DIN EN ISO 12677-2013 Chemical analysis of refractory products by X-ray fluorescence (XRF) - Fused cast-bead method (ISO 12677 2011) German version EN ISO 12677 2011《耐火制品的X射线荧光(XRF.pdf

1、February 2013 Translation by DIN-Sprachendienst.English price group 29No part of this translation may be reproduced without prior permission ofDIN Deutsches Institut fr Normung e. V., Berlin. Beuth Verlag GmbH, 10772 Berlin, Germany,has the exclusive right of sale for German Standards (DIN-Normen).I

2、CS 81.080!$F“1943591www.din.deDDIN EN ISO 12677Chemical analysis of refractory products by X-ray fluorescence (XRF) Fused cast-bead method (ISO 12677:2011);English version EN ISO 12677:2011,English translation of DIN EN ISO 12677:2013-02Chemische Analyse von feuerfesten Erzeugnissen durch Rntgenfluo

3、reszenz-Analyse(RFA) Schmelzaufschluss-Verfahren (ISO 12677:2011);Englische Fassung EN ISO 12677:2011,Englische bersetzung von DIN EN ISO 12677:2013-02Analyse chimique des matriaux rfractaires par fluorescence de rayons X Mthode de la perle fondue (ISO 12677:2011);Version anglaise EN ISO 12677:2011,

4、Traduction anglaise de DIN EN ISO 12677:2013-02SupersedesDIN EN ISO 12677:2012-01www.beuth.deDocument comprises 83 pagesIn case of doubt, the German-language original shall be considered authoritative.01.13DIN EN ISO 12677:2013-02 2 A comma is used as the decimal marker. National foreword This stand

5、ard has been prepared by Technical Committee ISO/TC 33 “Refractories” in collaboration with Technical Committee CEN/TC 187 “Refractory products and materials” (both secretariats are held by BSI, United Kingdom). The responsible German body involved in its preparation was the Normenausschuss Material

6、prfung (Materials Testing Standards Committee), Working Committee NA 062-02-61 AA Chemische Analyse von oxidischen Roh- und Werkstoffen. In ISO 12677:2011, Table H.5, (Case 1), the ratio of the sample to Li2B4O7is incorrect and should read Li2B4O7= 1:10 as in (Case 2) and (Case 3). This has been cor

7、rected in the German version and correspondingly in the English version. The DIN Standards corresponding to the International Standards referred to in this document are as follows: ISO 565 DIN ISO 565 ISO 3534-2 DIN ISO 3534-2 ISO 21068-1 DIN EN ISO 21068-1 ISO 21068-2 DIN EN ISO 21068-2 ISO 21068-3

8、 DIN EN ISO 21068-3 ISO 26845 DIN EN ISO 26845 Amendments This standard differs from DIN EN ISO 12677:2003-08 as follows: a) normative references have been updated; b) further examples of fluxes have been included in Annex C and of certified reference materials in Annexes D and E; c) values of furth

9、er reference materials have been added in Annex I; d) values of specific constituents have been added/corrected in all annexes; e) the standard has been editorially revised. Compared with DIN EN ISO 12677:2012-01, the following corrections have been made to the German version only: a) Subclause 5.8,

10、 NOTE: drfen has been replaced by knnen (can); b) Subclause 11.1: “MgK” has been replaced by “MgK”; c) Annex A, Table A.8, footnote a: “j)” has been added to indicate the flux; d) Annex H, Table H.8, column 8 (MgO),3rd line: the minus sign placed before “0,001 14” has been deleted; DIN EN ISO 12677:

11、2013-02 3 e) Annex I, headings of Table I.3 and I.4, column 9: “Mn2O3” has been corrected to read “Mn3O4”; f) Annex I, Table I.6, column 9, line 4: the value “0,000” has been corrected to read “0,002”; g) Annex I, Table I.8, column 3, lines 2 and 3: the following values have been corrected: “0,030”

12、has been added for (i) H and has been replaced by the sign “” for Limit fT; h) Annex I, Table I.8, column 8, line 3: the value “0,0170” has been corrected to read “0,170”; i) the standard has been editorially revised. Previous editions DIN 51001-1: 1983-07 DIN 51001-1 Supplement 1: 1987-08 DIN EN IS

13、O 12677: 2003-08, 2012-01 DIN EN ISO 12677:2013-02 4 National Annex NA (informative) Bibliography DIN EN ISO 21068-1, Chemical analysis of silicon-carbide-containing raw materials and refractory products Part 1: General information and sample preparation DIN EN ISO 21068-2, Chemical analysis of sili

14、con-carbide-containing raw materials and refractory products Part 2: Determination of loss on ignition, total carbon, free carbon and silicon carbide, total and free silica and total and free silicon DIN EN ISO 21068-3, Chemical analysis of silicon-carbide-containing raw materials and refractory pro

15、ducts Part 3: Determination of nitrogen, oxygen and metallic and oxidic constituents DIN EN 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

16、DIN ISO 565, Test sieves Metal wire cloth, perforated metal plate and electroformed sheet Nominal sizes of openings DIN ISO 3534-2, Statistics Vocabulary and symbols Part 2: Applied statistics EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN ISO 12677 October 2011 ICS 81.080 Supersedes EN ISO 12

