1、BSI Standards PublicationBS ISO 16565:2013Rubber Determination of 5-ethylidenenorbornene (ENB)or dicyclopentadiene (DCPD)in ethylene-propylene-diene(EPDM) terpolymersBS ISO 16565:2013 BRITISH STANDARDNational forewordThis British Standard is the UK implementation of ISO 16565:2013. Itsupersedes BS I
2、SO 16565:2008 which is withdrawn.The UK participation in its preparation was entrusted to TechnicalCommittee PRI/23, Test methods for rubber and non-blackcompounding ingredients.A list of organizations represented on this committee can beobtained on request to its secretary.This publication does not
3、 purport to include all the necessaryprovisions of a contract. Users are responsible for its correctapplication. The British Standards Institution 2013. Published by BSI StandardsLimited 2013ISBN 978 0 580 78995 3ICS 83.060Compliance with a British Standard cannot confer immunity fromlegal obligatio
4、ns.This British Standard was published under the authority of theStandards Policy and Strategy Committee on 31 July 2013.Amendments issued since publicationDate Text affectedBS ISO 16565:2013 ISO 2013Rubber Determination of 5-ethylidenenorbornene (ENB) or dicyclopentadiene (DCPD) in ethylene-propyle
5、ne-diene (EPDM) terpolymersCaoutchouc Dtermination du 5-thylidnenorbornne (ENB) ou du dicyclopentadine (DCPD) dans les terpolymers dthylne-propylne-dine (EPDM)INTERNATIONAL STANDARDISO16565Third edition2013-05-15Reference numberISO 16565:2013(E)BS ISO 16565:2013ISO 16565:2013(E)ii ISO 2013 All right
6、s reservedCOPYRIGHT PROTECTED DOCUMENT ISO 2013All rights reserved. Unless otherwise specified, no part of this publication may be reproduced or utilized otherwise in any form or by any means, electronic or mechanical, including photocopying, or posting on the internet or an intranet, without prior
7、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 officeCase postale 56 CH-1211 Geneva 20Tel. + 41 22 749 01 11Fax + 41 22 749 09 47E-mail copyrightiso.orgWeb www.iso.orgPublished in SwitzerlandBS IS
8、O 16565:2013ISO 16565:2013(E) ISO 2013 All rights reserved iiiContents PageForeword iv1 Scope . 12 Principle 13 Apparatus . 14 Test specimen preparation 24.1 Primary method . 24.2 Alternative method . 24.3 Alternative method for liquid polymer film preparation . 25 Acquisition of spectra 35.1 With a
9、 specimen shuttle . 35.2 Without a specimen shuttle . 36 Calibration of the spectrophotometer . 37 Diene determination 47.1 Preparation 47.2 Single absorbance spectrum . 47.3 Determination of film thickness 47.4 Determination of diene content . 48 Precision . 89 Test report . 9Annex A (normative) Pr
10、ocedure for spectral subtraction of water vapour 10Annex B (informative) Precision and bias .12Bibliography .14BS ISO 16565:2013ISO 16565:2013(E)ForewordISO (the International Organization for Standardization) is a worldwide federation of national standards bodies (ISO member bodies). The work of pr
11、eparing 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-governmental, i
12、n 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 described in the ISO/IE
13、C 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. www.iso.org/directivesAttention is drawn to the possibility that so
14、me 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 list of patent declar
15、ations received. www.iso.org/patentsAny trade name used in this document is information given for the convenience of users and does not constitute an endorsement.The committee responsible for this document is ISO/TC 45, Rubber and rubber products, Subcommittee SC 2, Testing and analysis.This third e
16、dition cancels and replaces the second edition (ISO 16565:2008), of which it constitutes a minor revision. The main changes are: a correction to the Scope concerning the range of termonomer content (either ENB or DCPD) to be determined and the locations of points A and B on Figure 1.iv ISO 2013 All
17、rights reservedBS ISO 16565:2013INTERNATIONAL STANDARD ISO 16565:2013(E)Rubber Determination of 5-ethylidenenorbornene (ENB) or dicyclopentadiene (DCPD) in ethylene-propylene-diene (EPDM) terpolymersWARNING Persons using this International Standard should be familiar with normal laboratory practice.
