DIN EN ISO 11357-5-2014 Plastics - Differential scanning calorimetry (DSC) - Part 5 Determination of characteristic reaction-curve temperatures and times enthalpy of reaction and d.pdf

1、July 2014Translation by DIN-Sprachendienst.English price group 10No 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 83

2、.080.01!%2p“2159577www.din.deDDIN EN ISO 11357-5Plastics Differential scanning calorimetry (DSC) Part 5: Determination of characteristic reaction-curve temperatures andtimes, enthalpy of reaction and degree of conversion(ISO 11357-5:2013);English version EN ISO 11357-5:2014,English translation of DI

3、N EN ISO 11357-5:2014-07Kunststoffe Dynamische Differenz-Thermoanalyse (DSC) Teil 5: Bestimmung von charakteristischen Reaktionstemperaturen und -zeiten,Reaktionsenthalpie und Umsatz (ISO 11357-5:2013);Englische Fassung EN ISO 11357-5:2014,Englische bersetzung von DIN EN ISO 11357-5:2014-07Plastique

4、s Analyse calorimtrique diffrentielle (DSC) Partie 5: Dtermination des tempratures et temps caractristiques de la courbe deraction, de lenthalpie de raction et du degr de transformation (ISO 11357-5:2013);Version anglaise EN ISO 11357-5:2014,Traduction anglaise de DIN EN ISO 11357-5:2014-07www.beuth

5、.deIn case of doubt, the German-language original shall be considered authoritative.Document comprises 15 pages06.14 DIN EN ISO 11357-5:2014-07 2 A comma is used as the decimal marker. National foreword The text of ISO 11357-5:2013 has been prepared by Technical Committee ISO/TC 61 “Plastics” (Secre

6、tariat: SAC, China) and has been taken over as EN ISO 11357-5:2014 by Technical Committee CEN/TC 249 “Plastics” (Secretariat: NBN, Belgium). The responsible German body involved in its preparation was the Normenausschuss Kunststoffe (Plastics Standards Committee), Working Committee NA 054-01-03 AA P

7、hysikalische, rheologische und analytische Prfungen. DIN 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 glass transition step height Part 3: D

8、etermination 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 of oxidation induction time (isot

9、hermal OIT) and oxidation induction temperature (dynamic OIT) Part 7: Determination of crystallization kinetics The DIN Standards corresponding to the International Standards referred to in this document are as follows: ISO 11357-1 DIN EN ISO 11357-1 National Annex NA (informative) Bibliography DIN

10、EN ISO 11357-1, Plastics Differential scanning calorimetry (DSC) Part 1: General principles EN ISO 11357-5 March 2014 ICS 83.080.01 English Version Plastics - Differential scanning calorimetry (DSC) - Part 5: Determination of characteristic reaction-curve temperatures and times, enthalpy of reaction

11、 and degree of conversion(ISO 11357-5:2013) Plastiques - Analyse calorimtrique diffrentielle (DSC) - Partie 5: Dtermination des tempratures et temps caractristiques de la courbe de raction, de lenthalpie de raction et du degr de transformation (ISO 11357-5:2013)Kunststoffe - Dynamische Differenz-The

12、rmoanalyse (DSC) -Teil 5: Bestimmung von charakteristischen Reaktionstemperaturen und -zeiten, Reaktionsenthalpie und Umsatz (ISO 11357-5:2013) This European Standard was approved by CEN on 6 March 2014. CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the co

13、nditions 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 CEN-CENELEC Management Centre or to any CEN member. This European Standard exi

14、sts 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 CEN-CENELEC Management Centre has the same status as the official versions. CEN members are the national st

15、andards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia,

16、Slovenia, Spain, Sweden, Switzerland, Turkey andUnited Kingdom. CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels 2014 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN ISO 11357-5:2014 EEUROPEAN COMMITTEE FOR STANDARD

17、IZATIONCOMIT EUROPEN DE NORMALISATIONEUROPISCHES KOMITEE FR NORMUNGEUROPEAN STANDARDNORME EUROPENNEEUROPISCHE NORM2DIN EN ISO 11357-5:2014-07 EN ISO 11357-5:2014 (E) Contents Page Foreword . 3 1 Scope . 4 2 Normative references. 4 3 Terms and definitions 4 4 Principle 4 5 Apparatus and materials . 5

