DIN EN ISO 11357-7-2015 Plastics - Differential scanning calorimetry (DSC) - Part 7 Determination of crystallization kinetics (ISO 11357-7 2015) German version EN ISO 11357-7 2015《.pdf

1、December 2015 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 83.080.01!%IS“2389348www.din.de

2、DIN EN ISO 11357-7Plastics Differential scanning calorimetry (DSC) Part 7: Determination of crystallization kinetics (ISO 11357-7:2015);English version EN ISO 11357-7:2015,English translation of DIN EN ISO 11357-7:2015-12Kunststoffe Dynamische Differenz-Thermoanalyse (DSC) Teil 7: Bestimmung der Kri

3、stallisationskinetik (ISO 11357-7:2015);Englische Fassung EN ISO 11357-7:2015,Englische bersetzung von DIN EN ISO 11357-7:2015-12Plastiques Analyse calorimtrique diffrentielle (DSC) Partie 7: Dtermination de la cintique de cristallisation (ISO 11357-7:2015);Version anglaise EN ISO 11357-7:2015,Tradu

4、ction anglaise de DIN EN ISO 11357-7:2015-12SupersedesDIN EN ISO 11357-7:2013-04www.beuth.deDTranslation by DIN-Sprachendienst.In case of doubt, the German-language original shall be considered authoritative.Document comprises 19 pages11.15 DIN EN ISO 11357-7:2015-12 2 A comma is used as the decimal

5、 marker. National foreword This document (EN ISO 11357-7:2015) has been prepared by Technical Committee ISO/TC 61 “Plastics” in collaboration with Technical Committee CEN/TC 249 “Plastics” (Secretariat: NBN, Belgium). The responsible German body involved in its preparation was DIN-Normenausschuss Ku

6、nststoffe (DIN Standards Committee Plastics), Working Committee NA 054-01-03 AA Physikalische, rheologische und analytische Prfungen. EN ISO 11357 consists of the following parts, under the general title Plastics Differential scanning calorimetry (DSC): Part 1: General principles Part 2: Determinati

7、on 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 times, enthalpy of reaction and

8、 degree of conversion Part 6: Determination of oxidation induction time (isothermal OIT) and oxidation induction tempera-ture (dynamic OIT) Part 7: Determination of crystallization kinetics The DIN Standards corresponding to the International Standards referred to in this document are as follows: IS

9、O 472 DIN EN ISO 472 ISO 11357-1 DIN EN ISO 11357-1 ISO 11357-3 DIN EN ISO 11357-3 Amendments This standard differs from DIN EN ISO 11357-7:2013-04 as follows: a) values to be recorded for isothermal crystallization have been revised, the starting time of the isothermal step (t = 0) has been added (

10、10.2.1), and Figures 2 to 6 have been revised accordingly; b) formulae A.1 and A.2 have been corrected; c) dated references have been changed to undated references. Previous editions DIN EN ISO 11357-7: 2013-04 DIN EN ISO 11357-7:2015-12 3 National Annex NA (informative) Bibliography DIN EN ISO 472,

11、 Plastics Vocabulary DIN EN ISO 11357-1, Plastics Differential scanning calorimetry (DSC) Part 1: General principles DIN EN ISO 11357-3, Plastics Differential scanning calorimetry (DSC) Part 3: Determination of temperature and enthalpy of melting and crystallization DIN EN ISO 11357-7:2015-12 4 This

12、 page is intentionally blank EN ISO 11357-7 September 2015 ICS 83.080.01 Supersedes EN ISO 11357-7:2013English VersionPlastics - Differential scanning calorimetry (DSC) -Part 7: Determination of crystallization kinetics(ISO 11357-7:2015)Plastiques - Analyse calorimtrique diffrentielle (DSC) -Partie

13、7: Dtermination de la cintique de cristallisation (ISO 11357-7:2015) Kunststoffe - Dynamische Differenz-Thermoanalyse(DSC) - Teil 7: Bestimmung der Kristallisationskinetik(ISO 11357-7:2015)This European Standard was approved by CEN on 31 July 2015. CEN members are bound to comply with the CEN/CENELE

14、C 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 CEN-CENELEC Management Centre or

15、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 own language and notified to the CEN-CENELEC Management Centre has the same status as the offic