18、 This International Standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this International Standard to establish appropriate safety and health practices and to ensure compliance with any national regulatory conditi
19、ons.1 ScopeThis International Standard specifies the methods to be used to determine the content of 5-ethylidenenorbornene (ENB) or dicyclopentadiene (DCPD) in ethylene-propylene-diene (EPDM) terpolymers in the 0,1 % to 10 % range.ENB and DCPD are dienes introduced into ethylene-propylene rubbers to
20、 generate specific cure properties. Since high precision for diene content determination is important, a Fourier transform infrared spectroscopic (FT-IR) method is utilized.NOTE The procedures for the mass fraction of ENB and the mass fraction of DCPD differ only in the location in the infrared (IR)
21、 of the peak being quantified.2 PrincipleA test specimen is moulded between two PTFE-coated aluminium or mylar sheets. The ENB content is determined from its infrared absorbance at 1 681 cm1to 1 690 cm1(a measure of the exocyclic double bond in ENB). The DCPD content is determined from its infrared
22、absorbance at 1 605 cm1to 1 610 cm1(a measure of the monocyclic double bond in DCPD).The second derivative of the absorbance is calculated and ratioed to an internal standard. For ENB, the resulting second-derivative peak near 1 690 cm1is related to the ENB mass fraction by calibrating the instrumen
23、t with known EPDM standards. For DCPD, the resulting second-derivative peak near 1 610 cm1is related to the DCPD mass fraction in the same way.For oil-extended polymers, the oil shall be extracted before the diene content is determined.3 Apparatus3.1 Carver-type press, capable of compressing films a
24、t 150 C and 10 MPa.3.2 Mould.3.2.1 The mould primarily used is made of a stainless-steel strip 400 m thick with an opening, which gives a specimen of the appropriate size for the specimen-film holder described in 3.4 (2 cm by 2 cm). The mould shall have approximately the same dimensions as the press
25、 platens.3.2.2 Alternatively, a thinner mould plate may be used. However, precision can be adversely affected at low diene levels. The precision of the method shall be determined when thinner films are utilized. For example, 127 m-thick stainless-steel foil with a 15 mm by 35 mm opening may be used
26、for the simultaneous determination of ethylene and diene. ISO 2013 All rights reserved 1BS ISO 16565:2013ISO 16565:2013(E)3.2.3 For liquid EPDMs, a ring washer of 22 mm outer diameter by 16 mm inner diameter and 400 m-thick is used as a spacer between salt plates (NaBr, NaCl) to set a fixed path len
27、gth. The spacer is sized to cover only the outer edge of the salt plates.3.3 PTFE-coated aluminium moulding sheets, type A, 36 m thick, or silicone release sheeting.3.4 Specimen-film holders: films may be moulded, cut out and transferred to a film holder. Magnetic-film holders are ideal. Alternative
28、ly, a mould sized to fit in the spectrophotometer specimen compartment, with an appropriate-sized opening, may be used to support the film without removal after compressing. A standard salt plate support is used for liquid samples prepared between salt plates.3.5 Infrared Fourier transform spectroph
29、otometer, capable of measuring absorbances in the range of 4 000 cm1to 600 cm1with a transmittance specification (accuracy) of 1 % T or better. The instrument shall be capable of spectral resolution of 2 cm1. A deuterated triglycine sulfate (DTGS) or, as an alternative, a mercury cadmium telluride (
30、MCT) detector shall be used.NOTE A specification for the evaluation of the analysis of infrared spectra is given in Reference.1The instrument shall be capable of spectral accumulation, averaging and subtracting. Water is the primary source of interference in this method. Methods, physical and electr
31、onic, which minimize the moisture level and moisture-level variation are required to obtain the highest precision. The preferred method is to use an instrument equipped with a dry-gas purge and specimen shuttle, which permits alternating and repetitive collection of single-beam specimen and backgrou
32、nd spectra (see Clause 5). Alternatively, should a specimen shuttle be unavailable, careful purging of the specimen compartment with dry nitrogen can yield satisfactory results. High precision of calibration-standard data is indicative of adequate purging. When moisture interference is not removed b
33、y purging, spectral subtraction of water vapour may be used. A procedure for further development of the method is described in Annex A.4 Test specimen preparation4.1 Primary methodPlace 0,20 g 0,05 g of the material to be analysed between two sheets (see 3.3) in the mould (see 3.2.1). Place the moul
