BS EN ISO 11409-1998 Plastics - Phenolic resins - Determination of heats and temperatures of reaction by differential scanning calorimetry《塑料 酚醛树脂 差示扫描量热法测定反应热和反应温度》.pdf

1、BRITISH STANDARD BS EN ISO 11409:1998 Plastics Phenolic resins Determination of heats and temperatures of reaction by differential scanning calorimetry The European Standard EN ISO 11409:1998 has the status of a BritishStandard ICS 83.080.10BSENISO11409:1998 This British Standard, having been prepar

2、ed under the directionof the Sector Board forMaterials and Chemicals, waspublished under the authorityofthe Standards Boardand comes into effect on 15November1998 BSI 05-1999 ISBN 0 580 30271 7 National foreword This British Standard is the English language version of EN ISO 11409:1998. It is identi

3、cal with ISO 11409:1993. The UK participation in its preparation was entrusted to Technical Committee PRI/42, Fibre reinforced thermosetting plastics and prepregs, which has the responsibility to: aid enquirers to understand the text; present to the responsible international/European committee any e

4、nquiries 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 Atte

5、ntion 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

6、 may be found in the BSI Standards Catalogue under the section entitled “International Standards Correspondence Index”, or by 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 Briti

7、sh 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, theEN ISO title page, page 2, the ISO title page, p

8、age ii, pages 1 to 6, 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. Date CommentsBSENISO11409:1

9、998 BSI 05-1999 i Contents Page National foreword Inside front cover Foreword 2 Foreword ii Text of ISO 11409 1ii blankEUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN ISO 11409 August 1998 ICS Descriptors: See ISO document English version Plastics Phenolic resins Determination of heatsandtemper

10、atures of reaction by differentialscanningcalorimetry (ISO 11409:1993) Plastiques Rsines phnoliques Dtermination des chaleurs et tempratures de raction par calorimtrie diffrentielle balayage (ISO 11409:1993) Kunststoffe Phenolharze Bestimmung der Reaktionswrmen und -temperaturen durch dynamische Dif

11、ferenzkalorimetrie (ISO11409:1993) This European Standard was approved by CEN on 13 June 1998. 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-da

12、te lists and bibliographical references concerning such national standards may be obtained on application to the Central Secretariat 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

13、 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, CzechRepublic, Denmark, Finland, France, Germany, Greece, Iceland, Ireland, Italy, Luxembourg

14、, Netherlands, Norway, Portugal, Spain, Sweden, Switzerland and United Kingdom. CEN European Committee for Standardization Comit Europen de Normalisation Europisches Komitee fr Normung Central Secretariat: rue de Stassart 36, B-1050 Brussels 1998 CEN All rights of exploitation in any form and by any

15、 means reserved worldwide for CEN nationalMembers. Ref. No. EN ISO 11409:1998 EENISO11409:1998 BSI 05-1999 2 Foreword The text of the International Standard from Technical Committee ISO/TC 61 “Plastics” of the International Organization for Standardization (ISO) has been taken over as an European St

16、andard by 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 February 1999, and conflicting national standards shal

17、l be withdrawn at the latest by February 1999. According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, CzechRepublic, Denmark, Finland, France, Germany, Greece, Iceland, Irelan

18、d, Italy, Luxembourg, Netherlands, Norway, Portugal, Spain, Sweden, Switzerland and the United Kingdom. Endorsement notice The text of the International Standard ISO11409:1993 has been approved by CEN as a European Standard without any modification. NOTENormative references to International Standard

19、s are listed in Annex ZA (normative). Contents Page Foreword 2 1 Scope 1 2 Normative references 1 3 Definitions 1 4 Test method 1 Annex A (informative) Bibliography Inside back cover Annex ZA (normative) Normative references to international publications with their relevant European publications Ins

