1、BS ISO 9924-1:2016Rubber and rubber products Determination of thecomposition of vulcanizatesand uncured compounds bythermogravimetryPart 1: Butadiene, ethylene-propylenecopolymer and terpolymer, isobutene-isoprene, isoprene and styrene-butadienerubbersBSI Standards PublicationWB11885_BSI_StandardCov
2、s_2013_AW.indd 1 15/05/2013 15:06BS ISO 9924-1:2016 BRITISH STANDARDNational forewordThis British Standard is the UK implementation of ISO 9924-1:2016. Itsupersedes BS ISO 9924-1:2000 which is withdrawn.The UK participation in its preparation was entrusted to TechnicalCommittee PRI/22, Testing and a
3、nalysis of rubber.A list of organizations represented on this committee can beobtained on request to its secretary.This publication does not purport to include all the necessaryprovisions of a contract. Users are responsible for its correctapplication. The British Standards Institution 2016. Publish
4、ed by BSI StandardsLimited 2016ISBN 978 0 580 92769 0ICS 83.060Compliance with a British Standard cannot confer immunity fromlegal obligations.This British Standard was published under the authority of theStandards Policy and Strategy Committee on 31 July 2016.Amendments issued since publicationDate
5、 Text affectedBS ISO 9924-1:2016 ISO 2016Rubber and rubber products Determination of the composition of vulcanizates and uncured compounds by thermogravimetry Part 1: Butadiene, ethylene-propylene copolymer and terpolymer, isobutene-isoprene, isoprene and styrene-butadiene rubbersCaoutchouc et produ
6、its base de caoutchouc Dtermination de la composition des vulcanisats et des mlanges non vulcaniss par thermogravimtrie Partie 1: Caoutchoucs butadine, copolymres et terpolymres thylne-propylne, isobutne-isoprne, isoprne et butadine-styrneINTERNATIONAL STANDARDISO9924-1Third edition2016-08-01Referen
7、ce numberISO 9924-1:2016(E)BS ISO 9924-1:2016ISO 9924-1:2016(E)ii ISO 2016 All rights reservedCOPYRIGHT PROTECTED DOCUMENT ISO 2016, Published in SwitzerlandAll rights reserved. Unless otherwise specified, no part of this publication may be reproduced or utilized otherwise in any form or by any mean
8、s, electronic or mechanical, including photocopying, or posting on the internet or an intranet, without prior written permission. Permission can be requested from either ISO at the address below or ISOs member body in the country of the requester.ISO copyright officeCh. de Blandonnet 8 CP 401CH-1214
9、 Vernier, Geneva, SwitzerlandTel. +41 22 749 01 11Fax +41 22 749 09 47copyrightiso.orgwww.iso.orgBS ISO 9924-1:2016ISO 9924-1:2016(E)Foreword iv1 Scope . 12 Normative references 23 Principle 24 Reagents 25 Apparatus . 26 Thermogravimetric analyser checks . 37 Procedure. 58 Expression of results 69 P
10、recision . 710 Test report . 7Annex A (informative) Precision . 8Bibliography 9 ISO 2016 All rights reserved iiiContents PageBS ISO 9924-1:2016ISO 9924-1:2016(E)ForewordISO (the International Organization for Standardization) is a worldwide federation of national standards bodies (ISO member bodies)
11、. 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
12、-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.The procedures used to develop this document and those intended for its further maintenance are describ
13、ed in the ISO/IEC Directives, Part 1. In particular the different approval criteria needed for the different types of ISO documents should be noted. This document was drafted in accordance with the editorial rules of the ISO/IEC Directives, Part 2 (see www.iso.org/directives).Attention is drawn to t
14、he possibility that some of the elements of this document may be the subject of patent rights. ISO shall not be held responsible for identifying any or all such patent rights. Details of any patent rights identified during the development of the document will be in the Introduction and/or on the ISO
15、 list of patent declarations received (see www.iso.org/patents).Any trade name used in this document is information given for the convenience of users and does not constitute an endorsement.For an explanation on the meaning of ISO specific terms and expressions related to conformity assessment, as w
16、ell as information about ISOs adherence to the World Trade Organization (WTO) principles in the Technical Barriers to Trade (TBT) see the following URL: www.iso.org/iso/foreword.html.The committee responsible for this document is ISO/TC 45, Rubber and rubber products, SC 2, Testing and analysis.This
17、 third edition cancels and replaces the second edition (ISO 9924-1:2000), of which it constitutes a minor revision with the following changes: precision clause moved to Annex A; NBR-related descriptions removed from Clause 9.ISO 9924 consists of the following parts, under the general title Rubber an
18、d rubber products Determination of the composition of vulcanizates and uncured compounds by thermogravimetry: Part 1: Butadiene, ethylene-propylene copolymer and terpolymer, isobutene-isoprene, isoprene and styrene-butadiene rubbers Part 2: Acrylonitrile-butadiene and halobutyl rubbers Part 3: Hydro
