1、raising standards worldwideNO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAWBSI Standards PublicationPD CEN/TR 10354:2011Chemical analysis of ferrous materials Analysis of ferro-silicon Determination of Si and Al by X-ray fluorescence spectrometryIncorporating corrigendum March
2、2012PD CEN/TR 10354:2011 PUBLISHED DOCUMENTNational forewordThis Published Document is the UK implementation ofThe UK participation in its preparation was entrusted to Technical Committee ISE/102, Methods of Chemical Analysis for Iron and Steel.A list of organizations represented on this committee c
3、an be obtained on request to its secretary.This publication does not purport to include all the necessary provisions of a contract. Users are responsible for its correct application. ISBN 978 0 580 77884 1 ICS 77.080.10 Compliance with a British Standard cannot confer immunity from legal obligations
4、.This Published Document was published under the authority of the Standards Policy and Strategy Committee on 30 November 2011.Amendments/corrigenda issued since publicationDate T e x t a f f e c t e dThe British Standards Institution 2012 Implementation of CEN correction noticePublished by BSI Stand
5、ards Limited 2012CEN/TR 10354:2011.31 March 201204 January 2012: Figures B.3 and B.4 replacedTECHNICAL REPORT RAPPORT TECHNIQUE TECHNISCHER BERICHT CEN/TR 10354 November 2011 ICS 77.080.10 English Version Chemical analysis of ferrous materials - Analysis of ferro-silicon - Determination of Si and Al
6、 by X-ray fluorescence spectrometryAnalyse chimique des matriaux ferreux - Analyse du ferro-silicium - Dtermination de Si et Al dans le ferro-silicium par spectromtrie de fluorescence de rayons X Chemische Analyse von Ferrolegierungen - Analyse von Ferrosilizium - Bestimmung von Si und Al in Ferrole
7、gierungen durch Rntgenfluoreszenzanalyse This Technical Report was approved by CEN on 24 April 2011. 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,
8、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 COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITE
9、E 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. CEN/TR 10354:2011: E2 Contents Page Foreword 3 1 Scope 4 2 Principle 4 3 Reagents .5 4 Apparatus .5 5 Safety precau
10、tions .5 6 Sampling .5 7 Procedure .6 8 Expression of results 7 9 Precision .7 10 Test report 8 Annex A (informative) Test samples used for the precision test .9 Annex B (informative) Detailed results obtained from the precision test 10 Annex C (informative) Calibration curve - Preparation of oxide
11、beads with pure metals and/or oxides . 17 Bibliography . 19 PD CEN/TR 10354:2011CEN/TR 10354: 2011 (E)3 Foreword This document (CEN/TR 10354:2011) 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. Attenti
12、on is drawn to the possibility that some of the elements of this 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. PD CEN/TR 10354:2011 CEN/TR 10354:2011 (E)4 1 Scope This Technical Report describes a X-ray f
13、luorescence (XRF) spectrometric method for the determination of Si and Al contents in ferro-silicon materials. The method is applicable to: Si contents between 40 % and 90 %; Al contents between 0,5 % and 6 %. The correction of the spectrometric measurement from spectral interferences on the analyti
14、cal lines used is essential. This Technical Report is valid for the analytical lines: Si K 7.126 (for element contents between 45 % and 90 %); Al K 8.339 (for element contents between 0,8 % and 6 %); Fe K 1.937 (for element contents between 10 % and 58 %). NOTE For matrix matching purposes, iron is
15、included in the analytical program to be prepared. Within the conditions here above, spectral interferences dont need to be calculated. 2 Principle Preparation of oxide beads, comprising the oxidation of the sample with strontium nitrate and its melting with lithium tetraborate, in a platinum crucib
16、le. The beads are irradiated by an X-ray beam of suitable energy. The secondary X-rays produced are dispersed by means of crystals and the corresponding intensities are measured by detectors at the selected wavelengths. The contents of the relevant elements are determined by relating the measured in
17、tensities of unknown samples to calibration curves recorded with beads prepared with certified reference materials. Fixed channel or sequential systems may be used to provide simultaneous or sequential determinations of element concentrations. PD CEN/TR 10354:2011 CEN/TR 10354:2011 (E)5 3 Reagents D
18、uring the analysis, use only reagents of recognised analytical grade. 3.1 Strontium Nitrate Sr(NO3)2 3.2 Sodium Carbonate Na2CO3 3.3 Lithium Tetraborate Li2B4O7 3.4 Sodium Iodide NaI 4 Apparatus 4.1 X-ray fluorescence spectrometer The spectrometer can be either a simultaneous or a sequential wavelen
