1、BSI Standards PublicationEuropean certified reference materials (EURONORM-CRMs) for the determination of thechemical composition of iron and steel products prepared under the auspices of theEuropean Committee for Iron and Steel Standardization (ECISS)PD CEN/TR 10317:2014National forewordThis Publish
2、ed Document is the UK implementation of CEN/TR 10317:2014.It supersedes PD CEN/TR 10317:2013 which is withdrawn.The UK participation in its preparation was entrusted to TechnicalCommittee ISE/102, Methods of Chemical Analysis for Iron and Steel.A list of organizations represented on this committee c
3、an be obtained onrequest to its secretary.This publication does not purport to include all the necessary provisions ofa contract. Users are responsible for its correct application. The British Standards Institution 2014.Published by BSI Standards Limited 2014ISBN 978 0 580 84752 3ICS 71.040.30; 77.1
4、50.10Compliance with a British Standard cannot confer immunity fromlegal obligations.This Published Document was published under the authority of theStandards Policy and Strategy Committee on 31 December 2014.Amendments/corrigenda issued since publicationDate Text affectedPUBLISHED DOCUMENTPD CEN/TR
5、 10317:2014TECHNICAL REPORT RAPPORT TECHNIQUE TECHNISCHER BERICHT CEN/TR 10317 November 2014 ICS 71.040.30; 77.150.10 Supersedes CEN/TR 10317:2013English Version European certified reference materials (EURONORM-CRMs) for the determination of the chemical composition of iron and steel products prepar
6、ed under the auspices of the European Committee for Iron and Steel Standardization (ECISS) Matriaux de rfrence certifis europens (EURONORM-MRC) destins la dtermination de la composition chimique des produits en acier et en fonte prpars sous les auspices du comit europen de normalisation du fer et de
7、 lacier (ECISS) Europische zrtifert Refrnzmateriln (EURONORM-ZRMs) fr die Bestimmung der chemischen Zusammensetzung von Eisen- und Stahlerzeugnissen, hergestellt unter der Schirmherrschaft des Europischen Komitees fr Eisen- und Stahlnormung (ECISS) This Technical Report was approved by CEN on 10 May
8、 2014. It has been drawn up by the Technical Committee ECISS/TC 102. 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, Ita
9、ly, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG CEN-CENELEC Management Centre: Ave
10、nue 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. CEN/TR 10317:2014 ECEN/TR 10317:2014 (E) 2 Contents Page Foreword 3 Introduction .4 1 Scope 5 2 Classification of EURONORM-CRMs .5 3 Preparation of th
11、e samples .6 3.1 EURONORM-CRMs of cast and wrought materials 6 3.2 EURONORM-CRMs of non-metallic materials 6 4 Certification 7 4.1 Main rules .7 4.2 Main content of the certificates 7 5 Sample presentation .9 6 Distribution of EURONORM-CRMs 9 7 Details of current EURONORM-CRMs 10 Bibliography . 11 P
12、D CEN/TR 10317:2014CEN/TR 10317:2014 (E) 3 Foreword This document (CEN/TR 10317:2014) has been prepared by Technical Committee ECISS/TC 102 “Methods of chemical analysis for iron and steel”, the secretariat of which is held by SIS. Attention is drawn to the possibility that some of the elements of t
13、his 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 CEN/TR 10317:2013. In comparison with the previous edition, CEN/TR 10317:2013, significant technical changes were made to the int
14、roduction and Clause 5 following the withdrawal of Bureau of Analysed Samples Limited from the Euronorm-CRM Producers Group in 2013. PD CEN/TR 10317:2014CEN/TR 10317:2014 (E) 4 Introduction ln accordance with the definition in ISO Guide 30, Amendment 1:2008, a Certified Reference Material (CRM) as d
15、escribed in this CEN Technical Report is a “reference material characterized by a metrologically valid procedure for one or more specified properties, accompanied by a certificate that provides the value of the specified property, its associated uncertainty, and a statement of metrological traceabil
16、ity”. Furthermore, it is accompanied by a certificate issued by the producing organization on behalf of the Co-ordinating Committee (COCOR) of ECISS after approval by the participating laboratories and all the producing organizations: a) France: 1) ArcelorMittal Maizires Research SA (AMMZ) former In
17、stitut de Recherches de la Sidrurgie Franaise (IRSID), 2) Centre Technique des Industries de la Fonderie (CTIF); b) Germany: Iron and Steel CRM Working Group (AGZRM) comprising: 1) BAM Bundesanstalt fr Materialforschung und -prfung, 2) Max-Planck-Institut fr Eisenforschung (MPI), 3) Stahlinstitut VD
18、Eh; c) Nordic Countries: Nordic CRM Working Group, (NCRMWG) comprising: 1) Swerea KIMAB former Swedish Institute for Metals Research (SIMR), 2) Jernkontoret. NOTE Bureau of Analysed Samples Ltd (BAS) - United Kingdom was a member of the EURONORM-CRM Producers Group from 1975 until 2013. Since 1968,
