1、BSI Standards PublicationBS EN ISO 12677:2011Chemical analysis of refractoryproducts by X-ray fluorescence(XRF) Fused cast-beadmethod (ISO 12677:2011)Incorporating corrigendum April 2014BS EN ISO 12677:2011National forewordThis British Standard is the UK implementation of EN ISO 12677:2011. It super
2、sedes BS EN ISO 12677:2003 and BS 1902-9.1:1987, which are withdrawn.The UK participation in its preparation was entrusted to Technical Committee RPI/1, Refractory products and materials.A list of organizations represented on this committee can be obtained on request to its secretary.This publicatio
3、n does not purport to include all the necessary provisions of a contract. Users are responsible for its correct application. The British Standards Institution 2014. Published by BSI Standards Limited 2014ISBN 978 0 580 85428 6ICS 81.080Compliance with a British Standard cannot confer immunity fromle
4、gal obligations.This British Standard was published under the authority of the Standards Policy and Strategy Committee on 31 October 2011.Amendments/corrigenda issued since publicationDate Text affected30 April 2014 Correction to supersession detailsBRITISH STANDARDEUROPEAN STANDARD NORME EUROPENNE
5、EUROPISCHE NORM EN ISO 12677 October 2011 ICS 81.080 English Version Chemical analysis of refractory products by X-ray fluorescence (XRF) - Fused cast-bead method (ISO 12677:2011) Analyse chimique des matriaux rfractaires par fluorescence de rayons X - Mthode de la perle fondue (ISO 12677:2011) Chem
6、ische Analyse von feuerfesten Erzeugnissen durch Rntgenfluoreszenz-Analyse (RFA) - Schmelzaufschluss-Verfahren (ISO 12677:2011) This European Standard was approved by CEN on 10 September 2011. CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions fo
7、r giving this European Standard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such national standards may be obtained on application to the CEN-CENELEC Management Centre or to any CEN member. This European Standard exists in thre
8、e official versions (English, French, German). A version in any other language made by translation under the responsibility of a CEN member into its own language and notified to the CEN-CENELEC Management Centre has the same status as the official versions. CEN members are the national standards bod
9、ies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Ki
10、ngdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG Management Centre: Avenue Marnix 17, B-1000 Brussels 2011 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN ISO 12677:2011: E
11、BS EN ISO 12677:2011EN ISO 12677:2011 (E) 3 Foreword This document (EN ISO 12677:2011) has been prepared by Technical Committee ISO/TC 33 “Refractories“ in collaboration with Technical Committee CEN/TC 187 “Refractory products and materials” the secretariat of which is held by BSI. This European Sta
12、ndard shall be given the status of a national standard, either by publication of an identical text or by endorsement, at the latest by April 2012, and conflicting national standards shall be withdrawn at the latest by April 2012. Attention is drawn to the possibility that some of the elements of thi
13、s 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 EN ISO 12677:2003. According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countri
14、es are bound to implement this European Standard: Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Sloveni
15、a, Spain, Sweden, Switzerland and the United Kingdom. Endorsement notice The text of ISO 12677:2011 has been approved by CEN as a EN ISO 12677:2011 without any modification. BS EN ISO 12677:2011ISO 12677:2011(E) ISO 2011 All rights reserved iiiContents Page Foreword . v 1 Scope 1 2 Normative referen
16、ces 1 3 Types of material . 1 4 Principle . 2 5 Apparatus . 2 6 Sample grinding 3 7 Loss on ignition (and/or drying) 4 8 Flux . 4 8.1 Choice of flux and ratio of flux to sample . 4 8.2 Compensations for moisture in flux 5 9 Fusion casting procedures. 5 9.1 Fusion of samples and casting of beads 5 9.