20、ide back cover Figure 1 Recommended design of sampleholder 3 Figure 2 Baseline construction and reaction temperatures for a phenolic novolak 4 Figure 3 Baseline construction and reaction temperatures for a phenolic resol 5ENISO11409:1998 ii BSI 05-1999 Foreword ISO (the International Organization fo

21、r 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

22、 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 Int

23、ernational 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 11409 was prepared by Technical Committee ISO/TC 61, Pla

24、stics, Sub-Committee SC 12, Thermosetting materials. Later, this International Standard will become part of a general standard concerning differential scanning calorimetry. Annex A of this International Standard is for information only. Descriptors: Plastics, thermosetting resins, phenoplasts, chemi

25、cal reactions, tests, determination, heat, temperature, calorimetry.ENISO11409:1998 BSI 05-1999 1 1 Scope 1.1 This International Standard specifies a method for the determination of heats and temperatures of reaction of phenolic resins by differential scanning calorimetry. 1.2 The method is applicab

26、le to phenolic resins with exothermic behaviour, such as resols or mixtures of novolaks with hexamethylenetetramine or other curing agents. 1.3 The method is useful for the characterization of products and for research. 2 Normative references The following standards contain provisions which, through

27、 reference in this text, constitute provisions of this International Standard. At the time of publication, the editions indicated were valid. All standards are subject to revision, and parties to agreements based on this International Standard are encouraged to investigate the possibility of applyin

28、g the most recent editions of the standards indicated below. Members of IEC and ISO maintain registers of currently valid International Standards. ISO 472:1988, Plastics Vocabulary. ISO 5725:1986, Precision of test methods Determination of repeatability and reproducibility for a standard test method

29、 by inter-laboratory tests. ISO 10082:1991, Plastics Phenolic resins Definitions and test methods. 3 Definitions For the purposes of this International Standard, the following definitions apply. 3.1 differential scanning calorimetry (DSC) a technique whereby the difference in energy absorbed or rele

30、ased by a polymer and by a reference material is measured as a function of temperature and/or time while the polymer and the reference are subjected to the same temperature schedule 3.2 phenolic resin generally, a class of resins made by polycondensation of phenol, its homologues and/or derivatives,

31、 with aldehydes or ketones. ISO 472 3.3 novolaks non-self-curing, soluble, fusible phenolic resins that remain stable when stored, the phenol nuclei of which are linked primarily by methylene bridges. Novolaks can be made to react further and crosslink by the addition of hardeners; heating is also u

32、sually necessary. ISO10082 see also novolak in ISO472 3.4 resols soluble, fusible phenolic resins which, in contrast to novolaks, contain methylol groups and methylene-ether and sometimes also methylene-amine bridges. Resols are self-curing; they crosslink into insoluble products when heated and/or

33、mixed with catalysts, without addition of further reaction components. Resols are perishable and can be stored for a limited time only ISO10082 see also resol in ISO472 NOTE 1In this document, the term “heat” and “heat of reaction” used throughout the text are equivalent to the terms “enthalpy” and

34、“enthalpy of reaction”. 4 Test method 4.1 Principle The heat flux (power) supplied to a test sample is measured as a function of time or temperature, while the test sample is subjected to a temperature schedule under a specified atmosphere. In practice, what is measured is the difference between the

35、 heat flux supplied to a sample holder containing the test sample and the heat flux supplied to a reference holder. A reaction is marked by the release of energy from the sample, resulting in an exothermic peak in the heating curve. Integration of the recorded peak area as a function of time gives a

36、 measure of the energy of the reaction. Observing the position of the reaction on the temperature axis provides the necessary temperature information. 4.2 Materials 4.2.1 Indium, for calibration of the apparatus (see4.5.1).ENISO11409:1998 2 BSI 05-1999 4.3 Apparatus 4.3.1 Differential scanning calor

37、imeter, having the following characteristics: a) heating or cooling rate of up to10 C/min; b) automatic recording of differential heat flow between the sample and reference material; c) sensitivity for measurement of heat flux or energy difference such that a precision of 1% is ensured; d) time-base