19、gth dispersive model and shall be optimised according to the manufacturer instructions. 4.2 Melting devices 4.3 Platinum crucibles 4.4 Nickel crucibles 4.5 Platinum dishes 5 Safety precautions They shall be in accordance with national regulations for X-ray equipment. X-ray equipment shall be used on
20、ly under the guidance and supervision of a responsible, qualified person. 6 Sampling Sampling shall be carried out in accordance with appropriate international or national standards for ferro alloys. PD CEN/TR 10354:2011 CEN/TR 10354:2011 (E)6 7 Procedure 7.1 Test sample preparation In a platinum cr
21、ucible (4.3), weigh 6,00 g of Li2B4O7(3.3) to the nearest 0,001 g. In a nickel crucible (4.4), weigh, to the nearest 0,001 g: 0,750 g of Sr(NO3)2(3.1); 2,500 g of Na2CO3(3.2); 1,000 g of Li2B4O7(3.3). Then, weigh 0,250 0 g of the sample, to the nearest 0,000 1 g and add it into the same nickel cruci
22、ble (4.4). Finally transfer into the nickel crucible (4.4) 0,020 g of NaI (3.4), weighted to the nearest 0,001 g. Carefully mix all the components added into the nickel crucible (4.4) and then completely pour the mixture contained in the nickel crucible (4.4) into the platinum crucible (4.3), onto t
23、he 6,00 g of Li2B4O7(3.3), whilst avoiding the contact of the mixture with the wall of the platinum crucible (4.3). Introduce the platinum crucible (4.3) in a furnace set up at the temperature of 650 C for 6 min, in order to oxidise the sample. Melt the sample at the temperature of 1 200 C, whilst m
24、ixing continuously and then pour the melted sample in a platinum dish (4.5) preheated with a Bunsen flame. Allow the so prepared bead to cool. 7.2 Preparation of the calibration curves Prepare the calibration of the X-ray fluorescence spectrometer by using oxide beads of ferro-silicon Certified Refe
25、rence Materials (CRMs). For each element, prepare a minimum of six oxide beads with different contents of Si, Al and Fe, in the same way as for the test samples (see 7.1), only using Certified Reference Materials. These Certified Reference Materials shall cover the entire calibration range. Use the
26、analytical line K 7.126 for Si, K 8.339 for Al and K 1.937 for Fe and plot the absolute intensities versus the related certified contents. NOTE The calibration curves can also be obtained by using oxide beads prepared with pure metals and/or oxides. Annex C describes the related preparation. 7.3 Spe
27、ctrometric measurements 7.3.1 Spectrometric measurements of the calibration and the re-calibration samples For each element (each analytical line) measure the related absolute intensity of the calibration samples together with the re-calibration samples according to the instrument manufacturer instr
28、uctions, at least four times each. NOTE 1 To compensate the instrumental day to day drift, re-calibration samples and procedures are required. PD CEN/TR 10354:2011 CEN/TR 10354:2011 (E)7 NOTE 2 Its advisable to prepare the re-calibration samples as described in 7.1. These samples can be internal ref
29、erence materials provided that their homogeneity has been carefully check, approved and recorded. Prepare the related calibration graphs by plotting the mean intensity values of the Certified Reference Materials beads against the corresponding Si and Al certified contents. Record the regression calc
30、ulations and store the relevant parameters, together with the corresponding coefficients of correlation, the standard error of estimate, the error of the slope and the confidence limits. Check the calibration trueness by measuring a set of Certified Reference Materials not used in the calibration an
31、d prepared as described in 7.1. The silicon and aluminium certified values of these samples shall cover at least the low, mid and top points of the corresponding calibration ranges. 7.3.2 Spectrometric measurements of the test samples Following the manufacturer instructions, measure the intensity of
32、 each test sample bead at least twice and calculate the mean value of the corresponding results. 8 Expression of results On the calibration curves, read the contents, expressed in percent (mass fraction) of the elements (Si, Al and Fe) determined in the test sample. 9 Precision Four laboratories in
33、two European countries participated in an inter laboratory test programme under the auspices of ECISS/TC 102/WG 5, involving three determinations of Al and Si at several levels. Each laboratory carried out two determinations under repeatability conditions as defined in ISO 5725-1, i.e. one operator,
34、 same apparatus, identical operating conditions, same calibration and a minimum period of time. The third determination was carried out on a different day using the same apparatus with a different calibration. Details on the samples used are given in Annex A and the results obtained are reported in