17、2 Automatic bead preparation . 7 9.3 Storage . 7 9.4 Special problems . 8 10 Calibration 8 10.1 Calibration standards 8 10.2 Reagents and series reference materials (SeRMs) 8 10.3 Calibration using reagents . 10 10.4 Calibration using SeRMs 15 11 Corrections 17 11.1 Line-overlap correction . 17 11.2
18、 Background correction . 17 11.3 Drift correction . 18 11.4 Calculation of results 18 11.5 Software requirements 19 12 Reproducibility and repeatability . 20 12.1 Fusion tests . 20 12.2 Frequency of instrument tests . 20 12.3 Maximum allowance differences of sample holders . 20 12.4 Sample measuring
19、 positions . 21 12.5 Instrument repeatability 21 12.6 Sequential systems . 21 12.7 Dead time . 22 12.8 Other tests 22 12.9 Flow gas . 22 13 Accuracy determined by certified reference materials . 22 13.1 Validation of synthetic calibrations . 22 13.2 Validation of SeRM calibrations . 22 13.3 Fresh be
20、ads of the CRMs or synthetic standards used to check SeRM calibrations 22 14 Definitions of limits of detection 23 15 Test report 23 BS EN ISO 12677:2011ISO 12677:2011(E) iv ISO 2011 All rights reservedAnnex A (normative) Calibration range and required detection limits 24 Annex B (normative) Correct
21、ions for tungsten carbide grinding media .28 Annex C (informative) Examples of fluxes/flux ratios .30 Annex D (normative) Examples of CRM to be used to check synthetic calibrations 32 Annex E (normative) Examples of SeRM 38 Annex F (normative) Equation for theoretical calculations 43 Annex G (normat
22、ive) Certified reference materials (CRMs) .44 Annex H (normative) Method of inter-element correction used to compensate for the effects of co-existing components when using SeRM for calibration 47 Annex I (normative) Standard deviations achieved with certified reference materials .68 Bibliography 75
23、 BS EN ISO 12677:2011ISO 12677:2011(E) ISO 2011 All rights reserved vForeword 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 technic
24、al 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 wi
25、th 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 Inte
26、rnational 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. Attention is drawn to the possibility that some of the elements of this document ma
27、y be the subject of patent rights. ISO shall not be held responsible for identifying any or all such patent rights. ISO 12677 was prepared by Technical Committee ISO/TC 33, Refractories. This second edition cancels and replaces the first edition (ISO 12677:2003), which has been technically revised.
28、Although the method in this International Standard has been considerably modified editorially and in layout, the technical changes are limited. Some minor corrections have been made to certain equations. The only significant changes are a reference to a further International Standard method (being p
29、repared) for the preparation of reduced materials for analysis by this standard, and instructions on how to add other constituents to calibrations at the end of 10.2.1, Purity and preparation of reagents. BS EN ISO 12677:2011BS EN ISO 12677:2011INTERNATIONAL STANDARD ISO 12677:2011(E) ISO 2011 All r
30、ights reserved 1Chemical analysis of refractory products by X-ray fluorescence (XRF) Fused cast-bead method 1 Scope This International Standard specifies a method for the chemical analysis of refractory and technical ceramic raw materials, intermediates and products, by means of the X-ray fluorescen
31、ce (XRF) fused cast-bead method. Typical materials that can be analysed by this standard are given in Clause 3. This International Standard is not applicable to non-oxide materials, such as silicon carbides or nitrides, etc. The method is applicable to a wide range of materials containing a wide ran
32、ge of elements. NOTE 1 The presence of significant amounts of certain elements, such as tin, copper, zinc and chromium, can present difficulties in the fusion process. In this case, the Bibliography can be referred to. NOTE 2 Constituents at concentrations greater than 99 % (on a dried basis) are re
33、ported by difference, provided that all likely minor constituents and any loss on ignition have been determined. These figures can also be checked by direct determination. 2 Normative references The following referenced documents are indispensable for the application of this document. For dated refe
34、rences, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies. ISO Guide 35:2006, Reference materials General and statistical principles for certification ISO 565, Test sieves Metal wire cloth, perforated metal plate