17、677:2003English 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) Chemische Analyse von feuerfesten Erzeugnissen du

18、rch 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 for giving this European Standard the status of

19、 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 three official versions (English, French, German)

20、. 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 bodies of Austria, Belgium, Bulgaria, Croatia, C

21、yprus, 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 Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION

22、 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: EContents Page Foreword . 4 1 Scope 5 2 Normat

23、ive references 5 3 Types of material . 5 4 Principle . 6 5 Apparatus . 6 6 Sample grinding 7 7 Loss on ignition (and/or drying) 8 8 Flux . 8 8.1 Choice of flux and ratio of flux to sample . 8 8.2 Compensations for moisture in flux 9 9 Fusion casting procedures. 9 9.1 Fusion of samples and casting of

24、 beads 9 9.2 Automatic bead preparation . 11 9.3 Storage . 11 9.4 Special problems . 12 10 Calibration 12 10.1 Calibration standards 12 10.2 Reagents and series reference materials (SeRMs) 12 10.3 Calibration using reagents . 14 10.4 Calibration using SeRMs 19 11 Corrections 21 11.1 Line-overlap cor

25、rection . 21 11.2 Background correction . 21 11.3 Drift correction . 22 11.4 Calculation of results 22 11.5 Software requirements 23 12 Reproducibility and repeatability . 24 12.1 Fusion tests . 24 12.2 Frequency of instrument tests . 24 12.3 Maximum allowance differences of sample holders . 24 12.4

26、 Sample measuring positions . 25 12.5 Instrument repeatability 25 12.6 Sequential systems . 25 12.7 Dead time . 26 12.8 Other tests 26 12.9 Flow gas . 26 13 Accuracy determined by certified reference materials . 26 13.1 Validation of synthetic calibrations . 26 13.2 Validation of SeRM calibrations .

27、 26 13.3 Fresh beads of the CRMs or synthetic standards used to check SeRM calibrations 26 14 Definitions of limits of detection 27 15 Test report 27 EN ISO 12677:2011 (E) DIN EN ISO 12677:2013-02 2Annex A (normative) Calibration range and required detection limits 28 Annex B (normative) Corrections

28、 for tungsten carbide grinding media .32 Annex C (informative) Examples of fluxes/flux ratios .34 Annex D (normative) Examples of CRM to be used to check synthetic calibrations 36 Annex E (normative) Examples of SeRM 42 Annex F (normative) Equation for theoretical calculations 47 Annex G (normative)

29、 Certified reference materials (CRMs) .48 Annex H (normative) Method of inter-element correction used to compensate for the effects of co-existing components when using SeRM for calibration 51 Annex I (normative) Standard deviations achieved with certified reference materials .71 Bibliography 79 EN

30、ISO 12677:2011 (E) DIN EN ISO 12677:2013-02 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 S

31、tandard 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 t

32、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 EN ISO 12677:2003. According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following count

33、ries 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, Slove

34、nia, 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. EN ISO 12677:2011 (E) DIN EN ISO 12677:2013-02 41 Scope This International Standard specifies a method for the chemical anal

35、ysis of refractory and technical ceramic raw materials, intermediates and products, by means of the X-ray fluorescence (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, su

36、ch as silicon carbides or nitrides, etc. The method is applicable to a wide range of materials containing a wide range 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, th

37、e Bibliography can be referred to. NOTE 2 Constituents at concentrations greater than 99 % (on a dried basis) are reported 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

38、references The following referenced documents are indispensable for the application of this document. For dated references, 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

39、 General and statistical principles for certification ISO 565, Test sieves Metal wire cloth, perforated metal plate and electroformed sheet Nominal sizes of openings ISO 26845, Chemical analysis of refractories General requirements for wet chemical analysis, atomic absorption spectrometry (AAS) and

40、inductively coupled plasma atomic emission spectrometry (ICP-AES) methods 3 Types of material Listed below are various 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 g

41、uide to those using this International Standard for the first time. a) High alumina 45 % Al2O3b) Alumino-silicate 7 % to 45 % Al2O3c) Silica 93 % SiO2d) Zircon e) Zirconia and zirconates f) Magnesia EN ISO 12677:2011 (E) DIN EN ISO 12677:2013-02 5 g) Magnesia/alumina spinel (70/30) h) Dolomite i) Li

42、mestone j) Magnesia/chromic oxide k) Chrome ore l) Chrome-alumina m) Alumina/magnesia spinel (70/30) 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

43、Some of the above material types can be accommodated for common calibrations (see 10.3.4). NOTE 2 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

44、 fusion into a bead prior to XRF analysis. Suitable procedures are described in ISO 21068-1, ISO 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 c

45、an be applied to the rest of the procedure. WARNING Failure to pretreat reduced materials, such as 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 t

46、o destroy its mineralogical and particulate composition. The resultant melt is cast into the shape 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

47、 is analysed by reference to previously determined calibration graphs or equations and applying corrections 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 i

48、n the same way as the samples. Certified reference materials (CRMs) may be used providing they meet 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

49、 being able to meet certain criteria of repeatability, sensitivity and accuracy. Provided that a 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 allo