1、 Reference number ISO/TR 12389:2009(E) ISO 2009TECHNICAL REPORT ISO/TR 12389 First edition 2009-05-01 Methods of testing cement Report of a test programme Chemical analysis by x-ray fluorescence Mthodes dessai des ciments Rapport dun programme dessais Analyse chimique par fluorescence X ISO/TR 12389
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6、s below or ISOs member body in the country of the requester. ISO copyright office Case postale 56 CH-1211 Geneva 20 Tel. + 41 22 749 01 11 Fax + 41 22 749 09 47 E-mail copyrightiso.org Web www.iso.org Published in Switzerland ii ISO 2009 All rights reservedISO/TR 12389:2009(E) ISO 2009 All rights re
7、served iiiContents Page Foreword iv Introduction.v 1 Scope 1 2 Test methods .1 2.1 General arrangements 1 2.2 Test method and constituents to be determined .2 3 Samples 2 3.1 Test samples2 3.2 Calibration standards2 3.3 Validation materials.2 3.4 Participating laboratories .3 4 Method for analysis o
8、f results3 4.1 Statistics.3 4.2 Definition of Q-laboratories 4 5 Results and considerations5 5.1 Laboratory number5 5.2 Validation results for all laboratories 5 5.3 Test results of Q-laboratories 12 6 Conclusions .26 6.1 Result of test sample analyses 26 6.2 Factors affecting conformity with the va
9、lidation criteria 27 6.3 Application to other international inter-laboratory testing .27 Annex A (informative) List of participating laboratories.28 Annex B (informative) Individual results of all laboratories .30 Annex C (informative) Questionnaire results.46 Annex D (informative) Other internation
10、al inter-laboratory round-robin analyses of cement48 Annex E (informative) Acknowledgements 51 Bibliography52 ISO/TR 12389:2009(E) iv ISO 2009 All rights reservedForeword ISO (the International Organization for Standardization) is a worldwide federation of national standards bodies (ISO member bodie
11、s). 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 n
12、on-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. International Standards are drafted in accordance with the rules given in the ISO/IEC Directives, Pa
13、rt 2. The main task of technical committees is to prepare International Standards. Draft International 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 castin
14、g a vote. In exceptional circumstances, when a technical committee has collected data of a different kind from that which is normally published as an International Standard (“state of the art”, for example), it may decide by a simple majority vote of its participating members to publish a Technical
15、Report. A Technical Report is entirely informative in nature and does not have to be reviewed until the data it provides are considered to be no longer valid or useful. Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. ISO shall not
16、 be held responsible for identifying any or all such patent rights. ISO/TR 12389 was prepared by Technical Committee ISO/TC 74, Cement and lime. ISO/TR 12389:2009(E) ISO 2009 All rights reserved vIntroduction This Technical Report summarizes the results of inter-laboratory testing of the chemical an
17、alysis of cement by x-ray fluorescence undertaken by laboratories in Japan, in Asian countries and in Europe. This testing programme was planned and conducted by the Committee on Cement Chemistry, Japan Cement Association and extended to the members of ISO in Asia and members of CEN/TC 51/WG 15 (Rev
18、ision of methods of testing cement) in Europe. A total of 42 laboratories participated. The wet method is a longstanding technique used for chemical analysis of cement. However, since this manner of analysis is extremely time-consuming, more rapid methods have been investigated, leading to the devel
19、opment of chemical analysis of cement by x-ray fluorescence (XRF method). As a result, Japanese Industrial Standard JIS R 5204 was established in July 2002. JIS R 5204 established a scheme to confirm the validity of calibration equations when the concentrations of a pair of validation beads made fro
20、m certified reference materials satisfy the criteria for both the repeatability limits and accuracy limits specified in JIS R 5204. Use of this validation system improves the repeatability and accuracy of results obtained by the JIS R 5204 method. Since an International Standard for this analysis me