16、ial 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, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands,

17、Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and United Kingdom. CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels 2015 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN ISO

18、 11357-7:2015 EEUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EUROPEAN COMMITTEE FOR STANDARDIZATIONCOMIT EUROPEN DE NORMALISATIONEUROPISCHES KOMITEE FR NORMUNGContents Page Foreword .3 1 Scope .4 2 Normative references4 3 Terms and definitions .4 4 Principle .5 5 Apparatus and materials5 6 Test

19、specimens 5 7 Test conditions and specimen conditioning .5 8 Calibration .5 9 Procedure 5 9.1 General 5 9.2 Loading the test specimen into the crucible . 6 9.3 Insertion of the crucibles into the instrument . 6 9.4 Melting of the polymer . 6 9.5 Isothermal crystallization . 6 9.6 Non-isothermal crys

20、tallization . 7 10 Expression of results .8 10.1 General 8 10.2 Methods of determination of crystallization kinetics . 8 10.2.1 Isothermal crystallization 8 10.2.2 Non-isothermal crystallization . 10 11 Precision . 11 12 Test report . 11 Annex A (informative) Equations for crystallization kinetics o

21、f polymers . 12 Bibliography . 14 2DIN EN ISO 11357-7:2015-12 EN ISO 11357-7:2015 (E) European foreword This document (EN ISO 11357-7:2015) 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

22、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 March 2016, and conflicting national standards shall be withdrawn at the latest by March 2016. Attention is drawn to the possibility that some

23、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 11357-7:2013. According to the CEN-CENELEC Internal Regulations, the national standards organizations

24、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, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Ne

25、therlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom. Endorsement notice The text of ISO 11357-7:2015 has been approved by CEN as EN ISO 11357-7:2015 without any modification. “ ”3DIN EN ISO 11357-7:2015-12EN ISO 11357-7:2015 (E)

26、1 ScopeThis part of ISO 11357 specifies two methods (isothermal and non-isothermal) for studying the crystallization kinetics of partially crystalline polymers using differential scanning calorimetry (DSC).It is only applicable to molten polymers.NOTE These methods are not suitable if the molecular

27、structure of the polymer is modified during the test.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 edi

28、tion of the referenced document (including any amendments) applies.ISO 472, Plastics VocabularyISO 11357-1, Plastics Differential scanning calorimetry (DSC) Part 1: General principlesISO 11357-3, Plastics Differential scanning calorimetry (DSC) Part 3: Determination of temperature and enthalpy of me

29、lting and crystallization3 Terms and definitionsFor the purposes of this document, the terms and definitions given in ISO 472, ISO 11357-1, ISO 11357-3, and the following apply.3.1crystallization kineticsdescription of the rate of crystallization of a material taking into account the effects of vari

30、ables such as time, temperature, pressure, stress, and molecular structureNote 1 to entry: These factors and also any additives, fillers, or contaminants can modify the crystallinity of the polymer at the end of crystallization.3.2relative crystallinityratio between the crystallinity at a particular

31、 point in time or a particular temperature and the crystallinity at the end of crystallizationNote 1 to entry: The relative crystallinity can be expressed either as a ratio or as a percentage if multiplied by 100.Note 2 to entry: In DSC, the relative crystallinity can be determined as the ratio betw

32、een the partial area of the crystallization peak, at each time or each temperature, and the total area of the peak.4DIN EN ISO 11357-7:2015-12 EN ISO 11357-7:2015 (E) 4 PrincipleThe principle is specified in ISO 11357-1.5 Apparatus and materials5.1 Differential scanning calorimeter, according to ISO

33、 11357-1.5.2 Crucibles, according to ISO 11357-1.It can be necessary to verify that the material used for the crucibles does not modify the crystallization kinetics of the polymer.5.3 Balance, according to ISO 11357-1.5.4 Calibration materials, according to ISO 11357-1.5.5 Purge gas, according to IS

34、O 11357-1.6 Test specimensTest specimens shall be as specified in ISO 11357-1.7 Test conditions and specimen conditioningTest conditions and specimen conditioning shall be as specified in ISO 11357-1.8 CalibrationThe calibration shall be done in accordance with ISO 11357-1.The linearity of the tempe