18、 6 Test specimens 5 7 Test conditions and specimen conditioning . 5 8 Calibration . 5 9 Procedure 5 9.1 General 5 9.2 Temperature-scanning method 5 9.3 Isothermal method . 5 10 Determination of results 7 10.1 Determination of characteristic temperatures and enthalpy of reaction (temperaturescanning

19、method) 7 10.2 Determination of characteristic times and enthalpy of reaction (isothermal method) . 7 10.3 Determination of degree of conversion . 9 11 Precision . 12 12 Test report . 12 Bibliography 13 ForewordThe text of ISO 11357-5:2013 has been prepared by Technical Committee ISO/TC 61 “Plastics

20、” of the International Organization for Standardization (ISO) and has been taken over as EN ISO 11357-5:2014 by 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 iden

21、tical text or by endorsement, at the latest by September 2014, and conflicting national standards shall be withdrawn at the latest by September 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

22、held responsible for identifying any or all such patent rights. 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, Esto

23、nia, Finland, Former Yugoslav Republic of Macedonia, France, 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

24、text of ISO 11357-5:2013 has been approved by CEN as EN ISO 11357-5:2014 without any modification. 3DIN EN ISO 11357-5:2014-07EN ISO 11357-5:2014 (E)WARNING Caution should be observed when working with materials which could give a runaway reaction or exhibit other dangerous behaviour.1 ScopeThis par

25、t of ISO 11357 specifies a method for the determination of reaction temperatures and times, enthalpies of reaction, and degrees of conversion using differential scanning calorimetry (DSC).The method applies to monomers, prepolymers, and polymers in the solid or liquid state. The material can contain

26、 fillers and/or initiators in the solid or liquid state.2 Normative referencesThe following documents, in whole or in part, are normatively referenced in this document and are indispensable for its application. For dated references, only the edition cited applies. For undated references, the latest

27、edition of the referenced document (including any amendments) applies.ISO 11357-1, Plastics Differential scanning calorimetry (DSC) Part 1: General principles3 Terms and definitionsFor the purposes of this document, the terms and definitions given in ISO 11357-1 and the following apply.3.1polymeriza

28、tionprocess of converting a monomer or a mixture of monomers into a polymer3.2crosslinkingprocess of multiple intermolecular covalent or ionic bonding between polymer chains3.3degree of conversionquantity of reacted product obtained during a reaction compared with the maximum possible quantity of th

29、e productNote 1 to entry: The degree of conversion will depend on both time and temperature.4 PrincipleThe principle is specified in ISO 11357-1.The test method described indicates the various stages of the reaction by means of DSC curves.4DIN EN ISO 11357-5:2014-07 EN ISO 11357-5:2014 (E) 5 Apparat

30、us and materialsThe apparatus and materials are specified in ISO 11357-1.6 Test specimensThe test specimens are specified in ISO 11357-1.If not specified otherwise, use a mass of 5 mg to 20 mg and adjust the specimen mass if the thermal effect is too high or too low.7 Test conditions and specimen co

31、nditioningFor polymers, the test conditions and specimen conditioning are specified in ISO 11357-1.For specimens releasing volatile components, it may be necessary to carry out conditioning and testing with the specimen enclosed in a gas-tight specimen crucible which is resistant to high temperature

32、 and pressure.Suitable conditioning procedures shall be agreed between involved parties and included in the test report.8 CalibrationThe calibration is specified in ISO 11357-1.9 Procedure9.1 GeneralThe test may use one of two different methods, depending on what information is required: temperature

33、-scanning method; isothermal method.9.2 Temperature-scanning methodThe temperature-scanning method is specified in ISO 11357-1.Carry out a temperature scan, from ambient temperature to a temperature high enough to record the whole of the reaction peak, at a scan rate in the range 5 K/min to 20 K/min

34、. Use the same scan rate for all tests which are intended to be comparative.The final temperature shall be lower than the temperature corresponding to the onset of decomposition of the polymer.A preliminary test can be useful in defining the decomposition temperature.9.3 Isothermal method9.3.1 Gener

