacity (ISO 11357-4:2014);English version EN ISO 11357-4:2014,English translation of DIN EN ISO 11357-4:2014-10Kunststoffe Dynamische Differenz-Thermoanalyse

3、(DSC) Teil 4: Bestimmung der spezifischen Wrmekapazitt (ISO 11357-4:2014);Englische Fassung EN ISO 11357-4:2014,Englische bersetzung von DIN EN ISO 11357-4:2014-10Plastiques Analyse calorimtrique diffrentielle (DSC) Partie 4: Dtermination de la capacit thermique massique (ISO 11357-4:2014);Version a

4、nglaise EN ISO 11357-4:2014,Traduction anglaise de DIN EN ISO 11357-4:2014-10SupersedesDIN EN ISO 11357-4:2013-04www.beuth.deIn case of doubt, the German-language original shall be considered authoritative.Document comprises 19 pages09.14 DIN EN ISO 11357-4:2014-10 2 A comma is used as the decimal m

5、arker. National foreword This document (EN ISO 11357-4:2014) has been prepared by Technical Committee ISO/TC 61 “Plastics” (Secretariat: SAC, China) in collaboration with Technical Committee ISO/TC 249 “Plastics” (Secretariat: NBN, Belgium). The responsible German body involved in its preparation wa

6、s the DIN-Normenausschuss Kunststoffe (DIN Standards Committee Plastics), Working Committee NA 054-01-03 AA Physikalische, rheologische und analytische Prfungen. DIN EN ISO 11357 consists of the following parts, under the general title Plastics Differential scanning calorimetry (DSC): Part 1: Genera

7、l principles Part 2: Determination of glass transition temperature and glass transition step height Part 3: Determination of temperature and enthalpy of melting and crystallization Part 4: Determination of specific heat capacity Part 5: Determination of characteristic reaction-curve temperatures and

8、 times, enthalpy of reaction and degree of conversion Part 6: Determination of oxidation induction time (isothermal OIT) and oxidation induction temperature (dynamic OIT) Part 7: Determination of crystallization kinetics The DIN Standards corresponding to the International Standards referred to in t

9、his document are as follows: ISO 472 DIN EN ISO 472 ISO 11357-1 DIN EN ISO 11357-1 Amendments This standard differs from DIN EN ISO 11357-4:2013-04 as follows: a) all normative references are now undated; b) throughout the document, the term “pan” has been replaced by “crucible”; in the German versi

10、on, the term Tiegel remains unchanged; c) the endothermic direction “a” has been added in all figures and keys. Previous editions DIN EN ISO 11357-4: 2013-04 DIN EN ISO 11357-4:2014-10 3 National Annex NA (informative) Bibliography DIN EN ISO 472, Plastics Vocabulary DIN EN ISO 11357-1, Plastics Dif

11、ferential scanning calorimetry (DSC) Part 1: General principles DIN EN ISO 11357-4:2014-10 4 This page is intentionally blank EN ISO 11357-4June 2014 ICS 83.080.01 Supersedes EN ISO 11357-4:2013English Version Plastics - Differential scanning calorimetry (DSC) - Part 4: Determination of specific hea

12、t capacity (ISO 11357-4:2014) Plastiques - Analyse calorimtrique diffrentielle (DSC) - Partie 4: Dtermination de la capacit thermique massique (ISO 11357-4:2014) Kunststoffe - Dynamische Differenz-Thermoanalyse (DSC) -Teil 4: Bestimmung der spezifischen Wrmekapazitt(ISO 11357-4:2014) This European S

13、tandard was approved by CEN on 10 July 2014. 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

14、 such national standards may be obtained on application to the CEN-CENELEC Management Centre or to any CEN 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 CEN member into its

15、 own language and notified to the CEN-CENELEC Management Centre has the same status as the official versions. CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, German

16、y, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and United Kingdom. CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels 2014 CEN All rights of exploi

17、tation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN ISO 11357-4:2014 EEUROPEAN COMMITTEE FOR STANDARDIZATIONCOMIT EUROPEN DE NORMALISATIONEUROPISCHES KOMITEE FR NORMUNGEUROPEAN STANDARDNORME EUROPENNEEUROPISCHE NORM2DIN EN ISO 11357-4:2014-10 EN ISO 11357-4:2