21、thod had not yet been established, the Japanese National Committee for ISO/TC 74 (J/TC 74) proposed the “Development of chemical analysis of cement by x-ray fluorescence” to ISO/TC 74 in June 2004. The English version of JIS R 5204 was included as the first working draft at that time. In order to in
22、troduce JIS R 5204 to Asian members of ISO/TC 74 and to promote technical exchange among them, an inter-laboratory testing programme was organized. This inter-laboratory testing was carried out with the participation of 16 laboratories in Japan and 14 outside Japan, mostly Asian members of ISO/TC 74
23、. As this first part of the round-robin testing was taking place, work was in progress within CEN committee TC 51/WG 15 to produce a standard method for the chemical analysis of cement by x-ray fluorescence. The Japanese Industrial Standard JIS R 5204 was accepted by this committee and, working join
24、tly with the Japanese co-opted member, was incorporated into the draft for ISO 29581-2. At the invitation of the Japanese Cement Association, members of CEN/TC 51/WG 15 were invited to join in the Japanese/Asian round robin and in 2005 twelve European laboratories participated. The results of their
25、testing are included in this report. Those laboratories that obtained analyses of JCA-CRM-1 and/or JCA-CRM-2 satisfying the criteria for both the repeatability limits and accuracy limits for all components were defined as “Q-laboratories”. A comparison of the results for “Q-laboratories” with those
26、obtained from other inter-laboratory testing for all constituents other than CaO indicates that the variation was equal to or smaller than that of wet analysis. The variation in results for CaO in “Q-laboratories” was slightly larger than that by wet analysis. Therefore, this inter-laboratory testin
27、g demonstrates that the accuracy of results obtained by the JIS R 5204/ISO 29581-2 method is generally the same as that for the wet method. TECHNICAL REPORT ISO/TR 12389:2009(E) ISO 2009 All rights reserved 1Methods of testing cement Report of a test programme Chemical analysis by x-ray fluorescence
28、 1 Scope This Technical Report describes the results of the inter-laboratory testing of the chemical analysis of cement by x-ray fluorescence. In the first instance, the inter-laboratory testing was carried out in Japan and in Asian countries in accordance with JIS R 5204:2002. A total of 30 laborat
29、ories, 16 in Japan and 14 outside Japan, participated in the original testing programme. A further 12 European laboratories participated in tests with the same materials in 2005 in accordance with EN 196-2, a development by CEN/TC 51/WG 15/TG 1 of JIS R 5204. The latest version, developed as ISO 295
30、81-2, is, as of the date of publication of this Technical Report, in the process of being circulated for technical enquiry. The test samples used were Portland cement conforming to CEM I of EN 197-1 and a mixture of Portland cement and blast furnace slag. The mixture corresponded to the composition
31、of Portland blast furnace slag cement, class B, specified in JIS R 5211 and CEM III/A of EN 197-1. Cement reference materials for x-ray fluorescence analysis (No. 601A) are used for the calibration standards, and certified reference materials JCA-CRM-1 and JCA-CRM-2 are used as the validation materi
32、als. Constituents analysed include SiO 2 , Al 2 O 3 , Fe 2 O 3 , CaO, MgO, SO 3 , Na 2 O, K 2 O, TiO 2 , P 2 O 5 , MnO and SrO. The loss on ignition is also determined. The ISO round robin is a method-performance study conducted under close to optimum conditions with clear calibration and measuremen
33、t guidelines. This is conducive to producing “best practice” values representative of the ideal situation. However, ISO 29581-2 is intended for use under everyday conditions in laboratories that operate to “good practice”. Annex D sets out the results of some international round robins carried out b
34、y a large number of laboratories demonstrating the suitability of ISO 29581-2 as a means for comparing the everyday performance of laboratories. 2 Test methods 2.1 General arrangements The outline of the inter-laboratory testing is shown in Table 1. ISO/TR 12389:2009(E) 2 ISO 2009 All rights reserve
35、dTable 1 Outline of the inter-laboratory testing Test method First part JIS R 5204:2002 Second part ISO 29581-1 Test samples JCA #1 Portland cement JCA #2 Cement made by mixing Portland cement with blast furnace slag (composition corresponding to Portland blast furnace slag cement Class B specified
