1、BS EN 10315:2006ICS 77.040.30; 77.140.20NO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAWBRITISH STANDARDRoutine method for analysis of high alloy steel by X-ray fluorescence spectrometry (XRF) by using a near by techniqueThis British Standard was published under the authority o
2、f the Standards Policy and Strategy Committee on 30 September 2009 BSI 2009ISBN 978 0 580 68841 6Amendments/corrigenda issued since publicationDate CommentsBS EN 10315:2006National forewordThis British Standard is the UK implementation of EN 10315:2006.The UK participation in its preparation was ent
3、rusted to TechnicalCommittee ISE/18, Sampling and analysis of iron and steel.A list of organizations represented on this committee can be obtained onrequest to its secretary.This publication does not purport to include all the necessary provisionsof a contract. Users are responsible for its correct
4、application. Compliance with a British Standard cannot confer immunityfrom legal obligations.BS EN 10315:2006EUROPEAN STANDARDNORME EUROPENNEEUROPISCHE NORMEN 10315July 2006ICS 77.040.30; 77.140.20English VersionRoutine method for analysis of high alloy steel by X-rayFluorescence Spectrometry (XRF)
5、by using a near by techniqueMthode de routine pour lanalyse des aciers fortementallis par spectromtrie de fluorescence de rayons X(SFRX) laide dune mthode de correctionStandardverfahren zur Analyse von hochlegiertem Stahlmittels Rntgenfluoreszenzspektroskopie (RFA) unterAnwendung eines Vergleichs-Ko
6、rrekturverfahrensThis European Standard was approved by CEN on 24 May 2006.CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this EuropeanStandard the status of a national standard without any alteration. Up-to-date lists and bibliogr
7、aphical references concerning such nationalstandards may be obtained on application to the Central Secretariat or to any CEN member.This European Standard exists in three official versions (English, French, German). A version in any other language made by translationunder the responsibility of a CEN
8、 member into its own language and notified to the Central Secretariat has the same status as the officialversions.CEN members are the national standards bodies of Austria, Belgium, Cyprus, Czech Republic, Denmark, Estonia, Finland, France,Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Li
9、thuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania,Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom.EUROPEAN COMMITTEE FOR STANDARDIZATIONCOMIT EUROPEN DE NORMALISATIONEUROPISCHES KOMITEE FR NORMUNGManagement Centre: rue de Stassart, 36 B-1050 Brussels 2006 C
10、EN All rights of exploitation in any form and by any means reservedworldwide for CEN national Members.Ref. No. EN 10315:2006: EBS EN 10315:2006EN 10315:2006 (E) 2 Contents Page Foreword3 1 Scope 4 2 Normative references 4 3 Principle5 4 Reagents.5 5 Apparatus .6 6 Safety precautions.7 7 Sampling.7 8
11、 Final sample preparation 7 9 Procedure .7 10 Calibration 8 11 Standardization9 12 Statistical Process Control (SPC) parameters9 13 ”Near by technique” method10 14 Test report 10 Annex A (normative) Precision 12 Annex B (normative) Graphical representation of precision data17 Bibliography 28 BS EN 1
12、0315:2006EN 10315:2006 (E) 3 Foreword This document (EN 10315:2006) has been prepared by Technical Committee ECISS/TC 20 “Methods of chemical analysis of ferrous products”, the secretariat of which is held by SIS. This European Standard shall be given the status of a national standard, either by pub
13、lication of an identical text or by endorsement, at the latest by January 2007, and conflicting national standards shall be withdrawn at the latest by January 2007. According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are bound to impleme
14、nt this European Standard: Austria, Belgium, 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 K
15、ingdom. BS EN 10315:2006EN 10315:2006 (E) 4 1 Scope This European Standard specifies a procedure on how to improve the performance of a routine XRF method, already in use for analysis of high alloy steels, by using a ”near by technique”. The ”near by technique” requires at least one target sample (p
16、referable a CRM) of a similar composition as the unknown sample. The method is applicable to elements within the concentration ranges according to Table 1: Table 1 Concentration ranges Element Concentration range, % (m/m) aSi 0,05 to 1,5 Mn 0,05 to 5,0 P 0,005 to 0,035 Cr 10 to 25 Ni 0,1 to 30 Mo 0,
17、1 to 6,5 Cu 0,02 to 1,5 Co 0,015 to 0,30 V 0,015 to 0,15 Ti 0,015 to 0,50 Nb 0,05 to 1,0 aThe concentration ranges specified, represents those ranges studied during the precision test. The procedure has the potential to be used outside those ranges but it needs to be validated by each laboratory in
