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 techniqueLicensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 15
2、/12/2009 08:00, Uncontrolled Copy, (c) BSIThis British Standard was published under the authority of 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
3、 Standard is the UK implementation of EN 10315:2006.The UK participation in its preparation was entrusted 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 p
4、urport to include all the necessary provisionsof a contract. Users are responsible for its correct application. Compliance with a British Standard cannot confer immunityfrom legal obligations.Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 15/12/2009 08:00, Uncontrolled Copy, (c) BSIBS EN 103
5、15:2006EUROPEAN STANDARDNORME EUROPENNEEUROPISCHE NORMEN 10315July 2006ICS 77.040.30; 77.140.20English VersionRoutine method for analysis of high alloy steel by X-rayFluorescence Spectrometry (XRF) by using a near by techniqueMthode de routine pour lanalyse des aciers fortementallis par spectromtrie
6、 de fluorescence de rayons X(SFRX) laide dune mthode de correctionStandardverfahren zur Analyse von hochlegiertem Stahlmittels Rntgenfluoreszenzspektroskopie (RFA) unterAnwendung eines Vergleichs-KorrekturverfahrensThis European Standard was approved by CEN on 24 May 2006.CEN members are bound to co
7、mply 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 bibliographical references concerning such nationalstandards may be obtained on application to the Central Sec
8、retariat 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 member into its own language and notified to the Central Secretariat has the same status as the offic
9、ialversions.CEN members are the national standards bodies of 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,
10、Sweden, Switzerland and United Kingdom.EUROPEAN COMMITTEE FOR STANDARDIZATIONCOMIT EUROPEN DE NORMALISATIONEUROPISCHES KOMITEE FR NORMUNGManagement Centre: rue de Stassart, 36 B-1050 Brussels 2006 CEN All rights of exploitation in any form and by any means reservedworldwide for CEN national Members.
11、Ref. No. EN 10315:2006: ELicensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 15/12/2009 08:00, Uncontrolled Copy, (c) BSIBS 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 Fi
12、nal 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 Licensed C
13、opy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 15/12/2009 08:00, Uncontrolled Copy, (c) BSIBS EN 10315:2006EN 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 hel
14、d by SIS. This European Standard shall be given the status of a national standard, either by publication 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 R
15、egulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands
16、, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom. Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 15/12/2009 08:00, Uncontrolled Copy, (c) BSIBS EN 10315:2006EN 10315:2006 (E) 4 1 Scope This European Standard specifies a procedure on how t
17、o 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 (preferable a CRM) of a similar composition as the unknown sample. The method is applicable to elements wit
18、hin 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 0,1 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 concentrati
19、on 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 every case. The method is applicable to analysis of either chill-cast or wrought samples having a diamete
20、r 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 high Mo and Cr concentrations, could have undesirable structural effects on the sample and could affect the
21、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. A variety of computer programs for corrections is commonly used and included in the software package fr
22、om 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 undated references, the latest edition of the referenced document (including any amendments) applies. EN I
23、SO 10280, Steel and iron Determination of titanium content Diantipyrylmethane spectrophotometric method (ISO 10280:1991) Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 15/12/2009 08:00, Uncontrolled Copy, (c) BSIBS EN 10315:2006EN 10315:2006 (E) 5 EN ISO 10700, Steel and iron Determination o
24、f 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 chemical
25、 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 conte
26、nts 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 ISO 493
27、8, 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 Deter
28、mination 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 spectrometric meth
29、od 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 waveleng
30、ths. 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 final
31、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 channe
32、l 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 for c
33、alibration or calibration verification shall be certified by internationally recognized bodies (see NOTE). Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 15/12/2009 08:00, Uncontrolled Copy, (c) BSIBS EN 10315:2006EN 10315:2006 (E) 6 NOTE A complete set of internationally recognised CRMs to
34、cover all elements at all concentration levels may not be available. Other CRMs could be used 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
35、, but adequate homogeneity data shall be available. Select the standardization samples in such 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 grind
36、er with 180-grit or finer aluminium oxide (see NOTE) belts or discs. Other preparation procedures 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 determin
37、ations and paper made of zirconium oxide will disable Zr determinations, and aluminium determinations 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 w
38、ritten for use with commercially available instruments. 5.3 X-ray tube Tube with a high-purity 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, ato
39、m no. approximately 25) of the check samples. The measurements should have been performed under 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
40、the same way but the check samples are treated as unknown samples, e.g. sample preparation is included. Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 15/12/2009 08:00, Uncontrolled Copy, (c) BSIBS EN 10315:2006EN 10315:2006 (E) 10 13 ”Near by technique” method 13.1 Principle Since this is a
41、 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 a wide range of different steels. In order to eliminate the effect of not having a calibration that covers a
42、ll 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 with known concentration (of the same steel grade), a correction of the calculated concentrations for the unk
43、nown 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 for a molybdenum concentration up to 3 % and an unknown sample with a concentration of 5 % is going to be mea
44、sured, 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 only CRMs from well recognized manufacturers; NOTE A complete set of internationally recognized CRMs to cover a
45、ll 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 possible, the CRM should have the same metallurgical history (micro structure); c) the certified values should be
46、 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 %): The CRM should not deviate more then 10 % relative; 2) minor elements ( 1 %): The CRM should not deviat
47、e 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 date of analysis. Full information of the CRM that has been used should be added; b) the method used, by refere
48、nce 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: Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 15/12/2009 08:00, Uncontrolled Copy, (c) BSIBS EN 10315:2006EN 10315:2006 (E) 1
49、1 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 operation 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 (NT
