BS EN 15063-1-2014 Copper and copper alloys Determination of main constituents and impurities by wavelength dispersive X-ray fluorescence spectrometry (XRF) Guidelines to the routi.pdf

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1、BSI Standards PublicationBS EN 15063-1:2014Copper and copper alloys Determination of mainconstituents and impuritiesby wavelength dispersive X-ray fluorescence spectrometry(XRF)Part 1: Guidelines to the routine methodBS EN 15063-1:2014 BRITISH STANDARDNational forewordThis British Standard is the UK

2、 implementation of EN 15063-1:2014.It supersedes BS EN 15063-1:2006 which is withdrawn.The UK participation in its preparation was entrusted to TechnicalCommittee NFE/34/1, Wrought and unwrought copper and copperalloys.A list of organizations represented on this committee can beobtained on request t

3、o its secretary.This publication does not purport to include all the necessaryprovisions of a contract. Users are responsible for its correctapplication. The British Standards Institution 2014. Published by BSI StandardsLimited 2014ISBN 978 0 580 83960 3ICS 77.040.20; 77.120.30Compliance with a Brit

4、ish Standard cannot confer immunity fromlegal obligations.This British Standard was published under the authority of theStandards Policy and Strategy Committee on 31 December 2014.Amendments issued since publicationDate Text affectedBS EN 15063-1:2014EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM

5、 EN 15063-1 December 2014 ICS 77.040.20; 77.120.30 Supersedes EN 15063-1:2006English Version Copper and copper alloys - Determination of main constituents and impurities by wavelength dispersive X-ray fluorescence spectrometry (XRF) - Part 1: Guidelines to the routine method Cuivre et alliages de cu

6、ivre - Dtermination des lments principaux et des impurets par spectromtrie de fluorescence X dispersion de longueur donde (FRX) - Partie 1 : Lignes directrices pour la mthode de routine Kupfer und Kupferlegierungen - Bestimmung von Hauptbestandteilen und Verunreinigungen durch wellenlngendispersive

7、Rntgenfluoreszenzanalyse (RFA) -Teil 1: Leitfaden fr das Routineverfahren This European Standard was approved by CEN on 8 November 2014. CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this European Standard the status of a national

8、 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). A version

9、 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, Cyprus, Czec

10、h Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and United Kingdom. EU

11、ROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels 2014 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 15063-1:2014 E

12、BS EN 15063-1:2014EN 15063-1:2014 (E) 2 Contents Page Foreword 3 Introduction .4 1 Scope 5 2 Principle 5 3 Terms and definitions .5 4 Instrumentation 7 4.1 Principles of X-ray fluorescence spectrometers 7 4.2 X-ray tubes .8 4.3 Vacuum system9 4.4 Test sample spinner 9 4.5 Filters 9 4.6 Collimators o

13、f slits 10 4.7 Analysing crystals 10 4.8 Counters 11 4.9 Simultaneous and sequential Instruments 12 5 Sampling and test sample preparation 12 6 Evaluation methods 12 6.1 General . 12 6.2 Dead time correction 12 6.3 Background correction 13 6.4 Line interference correction models. 13 6.5 Inter-elemen

14、t effects correction models 13 7 Calibration procedure 14 7.1 General . 14 7.2 Optimizing of the diffraction angle (2) 15 7.3 Selecting optimum conditions for detectors . 15 7.4 Selecting optimum tube voltage and current 15 7.5 Selecting minimum measuring times . 15 7.6 Selecting calibration samples

15、 . 15 7.7 Selecting drift control and recalibration samples . 16 7.8 Measuring the calibration samples . 16 7.9 Regression calculations 16 8 Method validation (accuracy and precision) 16 9 Performance criteria . 17 9.1 General . 17 9.2 Precision test 17 9.3 Performance monitoring 17 9.4 Maintenance

16、17 10 Radiation protection . 18 Annex A (informative) Example of calculating background equivalent concentration, limit of detection, limit of quantification and lower limit of detection . 19 Annex B (informative) Example of calculating line interference of one element to another 21 Annex C (informa