38、 precision of 1% over the time-base range from0,1min/cm to2,0min/cm (10,0cm/min to0,5cm/min) on the chart; e) temperature sensitivity such that the sample temperature is readable to at least 0,1 C; f) operating range preferably from20 C to300 C. 4.3.2 Area-measurement device, with an accuracyof 0,1%

39、. 4.3.3 Pressure-tight sample holders, inert to the test material, of high thermal conductivity, for example steel capsules, pressure-tight to at least2MPa 1)(see recommended design in Figure 1). NOTE 2If a differential scanning calorimeter with a high-pressure calorimeter cell is used, normal sampl

40、e holders should be used. 4.3.4 Analytical balance, preferably accurateto0,01mg. 4.4 Preparation of test samples 4.4.1 Since small quantities of materials are used, it is essential that test samples be representative of the material. 4.4.2 Prepare test samples of powdered or granular resins by remov

41、ing portions from various parts of the batch. Mix these thoroughly to ensure a representative test sample for the determination. Grind coarse granular materials with a device that does not generate heat to reduce the grain size and give a more uniform mixture. If not already present in the resin, ad

42、d the required amount of hexamethylenetetramine before grinding. 4.4.3 Unless otherwise specified, analyse samples as received. If the sample is heated prior to analysis, note this in the test report. Record any loss in mass as a result of the heat treatment. 4.5 Procedure Resins release volatile ma

43、tter on heating. Therefore phenolic resins must be analysed in hermetically sealed pressure-tight sample holders. 4.5.1 Calibration Carry out the calibration of the apparatus with respect to heat flux or energy difference, time base and heat axis following the apparatus manufacturers instructions, u

44、sing either an electrical method or a reference material, on each side of the reaction temperature. SeeAnnex A, references 1 and 2. 4.5.2 Determination 4.5.2.1 Select the appropriate heat-flow-axis sensitivity on the recorder to yield a25% to95% deflection on the recorder. NOTE 3A preliminary run us

45、ing a similar specimen may be made to provide this information. 4.5.2.2 If a recorder is used, select the appropriate scales for time and temperature on the recorder to yield an area of30cm 2to60cm 2 . 4.5.2.3 Start at a temperature at least30 C below the beginning of the reaction. 4.5.2.4 Into a cl

46、ean sample holder (4.3.3), weigh10mg2mg of sample to an accuracy of0,05mg using the balance (4.3.4). 4.5.2.5 Seal the sample holder so that it is pressure-tight. 4.5.2.6 Place the sample holder in the calorimeter(4.3.1). If specified by the manufacturer of the instrument, purge both chambers with pu

47、rge gas at the rate recommended. Typical rates are in the range10ml/min to50ml/min. 4.5.2.7 Heat the test sample preferably at5 C 1 C per minute. Other heating rates may be used, but shall be noted in the test report. Record the thermal curve which results. Reweigh the test sample on completion of s

48、canning. Discard the results if the mass loss exceeds 10% of the original mass of the test sample (see4.5.2.4). 4.5.2.8 Carry out determinations on at least two test samples, and report the average value of temperature and heat of each reaction. 4.5.3 Calculation 4.5.3.1 Calculation of heat of react

49、ion 4.5.3.1.1 On the time-based curve, construct a baseline by connecting the two points of the curve at which the curve deviates from the baseline (seeFigure 2 and Figure 3). 1) 2MPa =20bar Reference material Melting point Heat of fusion ( C) (J/g) Indium 156,6 28,42 0,36ENISO11409:1998 BSI 05-1999 3 Figure 1 Recommended design of sample holderENISO11409:1998 4 BSI 05-1999 Figure 2 Baseline construction and reaction temperatures for a phenolic novolakENISO11409:1998 BSI 05-1999 5 Figur