35、and electroformed sheet Nominal sizes of openings ISO 26845, Chemical analysis of refractories General requirements for wet chemical analysis, atomic absorption spectrometry (AAS) and inductively coupled plasma atomic emission spectrometry (ICP-AES) methods 3 Types of material Listed below are vario
36、us types of ceramic material that have been successfully analysed by this method and for which statistical data is available (see Annex I). The list is not exhaustive but serves as a guide to those using this International Standard for the first time. a) High alumina 45 % Al2O3b) Alumino-silicate 7
37、% to 45 % Al2O3c) Silica 93 % SiO2d) Zircon e) Zirconia and zirconates f) Magnesia BS EN ISO 12677:2011ISO 12677:2011(E) 2 ISO 2011 All rights reservedg) Magnesia/alumina spinel (70/30) h) Dolomite i) Limestone j) Magnesia/chromic oxide k) Chrome ore l) Chrome-alumina m) Alumina/magnesia spinel (70/
38、30) n) Zirconia-alumina-silica cast material (AZS) o) Calcium silicates p) Calcium aluminates q) Magnesium silicates A list of elemental ranges and required detection limits are given in Annex A. NOTE 1 Some of the above material types can be accommodated for common calibrations (see 10.3.4). NOTE 2
39、 Reduced materials, such as silicon carbide, cannot be determined directly by this International Standard and so are not listed above. Such materials require special methods both for loss on ignition and fusion into a bead prior to XRF analysis. Suitable procedures are described in ISO 21068-1, ISO
40、21068-2 and ISO 21068-3 and further methods are under development by the refractory standards system. Once reduced materials are suitably ignited and subsequently prepared as fused beads, this standard can be applied to the rest of the procedure. WARNING Failure to pretreat reduced materials, such a
41、s silicon carbide, properly not only leads to erroneous results but will also cause damage to valuable platinum alloy crucibles and dishes. 4 Principle The powdered sample is fused with a suitable flux to destroy its mineralogical and particulate composition. The resultant melt is cast into the shap
42、e of a glass bead which is then introduced into an XRF spectrometer. The intensities of the fluorescent X-rays of the required elements in the bead are measured and the chemical composition of the sample is analysed by reference to previously determined calibration graphs or equations and applying c
43、orrections for inter-element effects. The calibration equations and inter-element corrections are established from beads produced using pure reagents and/or series reference materials (SeRMs), prepared in the same way as the samples. Certified reference materials (CRMs) may be used providing they me
44、et all the requirements of 10.2.2 and 10.4.1. Because of the universality of the fused cast-bead technique, various fluxes and modes of calibration are permitted, providing they have been demonstrated as being able to meet certain criteria of repeatability, sensitivity and accuracy. Provided that a
45、laboratorys own methods conform to all the various criteria set down, they will be accepted as conforming to this International Standard. 5 Apparatus 5.1 Fusion vessels, of a non-wetted platinum alloy (Pt/Au 95 %/5 % is suitable). Lids, if used, shall be of a platinum alloy (not necessarily non-wett
46、ed). NOTE A useful guide to the care of platinum is given in Reference 5 of the Bibliography. 5.2 Casting moulds, of a non-wetted platinum alloy (Pt/Au 95 %/5 % is suitable). NOTE Vessels that serve both as fusion vessels and casting moulds can be used. BS EN ISO 12677:2011ISO 12677:2011(E) ISO 2011
47、 All rights reserved 35.3 Heat reservoir for casting mould (optional), required in special circumstances when using moulds of small sizes, so that the mould does not cool too rapidly when removed from the furnace. A small piece of flat refractory material is suitable, e.g. a piece of sillimanite bat
48、t with dimensions 10 mm 50 mm 50 mm. 5.4 Air jet (optional), required to cool the mould rapidly. This may be any device whereon a narrow jet of air can be directed to the centre of the base of the casting dish. A convenient way of doing this is to use the base of a Bunsen burner without a barrel to
49、serve as an air jet. NOTE In most cases, it is very important to cool the melt rapidly. This is necessary to obtain a homogeneous bead and to free the melt from the dish. A water-cooled metal plate may also be used. 5.5 Fusion apparatus, electric resistance furnaces or high-frequency induction furnaces that may be heated up to a fixed temperature of between 1 050 C and 1 250 C may be used. 5.6 Automatic fusion apparatus, for use in automatic bead preparation (see 9.2) where required. 5.7 Balance, capable of weighing to 0,1 mg.
