DIN EN 15063-1-2015 Copper and copper alloys - Determination of main constituents and impurities by wavelength dispersive X-ray fluorescence spectrometry (XRF) - Part 1 Guidelines .pdf

1、March 2015 Translation by DIN-Sprachendienst.English price group 13No 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).ICS

2、77.040.20; 77.120.30!%AR$“2304701www.din.deDDIN EN 15063-1Copper and copper alloys Determination of main constituents and impurities by wavelengthdispersive X-ray fluorescence spectrometry (XRF) Part 1: Guidelines to the routine method;English version EN 15063-1:2014,English translation of DIN EN 15

3、063-1:2015-03Kupfer und Kupferlegierungen Bestimmung von Hauptbestandteilen und Verunreinigungen durch wellenlngendispersiveRntgenfluoreszenzanalyse (RFA) Teil 1: Leitfaden fr das Routineverfahren;Englische Fassung EN 15063-1:2014,Englische bersetzung von DIN EN 15063-1:2015-03Cuivre et alliages de

4、cuivre Dtermination des lments principaux et des impurets par spectromtrie defluorescence X dispersion de longueur donde (FRX) Partie 1: Lignes directrices pour la mthode de routine;Version anglaise EN 15063-1:2014,Traduction anglaise de DIN EN 15063-1:2015-03SupersedesDIN EN 15063-1:2007-01www.beut

5、h.deIn case of doubt, the German-language original shall be considered authoritative.Document comprises 25 pages 03.15 DIN EN 15063-1:2015-03 2 A comma is used as the decimal marker. National foreword This document (EN 15063-1:2014) has been prepared by Technical Committee CEN/TC 133 “Copper and cop

6、per alloys” (Secretariat: DIN, Germany). The responsible German body involved in its preparation was the DIN-Normenausschuss Nichteisenmetalle (DIN Standards Committee Nonferrous Metals), Working Committee NA 066-02-06 AA Analysenverfahren fr NE-Metalle. Amendments This standard differs from DIN EN

7、15063-1:2007-01 as follows: a) the definitions of 3.1 and 3.2 have been modified; b) Clause 5 “Sampling and test sample preparation” has been revised; c) the standard has been editorially revised. Previous editions DIN EN 15063-1: 2007-01 EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 15063-1

8、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 cuivre - Dterm

9、ination 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 Rntgenfluore

10、szenzanalyse (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 standard wi

11、thout 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 in any othe

12、r 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, Czech Republic,

13、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. EUROPEAN COMMI

14、TTEE 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 EEN 15063-1:2

15、014 (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 of slits 10 4.7 Analysing cryst

16、als 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-element effects correction models 13

17、 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 7.7 Selecting drift cont

18、rol 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 17 10 Radiation protection . 1

19、8 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 (informative) Example of performance c

20、riteria obtained under repeatability conditions . 22 Bibliography . 23 DIN EN 15063-1:2015-03 EN 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 DIN. This European Standard

21、 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 the elements of this docume

22、nt 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 of analysis” to revise th

23、e 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 determination of main constituent

24、s 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, the following changes have

25、 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: Austria, Belgium, Bulgari

26、a, 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, Sweden, Switzerland, Turke

27、y and the United Kingdom. DIN EN 15063-1:2015-03 EN 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 precision over a wide

28、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 to be used for the a

29、nalysis of copper and copper alloys but it may also be applied to other materials. DINEN 15063-1:2015-03EN 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 dispersive X-ray fl

30、uorescence 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. Concentrations of elements

31、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 homogeneous and stable w

32、ith 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 procedure for one or

33、 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 material for testing p

34、urposes 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 high points of the

35、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 ranges used to rec

36、alibrate 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. DIN EN 15063-1:2015-03 EN 15063-1:2014(E)6 Note 2 to entry: No chemical analyses are necessary,

37、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 output to confor

38、m 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 initial measur

39、ed 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 the reference

40、 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 desired observati

41、on 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 entry: See Annex A

42、. 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 based on counting

43、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 confidence level

44、related to the limit of detection by a factor dependent on the method Note 1 to entry: See Annex A. DIN EN 15063-1:2015-03 EN 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 percent,

45、 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 concepts

46、 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 DIN EN 15063-1:2015-03 EN 15063-

47、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 compares

48、 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 alloys, 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