19、EURONORM-CRMs have been analysed by laboratories in most countries in the European Union (EU) or former European Community (EC). Pending their eventual replacement by EURONORM-CRMs, a number of former national CRMs prepared, analysed and certified by laboratories in Germany, France and the United Ki
20、ngdom respectively, were accepted as EURONORM-CRMs after their accuracy had been checked by other European laboratories. This procedure ceased in 1990. PD CEN/TR 10317:2014CEN/TR 10317:2014 (E) 5 1 Scope This Technical Report describes the classification, method of sample preparation, certification
21、main rules and certificate content of the EURONORM-CRMs. It also details the sample presentation of the various producers organizations and the distributing sources. 2 Classification of EURONORM-CRMs EURONORM-CRMs, prepared under the auspices of ECISS, are classified into two main groups: cast and w
22、rought materials: irons, steels, special alloys and ferro-alloys; non-metallic materials: raw materials (ores, concentrates, additives and refractories) and by-products (slags, dusts and similar materials). Besides this first generic classification, EURONORM-CRMs are grouped into the following categ
23、ories: a) From 001 to 099 high purity irons and unalloyed steels Normally no element has a content (mass fraction) greater than the limit values in the following list: 1) silicon, limit value 1,0 %; 2) manganese, limit value 1,5 %; 3) chromium and nickel, limit value for each 0,5 %; 4) cobalt, coppe
24、r and tungsten, limit value for each 0,3 %; 5) other elements, limit value for each 0,1 %; 6) boron, carbon, phosphorus, lead and sulphur, no limit value. b) From 101 to 199 low alloy steels The content of one or more elements is greater than the limit given for unalloyed steels but none exceeds 5 %
25、. The sum of these alloying elements remains under 10 %. c) From 201 299 highly alloyed steels The content of one or more elements is greater than 5 % or the sum of all these alloying elements is at least 10 %. Nevertheless the iron content will normally be greater than 50 %. d) From 301 to 399 - sp
26、ecial alloys The iron content is less than 50 %. e) From 401 to 499 pig irons and cast irons f) From 501 to 599 ferro-alloys g) From 601 to 699 ores, concentrates, sinters and miscellaneous materials h) From 701 to 799 additives and refractories PD CEN/TR 10317:2014CEN/TR 10317:2014 (E) 6 i) From 80
27、1 to 899 by-products, such as slags, dusts and similar materials The expression “-1” after a CRM number refers to the first issue of this CRM and “-2”, “-3”, etc. refer to replacement CRMs of generally similar composition, but not to a further bottling of the original CRM. NOTE This classification i
28、s used as a simple and convenient method of differentiating between samples of different types of materials. It has no other objective and does not replace existing European or International product specifications for metallic materials. 3 Preparation of the samples 3.1 EURONORM-CRMs of cast and wro
29、ught materials 3.1.1 High purity irons, steels and special alloys The material is obtained as cylindrical, square or rectangular billets or slabs. After the homogeneity has been verified, it is machined dry (avoiding excessive heat generation) on a suitable lathe or milling machine in order to produ
30、ce short chips; the chips are screened so that the fines can be removed. Some steel samples are produced by atomisation of the liquid metal. The whole preparation process provides a batch of generally more than 100 kg. This is blended in a cylindrical or cube shaped mixer before certification analys
31、is. Samples supplied in disc form are prepared from the most homogeneous parts of the rolled or forged material. If the finely divided sample is prepared by atomisation of the liquid metal, disc samples may be prepared by hot isostatic pressing of the powder. This process has been used where it is d
32、ifficult to obtain homogeneous solid material for spectrometric analysis by casting or forging. In all cases it is verified that the solid and finely divided samples are identical in chemical composition. 3.1.2 Pig irons and cast irons The metal in the form of solid or hollow cylinders is descaled;
33、its homogeneity is verified and then it is dry machined on a lathe. The turnings are separated into three sieve fractions, the dust being continually drawn off. Only the middle fraction is retained and homogenized before certification analysis and bottling. Some iron samples are produced by crushing
34、 the solid material or by atomisation of the liquid metal. 3.1.3 Ferro-alloys A bulk supply (usually more than 100 kg) of ferro-alloy material taken from production is crushed and ground to a suitable particle size. As there is the possibility with such material for the composition to vary with part