17、tive) Example of performance criteria obtained under repeatability conditions . 22 Bibliography . 23 BS EN 15063-1:2014EN 15063-1:2014 (E) 3 Foreword This document (EN 15063-1:2014) has been prepared by Technical Committee CEN/TC 133 “Copper and copper alloys”, the secretariat of which is held by DI

18、N. 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 June 2015 and conflicting national standards shall be withdrawn at the latest by June 2015. Attention is drawn to the possibility that some of th

19、e 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. This document supersedes EN 15063-1:2006. Within its programme of work, Technical Committee CEN/TC 133 requested CEN/TC 133/WG 10 “Methods

20、of analysis” to revise the following standard: EN 15063-1:2006, Copper and copper alloys Determination of main constituents and impurities by wavelength dispersive X-ray fluorescence spectrometry (XRF) Part 1: Guidelines to the routine method This is one of two parts of the standard for the determin

21、ation of main constituents and impurities in copper and copper alloys. The other part is: EN 15063-2, Copper and copper alloys Determination of main constituents and impurities by wavelength dispersive X-ray fluorescence spectrometry (XRF) Part 2: Routine method In comparison with EN 15063-1:2006, t

22、he following changes have been made: a) Definition 3.1 and 3.2 modified; b) Clause 5 modified; c) Editorial modifications have been made. According to the CEN-CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard:

23、Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, S

24、weden, Switzerland, Turkey and the United Kingdom. BS EN 15063-1:2014EN 15063-1:2014 (E) 4 Introduction Wavelength dispersive X-ray fluorescence spectrometry (XRF) has been used for several decades as an important analytical tool for production analysis. XRF is characterised by its speed and high pr

25、ecision over a wide concentration range and as the XRF-method in most cases is used as a relative method, the limitations are often connected to the quality of the calibration samples. The technique is well established and most of the physical fundamentals are well known. This guideline is intended

26、to be used for the analysis of copper and copper alloys but it may also be applied to other materials. BS EN 15063-1:2014EN 15063-1:2014 (E) 5 1 Scope This European Standard provides guidance on the concepts and procedures for the calibration and analysis of copper and copper alloys by wavelength di

27、spersive X-ray fluorescence spectrometry. 2 Principle An appropriately prepared test sample is 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 wavelengths. Concentrat

28、ions of elements are determined by relating the measured intensities of test samples to calibration curves prepared from reference materials. 3 Terms and definitions For the purposes of this document, the following terms and definitions apply. 3.1 reference material RM material, sufficiently homogen

29、eous and stable with respect to one or more specified properties which has been established to be fit for its intended use in a measurement process SOURCE: ISO GUIDE 30:1992/Amd.1:2008, definition 2.1 3.2 certified reference material CRM reference material characterized by a metrologically valid pro

30、cedure for one or more specified properties, accompanied by a certificate, that provides the value of the specified property, its associated uncertainty, and a statement of metrological traceability SOURCE: ISO GUIDE 30:1992/Amd.1:2008, definition 2.2 3.3 test sample representative quantity of mater

31、ial for testing purposes 3.4 calibration samples series of certified reference materials or if not available, reference materials used for calibration 3.5 drift control samples series of homogeneous materials that contain all the elements which have been calibrated and that cover the low, mid and hi

32、gh points of the calibration range for each element, used to detect variations over time in these points Note 1 to entry: Drift control samples can also be used for statistical process control (SPC) of the instrument. 3.6 recalibration samples samples at both low and high points in the calibration r

33、anges used to recalibrate the spectrometer Note 1 to entry: These samples are measured during the calibration procedure and the intensities obtained are stored in the computer according to the manufacturers instructions. BS EN 15063-1:2014EN 15063-1:2014 (E) 6 Note 2 to entry: No chemical analyses a

34、re necessary, but the homogeneity of these samples should be carefully evaluated. 3.7 calibration process to establish the curve(s) by measuring and calculating the best fit of net intensities for elemental concentrations of a number of calibration samples 3.8 recalibration adjusting instrumental ou