18、014 (E) Contents Page Foreword . 3 1 Scope . 4 2 Normative references. 4 3 Terms and definitions 4 4 Principle 5 4.1 General 5 4.2 Continuous-scanning method 6 4.3 Stepwise-scanning method . 7 5 Apparatus 7 6 Test specimen . 7 7 Test conditions and specimen conditioning . 7 8 Procedure 7 8.1 Selecti

19、on of crucibles 7 8.2 Setting up the apparatus and adjustment of isothermal baselines 8 8.3 Measurement of specific heat capacity of calibration material . 9 8.4 Specimen run 10 9 Determination of specific heat capacities . 10 9.1 Calculation of specific heat capacities 10 9.2 Numerical rounding of

20、the results 10 10 Precision and bias 11 11 Test report . 11 Annex A (informative) An approximate expression of the specific heat capacity of pure -alumina 3 to 5 12 Bibliography 15 ForewordThis document (EN ISO 11357-4:2014) has been prepared by Technical Committee ISO/TC 61 Plastics in collaboratio

21、n with Technical Committee CEN/TC 249 “Plastics” the secretariat of which is held by NBN. 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 December 2014, and conflicting national standards shall be

22、 withdrawn at the latest by December 2014. Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. CEN and/or CENELEC shall not be held responsible for identifying any or all such patent rights. This document supersedes EN ISO 11357-4:201

23、3. According to the CEN-CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France,

24、Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom. Endorsement notice The text of ISO 11357-4:2014 has been approved by CEN as EN ISO 1

25、1357-4:2014 without any modification. “ ”3DIN EN ISO 11357-4:2014-10EN ISO 11357-4:2014 (E)EN 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 and glas

26、s transition step height Part 3: Determination of temperature and enthalpy of melting and crystallization 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: Determination

27、 of oxidation induction time (isothermal OIT) and oxidation induction temperature (dynamic OIT) Part 7: Determination of crystallization kinetics 1 ScopeThis part of ISO 11357 specifies methods for determining the specific heat capacity of plastics by differential scanning calorimetry.2 Normative re

28、ferencesThe following documents, in whole or in part, are normatively referenced in this document and are indispensable for the application of this document. For undated references, the latest edition of the referenced document (including any amendments) applies.ISO 472, Plastics VocabularyISO 11357

29、-1, Plastics Differential scanning calorimetry (DSC) Part 1: General principlesISO 80000-1, Quantities and units Part 1: General3 Terms and definitionsFor the purposes of this document, the terms and definitions given in ISO 472 and ISO 11357-1 and the following apply.3.1calibration materialmaterial

30、 of known specific heat capacityNote 1 to entry: Usually, -alumina (such as synthetic sapphire) of 99,9 % or higher purity is used as the calibration material.3.2specific heat capacity (at constant pressure)cpquantity of heat necessary to raise the temperature of unit mass of material by 1 K at cons

31、tant pressureNote 1 to entry: It is given by the following formula:cp= m1Cp= m1(dQ/dT)p(1)where4DIN EN ISO 11357-4:2014-10 EN ISO 11357-4:2014 (E) m is the mass of material;cpis the heat capacity and is expressed in kilojoules per kilogram per K (kJkg1K1) or in joules per gram per K (Jg1K1); subscri

32、pt p indicates an isobaric process;dQ is the quantity of heat necessary to raise the temperature of the material by dT;Note 2 to entry: This formula is valid in a temperature range where a material shows no first-order phase transition.(dQ/dT) = (dt/dT) (dQ/dt) = (heating rate)1 (heat flow rate) (2)

33、Note 3 to entry: At phase transitions, there is a discontinuity in the heat capacity. Part of the heat is consumed to produce a material state of higher energy and it is not all used in raising the temperature. For this reason, the specific heat can only be determined properly outside regions of pha

34、se transitions.4 Principle4.1 GeneralEach measurement consists of three runs at the same scanning rate (see Figure 1):a) a blank run (empty crucibles in sample and reference holders);b) a calibration run (calibration material in sample holder crucible and empty crucible in reference holder);c) a spe

35、cimen run (specimen in sample holder crucible and empty crucible in reference holder).5DIN EN ISO 11357-4:2014-10EN ISO 11357-4:2014 (E)KeyX temperature T or time t1 blank run2 calibration run3 specimen runI isothermal baseline at start temperature TsII isothermal baseline at end temperature TfaEndo