35、icle size, homogeneity checks are carried out on several size fractions of the bulk material. Only those size fractions which are sufficiently similar to each other with respect to chemical composition are selected, and these are blended in a cube shaped or cylindrical mixer made of stainless steel
36、to produce the homogeneous product to be used to produce the CRM. 3.2 EURONORM-CRMs of non-metallic materials 3.2.1 Ores, Concentrates, Sinters and Miscellaneous Materials: Additives and Refractories The material is selected in such a way that it has the best composition and storage properties. Afte
37、r drying, crushing and grinding, it is screened to a suitable particle size and blended in a cube shaped or cylindrical mixer made of stainless steel. PD CEN/TR 10317:2014CEN/TR 10317:2014 (E) 7 The bulk sample is carefully stored in airtight containers. Where necessary a moisture absorber is placed
38、 inside the container. Throughout the whole preparation process the homogeneity is verified. 3.2.2 By-products, such as slags, dusts and similar materials The same rules apply for the preparation of the samples as for materials listed under 3.2.1. The certification analysis can only be carried out a
39、fter a long stabilization period, during which the composition is verified by means of numerous check analyses. 4 Certification 4.1 Main rules The certification of these EURONORM-CRMs is conducted following the guidelines in ISO Guides 30, 31, 34 and 35 and the standard ISO 11459 (see Bibliography).
40、 Chemical characterization of a candidate material is carried out in a certification interlaboratory test with approximately 20 laboratories from industry and research in Europe. Each laboratory is requested to analyse the elements to be determined four times under repeatability conditions but on se
41、parate portions of the sample, using a suitable analytical method of its choice. A statistical evaluation is carried out on all the individual values obtained for each element in order to confirm that they are distributed normally about the overall mean and to identify any outlying values. The aim,
42、for certification of each element or constituent is that, after elimination of statistical outliers, there remain at least 14 acceptable mean values, if possible achieved from different analytical methods. Certification with less than 14 acceptable mean values, but not less than 10, is also possible
43、 in situations where the concentration of the certified constituent is less than 10 g/g or where the constituent is considered difficult to analyse. 4.2 Main content of the certificates 4.2.1 General Each certificate presents a table, in which the laboratory means are presented together with the mea
44、n of the intralaboratory means, MM, the standard deviation of the intralaboratory means, SMand the intralaboratory standard deviation, Sw. The half-width confidence interval C (95 %) of the certified mass content, also reported in each certificate, is calculated from the formula: MC(95%)ntS= where n
45、 is the number of acceptable mean values; t is the Students value at the chosen probability with n-1 degrees of freedom. PD CEN/TR 10317:2014CEN/TR 10317:2014 (E) 8 Certificates also contain a table summarizing all the methods used. Suitable numbers in this table allow the users to identify the meth
46、od corresponding to each value reported on the table of the laboratory means, named above. An exhaustive list of the laboratories having participated on each certification analysis is given on the certificate of the corresponding EURONORM-CRM. The other statements which are also always included in e
47、ach certificate are described in 4.2.2, 4.2.3, 4.2.4 and 4.2.5. 4.2.2 Description of the sample The finely divided EURONORM-CRMs are supplied in glass bottles containing 100 g. These are annotated by the suffix “(C)”. Information about the particle size of the divided sample is also reported. Some E
48、URONORM-CRMs are also available in the form of solid discs normally approximately 38 mm in diameter x 20 mm to 30 mm thick. These are annotated by the suffix “(D)”. 4.2.3 Intended use and stability In the chip form samples are intended for the verification of analytical methods such as those used by
49、 the participating laboratories (including establishing the validity of a new analytical method and/or a standard method under development), for the calibration of analytical instruments in cases where the calibration with primary substances (pure metals or stoichiometric compounds) is difficult to achieve, and for establishing values for secondary reference materials. They will remain stable, provided that bottles remain sealed and are stored in a cool and dry atmosphere. When the bottle has been opened the lid shoul