36、in JIS R 5211 and CEM III/A of EN 197-1) Calibration standards Cement reference materials for x-ray fluorescence analysis, JCA No. 601A Validation materials JCA-CRM-1 Ordinary Portland cement JCA-CRM-2 Portland blast furnace slag cement Constituents determined SiO 2 , Al 2 O 3 , Fe 2 O 3 , CaO, MgO,
37、 SO 3 , Na 2 O, K 2 O, TiO 2 , P 2 O 5 , MnO, SrO, loss on ignition (LOI) 2.2 Test method and constituents to be determined The first phase of this inter-laboratory testing was based on JIS R 5204. The second phase of this inter- laboratory testing was based on ISO 29581-2. There were no substantial
38、 differences between the two methods. For the remainder of this report they will be referred to as “the XRF method”. Twelve constituents: SiO 2 , Al 2 O 3 , Fe 2 O 3 , CaO, MgO, SO 3 , Na 2 O, K 2 O, TiO 2 , P 2 O 5 , MnO, and SrO, determined by XRF method using glass beads, and loss on ignition wer
39、e to be evaluated. Although SO 3for Portland blast furnace slag cement was outside the scope of JIS R 5204, it was an option for Sample #2 in this testing. 3 Samples 3.1 Test samples Two test samples were used: Portland cement (Sample #1) conforming to EN 197-1 CEM I, and a cement mixture of Portlan
40、d cement and blast furnace slag (Sample #2). Sample #2 corresponded to the B-type Portland blast furnace slag cement specified in JIS R 5211 and CEM III/A of EN 197-1. Approximately 30 g of each sample was distributed. 3.2 Calibration standards Cement reference materials for x-ray fluorescence analy
41、sis (see NOTE), provided by the Japan Cement Association, were used for the calibration standards. Approximately 12 g of each standard of JCA No. 601A was distributed to the foreign laboratories. The only requirement was that seven or more calibration standards be used when making calibration equati
42、ons in accordance with the XRF method. NOTE JCA No. 601A is a set of 15 cement reference materials consisting of nine Portland cements and six Portland blast furnace slag cements. 3.3 Validation materials Validation of calibration equations was specified in the XRF method. Certified reference materi
43、als JCA-CRM-1 and JCA-CRM-2, provided by the Japan Cement Association, were used as the validation materials. Approximately 30 g of each CRM was distributed to the laboratories. ISO/TR 12389:2009(E) ISO 2009 All rights reserved 33.4 Participating laboratories 3.4.1 Japan An announcement of the inter
44、-laboratory testing was sent out to members of the Japan Cement Association. In response to the announcement, 16 laboratories registered as participants in this testing programme. A list of participating laboratories is shown in Annex A. 3.4.2 Asia An announcement of the inter-laboratory testing was
45、 sent out to Asian members registered as P-members or O-members in ISO/TC 74 (See NOTE). Sixteen laboratories responded to the announcement and expressed their desire to participate, and 14 laboratories registered for the programme. A list of participating laboratories is shown in the Annex A. NOTE
46、The announcement was sent out to member bodies registered in ISO/TC74, and to Cement Associations of the members; see Reference 10. 3.4.3 Europe Invitations were issued to the members of European Standards Organization Technical Committee TC 51, Cement and building limes, Working Group 15, Methods o
47、f testing cement, Task Group 1, Analysis by x-ray fluorescence, to nominate participating laboratories. Twelve laboratories undertook to participate. A list of participating laboratories is shown in Annex A. 4 Method for analysis of results 4.1 Statistics Symbols and definitions of statistical terms
48、 used in this report are shown in Table 2. Table 2 Definitions of the statistical terms Statistical term Abbreviation/symbol Definition of the statistical termaAverage Av./ x in i i x x n = = = 1Maximum value Max. Maximum value in the data Minimum value Min. Minimum value in the data Range Range is
49、equal to max. minus min. Standard deviation S.D./ () n i i xx n = = 2 1 1Coefficient of variation C.V./C VC x = V 100 , expressed as a percentage an is the number of laboratories; x is the mean value of a pair of results from each laboratory. ISO/TR 12389:2009(E) 4 ISO 2009 All rights reserved4.2 Definition of Q-laboratories 4.2.1 General In this inter-laboratory testing, a Q-laboratory is one where the concentration of a pair of validation beads made from certified reference materials satisfies the criteria f