18、every case. The method is applicable to analysis of either chill-cast or wrought samples having a diameter of at least 25 mm and with a carbon concentration of less than 0,3 % (see NOTE). Other elements should have a concentration below 0,2 %. NOTE High carbon concentrations, in combination with hig
19、h Mo and Cr concentrations, could have undesirable structural effects on the sample and could affect the determination of phosphorus and chromium, in particular. Matrix effects exist between the elements listed. To compensate for those inter-element effects, mathematical corrections shall be applied
20、. A variety of computer programs for corrections is commonly used and included in the software package from the manufacturers. 2 Normative references The following referenced documents are indispensable for the application of this document. For dated references, only the edition cited applies. For u
21、ndated references, the latest edition of the referenced document (including any amendments) applies. EN ISO 10280, Steel and iron Determination of titanium content Diantipyrylmethane spectrophotometric method (ISO 10280:1991) BS EN 10315:2006EN 10315:2006 (E) 5 EN ISO 10700, Steel and iron Determina
22、tion of manganese content Flame atomic spectrometric method (ISO 10700:1994) EN ISO 10714, Steel and iron Determination of phosphorus content Phosphovanadomolybdate spectrophotometric method (ISO 10714:1992) EN ISO 14284, Steel and iron Sampling and preparation of samples for the determination of ch
23、emical composition (ISO 14284:1996) CR 10299, Guidelines for the preparation of standard routine methods with wavelength-dispersive X-ray fluorescence spectrometry ISO 4829-1, Steel and cast iron Determination of total silicon content Reduced molybdosilicate spectrophotometric method Part 1: Silicon
24、 contents between 0,05 and 1,0 % ISO 4829-2, Steel and iron Determination of total silicon content Reduced molybdosilicate spectrophotometric method Part 2: Silicon contents between 0,01 and 0,05 % ISO 4937, Steel and iron Determination of chromium content Potentiometric or visual titration method I
25、SO 4938, Steel and iron Determination of nickel content Gravimetric or titrimetric method ISO 4942, Steel and iron Determination of vanadium content N-BPHA spectrophotometric method ISO 4946, Steel and cast iron Determination of copper content 2,2-Diquinolyl spectrophotometric method ISO 9441, Steel
26、 Determination of niobium content PAR spectrophotometric method ISO 11652, Steel and iron Determination of cobalt content Flame atomic absorption spectrometric method ISO/TS 13899-1, Steel Determination of Mo, Nb and W contents in alloyed steel Inductively coupled plasma atomic emission spectrometri
27、c method Part 1: Determination of Mo content 3 Principle The sample is finished to a clean uniform surface and then irradiated by an X-ray beam of high energy. The secondary X-rays produced are dispersed by means of crystals and the intensities are measured by detectors at selected characteristic wa
28、velengths. The measuring time is set to reach below a specified counting statistical error. Preliminary concentrations of the elements are determined by relating the measured intensities of unknown samples to analytical curves prepared from reference materials, CRM or RM, of known compositions. The
29、final concentrations are calculated by using the results obtained by measuring a CRM of the same grade. The correction is made for the elements of interest by using the difference between the certified value and the value obtained during the measurement of the CRM (the “near by technique“). A fixed
30、channel or a sequential system may be used to provide simultaneous or sequential determinations of element concentrations. 4 Reagents 4.1 P10 gas (90 % argon mixed with 10 % methane) for the gas-flow proportional detector. 4.2 A set of Certified Reference Materials (CRM). All reference material used
31、 for calibration or calibration verification shall be certified by internationally recognized bodies (see NOTE). BS EN 10315:2006EN 10315:2006 (E) 6 NOTE A complete set of internationally recognised CRMs to cover all elements at all concentration levels may not be available. Other CRMs could be used
32、 if the material is certified by referee procedures based on SI units. 4.3 Reference materials used for standardization or for statistical process control (SPC samples) of the method need not to be certified, but adequate homogeneity data shall be available. Select the standardization samples in suc
33、h a way that they cover at least the low and top end of the concentration range for each element. 4.4 Pure ethanol. 5 Apparatus 5.1 Sample preparation equipment For the final preparation, use a surface grinder with 180-grit or finer aluminium oxide (see NOTE) belts or discs. Other preparation proced
34、ures are also possible (turning, for example). But in each case, the surfaces of CRMs, RMs and samples shall be prepared under the same conditions. NOTE Paper made of silicon carbide will disable Si determinations and paper made of zirconium oxide will disable Zr determinations, and aluminium determ