19、carbon rubbers, halogenated rubbers and polysiloxane rubbers after extractioniv ISO 2016 All rights reservedBS ISO 9924-1:2016INTERNATIONAL STANDARD ISO 9924-1:2016(E)Rubber and rubber products Determination of the composition of vulcanizates and uncured compounds by thermogravimetry Part 1: Butadie
20、ne, ethylene-propylene copolymer and terpolymer, isobutene-isoprene, isoprene and styrene-butadiene rubbersWARNING Persons using this part of ISO 9924 should be familiar with normal laboratory practice. This part of ISO 9924 does not purport to address all of the safety problems, if any, associated
21、with its use. It is the responsibility of the user to establish appropriate safety and health practices and to ensure compliance with any national regulatory conditions.1 Scope1.1 This part of ISO 9924 specifies a thermogravimetric method for the determination of the total organic content, carbon bl
22、ack content and ash in vulcanizates and uncured compounds. The loss in mass at 300 C is an approximate guide to the volatile-matter content of the compound.1.2 The method is suitable for the analysis of rubber compounds and vulcanizates containing the following rubbers occurring alone or as mixtures
23、:a) polyisoprene of natural or synthetic origin;b) polybutadiene;c) styrene-butadiene copolymers;d) isobutylene-isoprene copolymers;e) ethylene-propylene copolymers and related terpolymers.NOTE The field of application of the method may be extended to the analysis of compounds containing rubbers dif
24、ferent from those given in this subclause, provided that the applicability of the method is tested beforehand using known compounds or vulcanizates having a similar composition. Other compounds are covered in ISO 9924-2.1.3 The method is not suitable for rubbers containing polymers which form a carb
25、onaceous residue during pyrolysis, such as many chlorine- or nitrogen-containing rubbers.1.4 The method is also not suitable for materials containing additives which cause the formation of carbonaceous residues during pyrolysis, such as cobalt and lead salts or phenolic resins.1.5 The method is not
26、suitable for compounds containing mineral fillers, such as carbonates or hydrated aluminium oxides, which decompose in the temperature range from 25 C to 650 C, unless suitable corrections based on prior knowledge of filler behaviour can be made. ISO 2016 All rights reserved 1BS ISO 9924-1:2016ISO 9
27、924-1:2016(E)1.6 The method is not suitable for the determination of the total polymer content of compounds or vulcanizates containing non-rubber organic ingredients that cannot be completely removed by solvent extraction carried out in accordance with ISO 1407.2 Normative referencesThe following do
28、cuments, 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 edition of the referenced document (including any amendments) applies.ISO 1407, Rubber Determi
29、nation of solvent extract3 Principle3.1 A weighed test portion is heated, following a pre-set programme, from 70 C to 300 C in a stream of nitrogen and is maintained at 300 C for 10 min. The loss in mass indicates, approximately, the total content of non-rubber organic matter volatile at 300 C. In g
30、eneral, this value is not equivalent to the value of the solvent extract.3.2 The oven temperature is then raised to 550 C, still in a stream of nitrogen, and maintained at 550 C for 15 min. The organic matter which was undistilled at 300 C and the polymer distill off, and the loss in mass between 70
31、 C and 550 C represents the total organic matter content.NOTE The total rubber content is calculated by subtracting the value of the solvent extract, determined in accordance with ISO 1407, from the total organic content, provided that all non-rubber ingredients can be extracted.3.3 The oven tempera
32、ture is raised from 550 C to 650 C in a stream of nitrogen, then the gas is changed from nitrogen to air or oxygen, or a mixture of air or oxygen, and the temperature is maintained at 650 C for 15 min or until no further loss in mass is observed. The carbon black is burnt off, and the loss in mass i
33、n the oxidizing atmosphere at 650 C, thus represents the carbon black content. A balanced flow of gas is maintained throughout the changeover to avoid buoyancy effects.3.4 The mass of the residue at 650 C represents the ash.4 Reagents4.1 Dry nitrogen, with an oxygen content of less than 10 mg/kg (pp
34、m).4.2 Dry air or oxygen.5 Apparatus5.1 Thermogravimetric analyser.There are many types of analyser commercially available. All should be suitable for use with this part of ISO 9924, but their suitability should be checked using the procedure in Clause 6. Calibrate and operate the thermogravimetric
35、analyser in accordance with the manufacturers instructions.The basic components of an analyser are as follows.5.1.1 Thermogravimetric balance.5.1.2 Electrically heated, thermo-regulated oven.2 ISO 2016 All rights reservedBS ISO 9924-1:2016ISO 9924-1:2016(E)5.1.3 Temperature programmer, for the oven.