35、Annex B. The sets of data available were too few for a statistical evaluation based on ISO 5725-2 and ISO 5725-3. Only Mandels h and k statistics were used (see Figures B.1 to B.4) rather for illustrative purposes. A short comment on the suitability of the data presented is also given in Annex B. PD
36、 CEN/TR 10354:2011 CEN/TR 10354:2011 (E)8 10 Test report The test report shall contain the following information: a) identification of the test sample; b) method used; c) results; d) any unusual characteristics noted during the determination; e) any operation not included in this Technical Report or
37、 in the document to which reference is made or regarded as optional; f) date of the test and/or date of preparation or signature of the test report; g) signature of the responsible person. PD CEN/TR 10354:2011 CEN/TR 10354:2011 (E)9 Annex A (informative) Test samples used for the precision test The
38、test samples used are listed in Table A.1, here below. Elements and/or contents reported in grey cells were out of the scope of the precision test. Table A.1 Composition of the test samples used for the precision test Sample label Al (%) Ti (%) P (%) Si (%) Fe (%) B (%) NBS 59 A 0,35 0,016 48,1 50,0
39、 0,058 DL 2307 6,01 0,073 0,020 55,9 12,6 NBS 58 A 0,95 0,051 0,009 73,2 25,2 0,001 IPT 56 0,31 0,020 0,022 75,0 24,1 ECRM 582-2 1,15 0,225 0,018 75,2 21,4 0,005 JSS 720-4 1,52 0,032 76,4 ECRM 529-1 0,86 0,090 0,032 91,1 6,2 PD CEN/TR 10354:2011 CEN/TR 10354:2011 (E)10 Annex B (informative) Detailed
40、 results obtained from the precision test B.1 Aluminium results B.1.1 Results Table B.1 Aluminium ECRM 529-1 NBS 58 A ECRM 582-2 JSS 720-4 DL 2307 Day 1 Day 2 Day 1 Day 2 Day 1 Day 2 Day 1 Day 2 Day 1 Day 2 LAB 1 Individual values 0,739 0 0,752 7 0,858 1 0,871 3 1,034 4 1,021 6 1,362 3 1,321 5 5,958
41、 9 6,010 8 0,792 8 0,858 1 1,009 7 1,368 5 5,998 6 Laboratory mean0,761 5 0,862 5 1,021 9 1,350 8 5,989 4 LAB 2 Individual values 0,932 7 0,941 3 0,993 8 0,959 3 1,264 0 1,259 5 1,542 4 1,534 4 6,155 4 6,154 5 0,971 5 1,017 6 1,263 9 1,524 1 6,264 3 Laboratory mean0,948 5 0,990 2 1,262 5 1,533 6 6,1
42、91 4 LAB 4 Individual values 0,909 9 0,889 1 1,082 4 1,004 5 1,032 1 1,403 0 1,729 3 1,495 9 5,941 4 6,006 0 0,902 9 1,028 9 1,099 8 1,800 8 5,904 7 Laboratory mean 0,900 6 1,038 6 1,178 3 1,675 3 5,950 7 LAB 6 Individual values 0,930 3 0,937 2 1,106 9 1,369 3 1,310 3 1,257 9 1,795 2 1,650 4 6,341 6
43、 6,072 8 0,970 0 1,379 2 1,271 0 1,748 4 6,155 3 Laboratory mean 0,945 8 1,285 1 1,279 7 1,731 3 6,189 9 Mean value (%) 0,889 1 0,963 8 1,185 6 1,572 8 6,080 4 0,087 9 - 0,117 8 0,169 8 0,128 3 CV (%)9,88 - 9,93 10,8 2,11 Certified value (%) 0,86 0,95 1,15 1,52 6,01PD CEN/TR 10354:2011 CEN/TR 10354:
44、2011 (E)11 Figure B.1 Aluminium Mendels k test for intra laboratory consistency (99 % confidence level) Figure B.2 Aluminium Mendels h test for between laboratory consistency (99 % confidence level) PD CEN/TR 10354:2011 CEN/TR 10354:2011 (E)12 B.1.2 Comments on the suitability of the data for alumin
45、ium Based on the data presented in Table B.1 and on the Mendels statistics from Figures B.1 and B.2, some results from Laboratories 4 and 6 show intralaboratory reproducibility discrepancies and Laboratories 1 (low) and 6 (high) show systematic tendencies regarding the content levels. However, no re
46、moval of these rather doubtful data was carried out, taking into account the reduced size of the population under concern. The mean values of the individual means are in a sufficiently good agreement with the “referee values“ of the samples used, except for sample NBS 58 A. This is due to the very h
47、igh result produced by Laboratory 6 for this sample. Besides this specific case, the trueness of the determinations is rather acceptable. In opposite, it should be underlined that the “precision“ of this determination might be not suitable enough when accurate results are required. PD CEN/TR 10354:2
48、011 CEN/TR 10354:2011 (E)13 B.2 Silicon results B.2.1 Results Table B.2 Silicon NBS 59 A DL 2307 NBS 58 A IPT 56 ECRM 582-2 Day 1 Day 2 Day 1 Day 2 Day 1 Day 2 Day 1 Day 2 Day 1 Day 2 LAB 1 Individual values 47,307 3 47,602 1 57,085 1 57,385 4 73,580 7 73,785 1 75,930 7 76,276 1 75,526 8 75,779 6 47
49、,327 5 57,177 0 73,259 4 75,641 5 75,308 8 Laboratory mean47,412 3 57,215 8 73,541 7 75,949 4 75,538 4 LAB 2 Individual values 47,832 8 48,302 7 57,142 8 57,616 9 73,557 8 73,782 4 75,452 6 75,741 0 75,071 9 75,407 0 48,049 8 57,267 4 73,512 3 75,294 3 75,879 2 Laboratory mean48,061 8 57,342 4 73,617 5 75,496 0 75,452 7 LAB 4 Individual values 47,931 4 48,234 8 54,847 6 56,227 7 73,179 1 72,865 3 75,372 6 74,737 0 75,327 8 74,892 6 48,601 6 55,158 2 73,111 8 75,048 0 75,598 1 Laboratory mean 48,255 9 55,411 2 73,0