35、inations also sometimes as zirconium oxide is often contaminated by aluminium oxide. 5.2 X-ray fluorescence spectrometer A simultaneous or sequential wavelength dispersive spectrometer. This test method is written for use with commercially available instruments. 5.3 X-ray tube Tube with a high-purit
36、y element target. Rhodium is recommended for analysis of steel. 5.4 Analysing crystals To cover all elements specified in this method, flat or curved crystals made of LiF(200) and PE (for light elements, atom no. approximately 25) of the check samples. The measurements should have been performed und
37、er reproducibility conditions within laboratory (same instrument, same sample, different sample cups, different operators, and different days). Control charts for checking method performance are built up in the same way but the check samples are treated as unknown samples, e.g. sample preparation is
38、 included. BS EN 10315:2006EN 10315:2006 (E) 10 13 ”Near by technique” method 13.1 Principle Since this is a routine method, it is assumed that most users have their instrument already calibrated for steel (often optimized for in-house purposes). The concentration range given in Clause 1 represents
39、a wide range of different steels. In order to eliminate the effect of not having a calibration that covers all different kinds of steel or to improve (minimize) the uncertainty in the reported values a ”Near by technique” method could be used. By measuring the unknown sample together with a sample w
40、ith known concentration (of the same steel grade), a correction of the calculated concentrations for the unknown sample can be done. NOTE Be careful when using this method outside the calibrated range, but still within the range given in Clause 1. As an example, if the routine method is calibrated f
41、or a molybdenum concentration up to 3 % and an unknown sample with a concentration of 5 % is going to be measured, ensure that the detector is not saturated due to high intensities. If that is the case, a new calibration should be done covering that range. 13.2 Criteria for selecting CRMs a) Use onl
42、y CRMs from well recognized manufacturers; NOTE A complete set of internationally recognized CRMs to cover all steel grades are not available today. Other CRMs could be used (e.g. in-house RMs) if they are certified by referee procedures based on SI units, for those elements of interest. b) if possi
43、ble, the CRM should have the same metallurgical history (micro structure); c) the certified values should be followed by a calculated uncertainty; d) the closeness in composition between the unknown and the CRM is critical. As a rule of thumb, the following rules could be used: 1) major elements ( 1
44、 %): The CRM should not deviate more then 10 % relative; 2) minor elements ( 1 %): The CRM should not deviate more than 50 % relative. 14 Test report The test report shall include the following information: a) all information necessary for the identification of the sample, the laboratory and the dat
45、e of analysis. Full information of the CRM that has been used should be added; b) the method used, by reference to this European Standard, i.e. EN 10315; c) the results and the form in which they are expressed. Report the corrected values as shown in the following example: BS EN 10315:2006EN 10315:2
46、006 (E) 11 EXAMPLE Element Certified Reference Material “Target sample” DifferenceC Unknown measured Unknown corrected Certified value Measured Si 1,23 1,25 - 0,02 1,35 1,33 Mn 4,26 4,16 0,10 4,49 4,59 P 0,024 0,020 0,004 0,015 0,019 d) any unusual features noted during the determination; e) any ope
47、ration not specified in this European Standard or any optional operation which may have influenced the results. A precision test was performed within ECISS/TC 20/WG 1 during 2001/2002 using the ”near by technique” method (NTM). Eleven laboratories from five countries participated in the test. Altoge
48、ther one set of 15 unknown test samples and another 15 target samples were circulated between the participating laboratories, see Table A.1. During the statistical calculations those criteria formulated in 13.2 d), have been followed. BS EN 10315:2006EN 10315:2006 (E) 12 Annex A (normative) Precisio
49、n Table A.1 Composition of test- and target samples, target samples in italics Sample C Si Mn P Cr Ni Mo Cu Co V Ti Nb N SS9911 0,055 0,63 1,673 0,016 17,178 10,155 0,22 0,212 0,159 0,127 0,445 SS9912 0,062 0,48 1,219 0,031 17,207 9,350 0,21 0,282 0,149 0,065 0,509 SS9921 0,031 0,071 0,048 0,007 12,608 8,354 2,145 0,053 0,026 0,016 SS9922 0,035 0,091 0,062 0,008 12,604 8,315 2,236 0,042 0,038 0,050 SS9931 0,022 0,618 1,691 0,031 18,648 8,234 0,697 0,538 0,287 0,117 SS9932 0,063 0,447 1,739 0,025 18,240