36、5.1.4 Switching device, allowing a stream of nitrogen or a stream of air or oxygen (or a mixture of nitrogen and air or oxygen) to flow through the oven at a predetermined and constant flow rate.5.1.5 X/Y recorder, for recording the temperature/mass plot. Alternatively, temperature/time and mass/tim
37、e plots may be recorded simultaneously using a two-pen Y/T recorder.5.1.6 Auxiliary equipment for producing differential curves (useful but not mandatory for this part of ISO 9924).5.2 Analytical balance, capable of weighing to 0,1 mg.6 Thermogravimetric analyser checks6.1 Measurement of purge time,
38、 tp6.1.1 Place a test portion of carbon black or black-filled rubber, as specified in the manufacturers instructions, in the thermobalance sample pan and heat to 650 C in a stream of nitrogen, at the maximum rate allowed by the temperature programmer.6.1.2 Maintaining the temperature at 650 C, intro
39、duce air or oxygen and allow the test portion to combust fully.6.1.3 When there is no further mass change, switch off the oven heater and allow the oven to cool to room temperature, maintaining the air or oxygen flow. At this point, the oven will have been thoroughly purged with air or oxygen. The f
40、ollowing operations are designed to determine the time, tp, required to completely restore the inert atmosphere of nitrogen.6.1.4 With the oven at 25 C 5 C, introduce a fresh test portion of carbon black, of mass as specified in the manufacturers instructions, into the balance pan and close the appa
41、ratus.6.1.5 Record the time, t1, switch over to nitrogen gas flow, and set the oven temperature to increase to 650 C at as fast a rate as practicable and then remain constant.6.1.6 Observe the thermogravimetric analyser mass trace and, when this no longer indicates a mass loss with time, note the ti
42、me t2.As a check, the pan should still contain carbon black since the mass loss should be constant if not all the carbon black has burned off during the heating time.6.1.7 The purge time, tp, which is the time required to purge all oxygen from the system, is given by Formula (1):tp= t2 t1(1)6.2 Disc
43、rimination between carbon black and calcium carbonate6.2.1 Calcium carbonate will decompose to calcium oxide when heated to 800 C. Carbon black is thermally stable up to this temperature in a nitrogen atmosphere. In air or oxygen, however, carbon black will be oxidized to carbon dioxide at 800 C. IS
44、O 2016 All rights reserved 3BS ISO 9924-1:2016ISO 9924-1:2016(E)6.2.2 Provided that nitrogen having a low enough concentration of oxygen is used, that purging is carried out for a time greater than the purge time determined in 6.1, that there are no leaks in the apparatus, and that the oven design a
45、nd gas flow rate ensure that all carbon dioxide is swept out from the sample chamber, there should be no problem in distinguishing between, and measuring separately, black and whiting (calcium carbonate). To check the operation of the thermogravimetric analyser, carry out the following procedure:6.2
46、.3 Grind together equal (to within 1 %) masses of analytical-grade calcium carbonate and the purest grade of carbon black available.6.2.4 Purge the apparatus with nitrogen for 10 min beyond the purge time, tp.6.2.5 Switch on the recorder and set the oven temperature to 25 C 5 C.6.2.6 Into the thermo
47、gravimetric analyser balance pan, introduce a mass of the carbon black/calcium carbonate mixture (see 6.2.3) as specified in the manufacturers instructions.6.2.7 Close the apparatus and purge with a stream of nitrogen at a constant and predetermined flow rate which is in accordance with the manufact
48、urers instructions. Continue purging with nitrogen for a time which is greater than the purge time, tp(see 6.1).6.2.8 Raise the oven temperature to 800 C at a rate of 10 C/min.6.2.9 Maintain the oven temperature at 800 C until the mass indicated on the mass/temperature (or mass/time) plot is constan
49、t, then lower the temperature to 300 C.6.2.10 Switch from the stream of nitrogen to a stream of air or oxygen, or partly replace the nitrogen by air or oxygen. Adjust the total flow rate of the gas flowing through the apparatus so that there is no discernible change in the apparent mass of the sample. This procedure corrects for changes in buoyancy of the balance pan and test portion in gases of different density.6.2.11 Raise the oven temperature to 800 C as rapidly as possible and mai