35、alThe isothermal method can be carried out in two different ways once the specimen is loaded into the DSC sample holder: at constant temperature;5DIN EN ISO 11357-5:2014-07EN ISO 11357-5:2014 (E) starting at ambient temperature and heating as quickly as possible to reach the constant measurement tem

36、perature.NOTE The choice of procedure will depend on the model of calorimeter used for the test. The measurement temperature is selected on the basis of a trial run in the temperature-scanning mode. The temperature is intended to be in the vicinity of the temperature at which the peak obtained in th

37、e scanning mode begins.9.3.2 Constant-temperature methoda) Place the reference crucible in the calorimeter.b) Set the instrument to the desired measurement temperature.c) Let the calorimeter stabilize at the selected temperature for 5 min.d) Place the crucible containing the specimen in the calorime

38、ter.e) Record the DSC curve.f) Remove the crucible containing the specimen and let it cool down to ambient temperature.g) Place the crucible containing the specimen back in the calorimeter.h) Record the DSC curve again (the second curve will be subtracted from the first to correct for the calorimete

39、r perturbation caused by the introduction of the crucible).NOTE When using this procedure, it is difficult to ensure that the manual operation by which the crucible is introduced into the calorimeter is carried out repeatedly for the determination and the blank run. Also, changes to the state of the

40、 specimen can have occurred during the reaction. Subtraction of the two curves can therefore introduce an error.9.3.3 Procedure starting at ambient temperaturea) Place both crucibles (reference and specimen) in the calorimeter at ambient temperature.b) Increase the calorimeter temperature, at the hi

41、ghest possible rate, to the selected measurement temperature.c) Record the DSC curve.d) Allow the calorimeter to cool down to ambient temperature.e) Repeat the process without removing the crucibles, and record the DSC curve again (the second curve will be subtracted from the first to correct for th

42、e calorimeter perturbation caused by the rapid heating process).NOTE When using this procedure, changes to the state of the specimen can have occurred during the reaction. Subtraction of the two curves can therefore introduce an error.9.3.4 Residual enthalpyAt the end of an isothermal run performed

43、in accordance with 9.3.2 or 9.3.3, cool down the instrument to ambient temperature with the specimen still inside the sample holder. Then, heat up the specimen to a temperature below specimen decomposition at the same rate as in a temperature scan in order to determine whether there is any residual

44、enthalpy (i.e. whether any additional reaction occurs). Add this enthalpy to the isothermal value to obtain the total enthalpy of reaction.6DIN EN ISO 11357-5:2014-07 EN ISO 11357-5:2014 (E) 10 Determination of results10.1 Determination of characteristic temperatures and enthalpy of reaction (temper

45、ature-scanning method)See Figure 1. See also ISO 11357-1.KeydQ/dt heat flow rateT temperatureaEndothermic direction.Figure 1 DSC curve with exothermic peak (temperature-scanning method)The temperatures shown in Figure 1 are:Ti,ronset of reaction, corresponding to the point at which the DSC curve dep

46、arts from the initial extrapolated baseline;Tei,rextrapolated onset temperature, corresponding to the point at which the initial extrapolated baseline is intersected by the tangent to the curve at the point of inflection, both on the low-temperature side of the curve;Tp,rmaximum reaction rate, corre

47、sponding to the top of the peak;Tef,rextrapolated end temperature, corresponding to the point at which the final extrapolated baseline is intersected by the tangent to the curve at the point of inflection, both on the high-temperature side of the curve;Tf,rend of reaction, corresponding to the retur

48、n of the DSC curve to the final extrapolated baseline.The enthalpy of reaction Hr, in joules per gram, is obtained by integrating the area between the reaction peak and the interpolated baseline from Ti,rto Tf,r.10.2 Determination of characteristic times and enthalpy of reaction (isothermal method)E

49、ach procedure (9.3.2 and 9.3.3) may require a different length of time for the reaction to begin.Note the time t0,rwhen the specimen reaches temperature equilibrium. Typically, t0,ris the time at which the DSC curve comes back to the isothermal baseline obtained by connecting the horizontal parts 7DIN EN ISO 11357-5:2014-07EN ISO 11357-5:2014 (E)of the DSC curve before and after the isothermal reaction peak. Measure the following times from this