34、d between the press platens heated to 125 C 5 C and apply 4 MPa pressure for 60 s 10 s.Should the material be highly viscous, the mould may be heated to 175 C 5 C.Cool the material to ambient temperature. Cut out a piece of film of approximately 15 mm by 50 mm. Detach the specimen film from the shee
35、ts (see 3.3), and position it on the spectrophotometer specimen compartment window.4.2 Alternative methodWhen using the thinner mould described in 3.2.2, place a small piece (0,04 g to 0,06 g) of the material to be analysed in the mould opening between two sheets (see 3.3) and compress as in 4.1. Re
36、move the mould from the press, turn it over and compress it again. Then, remove the mould from the press and allow it to cool to ambient temperature. When cool, carefully remove the sheets (see 3.3), allowing the specimen film to remain attached to the mould.4.3 Alternative method for liquid polymer
37、 film preparationPlace a washer (see 3.2.3) on top of a salt plate. Place a small amount (about 0,3 g) of the liquid EPDM polymer to be analysed in the centre of the washer, filling the hole completely. Place a second salt plate on top of the filled washer. Gently place a 1 kg weight on top of the s
38、alt plate/washer assembly and allow the weighted assembly to sit for 2 min to 3 min. (For viscous samples, it may be necessary to warm the sample prior to compressing.) Remove the 1 kg weight and, if necessary, allow to cool. Wipe off any excess material that might have been pressed out of the assem
39、bly. Hold the assembly up to the light and 2 ISO 2013 All rights reservedBS ISO 16565:2013ISO 16565:2013(E)inspect for bubbles and/or voids. Should there be imperfections, repeat the preparation with a larger amount of material.5 Acquisition of spectra5.1 With a specimen shuttle5.1.1 The data-acquis
40、ition parameters shall be: resolution: 2 cm1; scans/scan time: total scan time, split between specimen scans and background scans, about 90 s.5.1.2 Place the test specimen in the specimen compartment, allow purge to be re-established and, in alternating fashion, collect single-beam specimen and empt
41、y specimen compartment spectra. Eight passes of the shuttle shall be made (eight specimen and eight empty-compartment collections), collecting four scans at each position.5.1.3 Calculate the specimen absorbance spectrum as log10of the ratio of the accumulated single-beam specimen to the empty-compar
42、tment spectrum using Formula (1):A = log10(P/P0) (1)whereA is the absorbance of the specimen at a given wavelength;P0is the empty specimen compartment light-beam intensity at that wavelength;P is the single-beam specimen light-beam intensity at that wavelength.5.2 Without a specimen shuttle5.2.1 The
43、 data-acquisition parameters shall be: resolution: 2 cm1; scans/scan time: background scans: 32 scans, 120 s total; specimen scans: 32 scans, 120 s total.5.2.2 Establish a dry atmosphere inside the empty specimen compartment and collect the empty specimen compartment spectra.5.2.3 Place the test spe
44、cimen in the specimen compartment and re-establish a dry atmosphere inside the compartment. Collect the single-beam specimen spectra and calculate the specimen absorption spectrum as described in 5.1.3.6 Calibration of the spectrophotometer6.1 Obtain a series of known standards covering the diene co
45、ntent range 0 % to 10 %. Calibration may be based on secondary standards qualified by other laboratories using this method or, more generally, by primary standards whose diene content is well known. Primary standards may be established via use of proton nuclear magnetic resonance (1H-NMR), in conjun
46、ction with other techniques. The ENB ISO 2013 All rights reserved 3BS ISO 16565:2013ISO 16565:2013(E)calibration standards1)employed in the development of this method were determined by a combination of refractive index and H-NMR (utilizing samples dissolved in deuterated o-dichlorobenzene at 120 C;
47、 the ENB assignment was based exclusively on the exocyclic olefinic protons of ENB). The DCPD standards1)were determined by a similar H-NMR technique involving the cyclic olefinic protons of DCPD. The use of four standards at the (copolymer) 2 %, 5 % and 10 % levels is the minimum recommended.6.2 Us
48、ing the procedure in Clause 5, acquire a minimum of five absorbance spectra for each of the calibration standards described in 6.1. Several repetitions on separate specimens of each standard may be averaged to improve the accuracy of the calibration.6.3 Using the procedure in Clause 7, calculate the
49、 ratio of the second-derivative diene peak height to the internal thickness gauge for each of the spectra acquired.6.4 Calculate a linear calibration line (diene peak ratio versus assigned values of the standards as mass fraction in per cent of diene) by computing a slope and intercept using standard least-squares linear-regression techniques.7 Diene determination7.1 PreparationPrepare the specimen film as described in Clause 4.7.2 Single absorbance spectrumCollect a single absorbance spectru