35、tput to conform to the calibration Note 1 to entry: To compensate for day to day instrumental variation, a set of recalibration samples are measured at the minimum low concentration and at a high concentration for each element (two-points recalibration). The measured intensities are compared to the

36、initial measured intensities stored during the calibration procedure and the recalibration coefficients are calculated. Calibration constants are not changed. 3.9 reference measurements measurements carried out to determine intensities for reference materials Note 1 to entry: Initial intensities for

37、 the reference materials are stored during the calibration procedure and the intensities are updated to compensate for day to day variations. 3.10 spectral background background caused by radiation energy of a wavelength corrected for its position in the spectrum, but not directly related to the des

38、ired observation Note 1 to entry: For a spectral line, spectral background may consist of other lines, bands or continuous radiation. 3.11 background equivalent concentration concentration of analyte, which, when it is excited, provides a net intensity equal to the spectral background Note 1 to entr

39、y: See Annex A. 3.12 limit of detection minimum concentration at which the signal generated by a given element can be positively recognised with a specified confidence level above any background signals Note 1 to entry: See Annex A. 3.13 lower limit of detection calculated minimum concentration base

40、d on counting statistical error at which the signal generated by a given element can be positively recognised, with a specified confidence level, above any background signals Note 1 to entry: See Annex A. 3.14 limit of quantification smallest concentration that can be determined with a specified con

41、fidence level related to the limit of detection by a factor dependent on the method Note 1 to entry: See Annex A. BS EN 15063-1:2014EN 15063-1:2014 (E) 7 3.15 sensitivity rate of change of signal with change in concentration Note 1 to entry: See Annex A. Sensitivity is expressed as counts per second

42、 percent, and derived by difference in signals between a sample with a high concentration and one with a low concentration divided by the difference in concentrations. 4 Instrumentation 4.1 Principles of X-ray fluorescence spectrometers The principles of two different X-ray fluorescence spectrometer

43、 concepts are shown in Figures 1 and 2. Each detail is described in the following sub-clauses. Key 1 Crystal 5 Spinner 2 Primary collimator 6 Counter 3 X-ray tube 7 Secondary collimator 4 Test sample Figure 1 Plane crystal spectrometer geometry, used in sequential instruments BS EN 15063-1:2014EN 15

44、063-1:2014 (E) 8 Key 1 Crystal 5 Spinner 2 Source slit 6 Counter 3 X-ray tube 7 Detector slit 4 Test sample Figure 2 Curved crystal spectrometer geometry, used in simultaneous instruments 4.2 X-ray tubes Two different types of X-ray tubes are used: side-window tubes or end-window tubes. Table 1 comp

45、ares these two types. More favourable measuring conditions are usually obtained for elements with a low atomic number (Z 20) with an end-window tube due to the thinner window. Different high purity elements such as Rh, Ag, W, Cr or Au are used as anode materials. For analysing copper and copper allo

46、ys, rhodium is usually used as the anode material in a multipurpose tube as it provides good excitation conditions for all elements of interest. If possible, the anode material should not be the same as the element to be determined. Table 1 Comparison between end-window and side-window tubes Feature

47、 End-window tubes Side-window tubes Cooling Two cooling circuits a) Direct cooling with deionised water b) Indirect cooling with tap water One cooling circuit Direct cooling with tap water Window Slight thermal stressing: Thinner window Greater thermal stressing: Thicker window Service Life 20 000 h

48、 5 000 h The applicability of common anode materials is summarised in Table 2. BS EN 15063-1:2014EN 15063-1:2014 (E) 9 Table 2 Anode materials for X-ray tubes and corresponding fields of application Anode material Application Rh Good excitation conditions for elements with a low or high atomic numbe

49、r. Cr Good excitation conditions for elements with a low atomic number, especially for K, Ca and Ti. Not so good for elements with a high atomic number. Mo Good excitation conditions for elements with a high atomic number, especially for Rb and Sr. W Good excitation conditions for elements with a high atomic number, especially for Fe and Ni. Au Good excitation conditions for elements with a high atomic number, especially for Cu and Zn. Ag Equivalent to Rh. Ag is used if Rh lines interfere with element of interest. Double anode Different applicati