35、rature scale in the heating and cooling modes shall be checked using materials which do not supercool. The use of the liquid-liquid transition of liquid crystals, such as 4,4-azoxyanisole, is recommended.9 Procedure9.1 GeneralThe study of the crystallization kinetics of polymers can be done in an is

36、othermal or a non-isothermal mode.5DIN EN ISO 11357-7:2015-12EN ISO 11357-7:2015 (E)The relative crystallinity is given by the ratio of the partial enthalpy of crystallization, at each time or each temperature, and the total enthalpy of crystallization Hc, as given in Formula (1):tT tTHor or c= (1)w

37、heretand Htare the relative crystallinity and the enthalpy of crystallization at a given time in the isothermal mode;Tand HTare the relative crystallinity and the enthalpy of crystallization at a given tempera-ture in the non-isothermal mode.9.2 Loading the test specimen into the crucibleThe loading

38、 of the test specimen shall be done as specified in ISO 11357-1.To avoid self-heating, the mass of the specimen shall be chosen based on the heat evolved by the crystallization of the material. If the object of the measurements is to compare various grades of a polymer, maintain the mass within 0,5

39、mg.9.3 Insertion of the crucibles into the instrumentThe crucibles shall be inserted into the instrument as specified in ISO 11357-1.9.4 Melting of the polymerPrior to isothermal or non-isothermal crystallization, all crystalline elements in the sample that could modify the crystallization kinetics

40、shall be molten completely.This is usually achieved by heating at a rate of 10 K/min or 20 K/min to a temperature of 30 K above the extrapolated end melting temperature and holding at this temperature for 3 min to 5 min.NOTE Preliminary trials can be done to optimize these conditions and to prevent

41、this step from changing the molecular structure of the polymer.9.5 Isothermal crystallizationAt the end of the melting stage, cool the specimen as quickly as possible to the selected temperature at which isothermal crystallization shall be measured.A schematic representation of an isothermal crystal

42、lization run is shown in Figure 2.The time t0, at which the selected temperature is reached, is the start of the isothermal step.Isothermal crystallization starts at initial crystallization time, ti, which is obtained by the intersection point of the slope of the crystallization peak onset with a li

43、near baseline obtained by interpolation between peak start and end.The time tfat which the isothermal step ends (i.e. the time to obtain a complete crystallization curve) depends on the crystallization rate. If not clear from the DSC curve, it shall be set to five times the time taken to reach the m

44、aximum crystallization rate, tmax.Carry out at least three runs at different temperatures.The isothermal temperatures are limited by the specifications of the instrument and data shall be rejected when the crystallization starts during cooling (see Figure 1).NOTE Limiting instrument factors can be e

45、.g. too high thermal lag or insufficient cooling capabilities.6DIN EN ISO 11357-7:2015-12 EN ISO 11357-7:2015 (E) Key1 DSC signal2 temperature plotdQ/dt heat flow ratet timeaExothermic direction.Figure 1 Bad isothermal run: Crystallization started before isothermal temperature reachedKey1 DSC signal

46、2 temperature plotdQ/dt heat flow ratet timeaExothermic direction.Figure 2 Good isothermal run9.6 Non-isothermal crystallizationAt the end of the melting stage, cool the specimen at the selected constant cooling rate to at least 10 K to 20 K below the final crystallization temperature.7DIN EN ISO 11

47、357-7:2015-12EN ISO 11357-7:2015 (E)Carry out at least three runs at different cooling rates.NOTE It is recommended that the cooling rates used are close to the highest rate at which the instrument is able to maintain the rate linear over the whole cooling-temperature range.10 Expression of results1

48、0.1 GeneralSee also ISO 11357-3.NOTE The values calculated in 10.2.1 and 10.2.2 can be used to compare different polymers.The study of the crystallization kinetics of polymers is still evolving and there are many models to describe the kinetics. The literature has to be used for the actual determina

49、tion of the kinetics (see Annex A).10.2 Methods of determination of crystallization kinetics10.2.1 Isothermal crystallizationFor each run at a specific isothermal temperature, determine the variation in as a function of time (t) and record the following values (see Figure 3 and Figure 4): starting time of the isothermal step (t = 0) t0 initial crystallization times ti time to reach the maximum crystallization rate tmax(mea