36、thermic direction.Figure 1 Schematic drawing of typical DSC curves for specific heat capacity measurement (blank, calibration and specimen runs) after baseline adjustment4.2 Continuous-scanning methodBased on the DSC principle (see ISO 11357-1) and the definition of specific heat capacity given in 3

37、.2, the following relations can be obtained:mc PPsppspspecimenrunblankrun (3)mc PPcalpcalcalibrationrun blankrun (4)where P is the heat flow rate (dQ/dt); superscripts sp and cal represent specimen and calibration material, respectively (see Figure 1).When Pspecimen run, Pcalibration runand Pblank r

38、unare measured, cpspcan be calculated using Formula (6), since the values of cpcal, mspand mcalare known:mcmcPPsppspcalpcalspecimenrunblankruncalibrationrun=bblankrun(5)ccmP PmPpsppcalcalspecimenrunblankrunspcalibrationrun=()Pblankrun(6)6DIN EN ISO 11357-4:2014-10 EN ISO 11357-4:2014 (E) 4.3 Stepwis

39、e-scanning methodIn the stepwise-scanning method, the total temperature range to be scanned is divided into small intervals and a complete determination consisting of the three runs mentioned in 4.1 is performed for each temperature interval. Upon integration of the heat flow rate curve, the total h

40、eat Q consumed in the interval can be obtained. Dividing Q by the temperature interval T and the mass of the specimen gives the specific heat see Formula (1):mcQTQTsppspsppblankp(7)mcQTQTcalpcalcalpblankp(8)Keeping the temperature intervals T constant, combining Formulae (7) and (8) results in:ccmmQ

41、QQQpsppcalcalspsp blankcalblank= (9)5 Apparatus5.1 DSC apparatus. See ISO 11357-1.5.2 Crucibles. See ISO 11357-1.The crucibles for the test specimen and the reference specimen (calibration material) shall be of the same shape and material and their masses shall not differ by more than 0,1 mg.NOTE Th

42、e same blank run and calibration run can be used for several measurements, if the instrument is sufficiently stable and the difference in mass between the calibration material crucible and the empty crucible is corrected for. An adequate correction can be obtained by adding the term cp, crucible(T)m

43、 to the heat flow rate of the calibration run, where cp,crucible(T) is the specific heat capacity of the calibration crucible as a function of temperature, is the heating rate and m is the difference in mass between the calibration crucible and the empty crucible. The same procedure can also be used

44、 for correcting differences in mass between the specimen run and the blank run.5.3 Analytical balance. See ISO 11357-1.6 Test specimenSee ISO 11357-1.7 Test conditions and specimen conditioningSee ISO 11357-1.8 Procedure8.1 Selection of cruciblesPrepare three crucibles and their lids and weigh the c

45、rucibles together with their lids. The total mass shall not differ by more than 0,1 mg (see 5.2). In other respects, such as material, size, crucible type (open or sealed), the crucibles shall be identical.7DIN EN ISO 11357-4:2014-10EN ISO 11357-4:2014 (E)8.2 Setting up the apparatus and adjustment

46、of isothermal baselines8.2.1 Place a pair of empty crucibles with lids in the DSC sample and reference holders.8.2.2 If using a continuous-scan programme:a) Set the start and end temperatures (Tsand Tf). The start temperature Tsshould be at least 30 K lower than that at which data are first required

47、.NOTE 1 When more precise results are required over a wide temperature range, the overall range can be divided into two (or more) smaller ranges, each 50 K to 100 K wide. The start temperature Tsof the second range should be 30 K lower than the end temperature Tfof the first temperature range to ens

48、ure sufficient overlap.b) Set the scanning rate.c) Set the time interval between the isothermal stages I and II (see Figure 1) and allow the respective isothermal baselines to stabilize. This interval will usually be between 2 min and 10 min.NOTE 2 Some calorimeters, e.g. those of the Calvet type, m

49、ay need up to 30 min before the baseline stabilizes.8.2.3 If using a stepwise-scan programme:When the specific heat capacities of the samples do not significantly depend on the temperature, the stepwise-scanning method can be used in which the integration of the heat flow over small temperature intervals gives a set of