ISO/TR 12389:2009

TECHNICAL ISO/TR
REPORT 12389
First edition
2009-05-01
Methods of testing cement — Report of a
test programme — Chemical analysis by
x-ray fluorescence
Méthodes d'essai des ciments — Rapport d'un programme d'essais —
Analyse chimique par fluorescence X

Reference number
©
ISO 2009
PDF disclaimer
This PDF file may contain embedded typefaces. In accordance with Adobe's licensing policy, this file may be printed or viewed but
shall not be edited unless the typefaces which are embedded are licensed to and installed on the computer performing the editing. In
downloading this file, parties accept therein the responsibility of not infringing Adobe's licensing policy. The ISO Central Secretariat
accepts no liability in this area.
Adobe is a trademark of Adobe Systems Incorporated.
Details of the software products used to create this PDF file can be found in the General Info relative to the file; the PDF-creation
parameters were optimized for printing. Every care has been taken to ensure that the file is suitable for use by ISO member bodies. In
the unlikely event that a problem relating to it is found, please inform the Central Secretariat at the address given below.

©  ISO 2009
All rights reserved. Unless otherwise specified, no part of this publication may be reproduced or utilized in any form or by any means,
electronic or mechanical, including photocopying and microfilm, without permission in writing from either ISO at the address below or
ISO's 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 copyright@iso.org
Web www.iso.org
Published in Switzerland
ii © ISO 2009 – All rights reserved

Contents 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 samples.2
3.2 Calibration standards.2
3.3 Validation materials.2
3.4 Participating laboratories .3
4 Method for analysis of results.3
4.1 Statistics.3
4.2 Definition of Q-laboratories .4
5 Results and considerations.5
5.1 Laboratory number.5
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 validation 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 international inter-laboratory round-robin analyses of cement.48
Annex E (informative) Acknowledgements .51
Bibliography.52

Foreword
ISO (the International Organization for 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 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.
International Standards are drafted in accordance with the rules given in the ISO/IEC Directives, Part 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 casting 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 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 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.

iv © ISO 2009 – All rights reserved

Introduction
This Technical Report summarizes the results of inter-laboratory testing of the chemical analysis 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 (Revision 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
development 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 from 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 method 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 introduce 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.
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 jointly 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 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 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
testing 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)

Methods of testing cement — Report of a test programme —
Chemical analysis by x-ray fluorescence
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 laboratories, 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 29581-2, 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 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 materials.
Constituents analysed include SiO , Al O , Fe O , CaO, MgO, SO , Na O, K O, TiO , P O , MnO and SrO.
2 2 3 2 3 3 2 2 2 2 5
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 measurement 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 by 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.
Table 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 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 , Al O , Fe O , CaO, MgO, SO , Na O, K O, TiO ,
2 2 3 2 3 3 2 2 2
P O , MnO, SrO, loss on ignition (LOI)
2 5
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 differences between the two
methods. For the remainder of this report they will be referred to as “the XRF method”.
Twelve constituents: SiO , Al O , Fe O , CaO, MgO, SO , Na O, K
...