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 part of 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 fluorescence spectrometry.
Kupfer und Kupferlegierungen - Bestimmung von Hauptbestandteilen und Verunreinigungen durch wellenlängendispersive Röntgenfluoreszenzanalyse (RFA) - Teil 1: Anleitungen für das Routineverfahren
Dieser Teil dieser Europäischen Norm bietet eine Anleitung zu Konzepten und Arbeitsabläufen für die Kalibrierung
und Analyse von Kupfer und Kupferlegierungen durch Röntgenfluoreszenzanalyse.
Cuivre et alliages de cuivre - Profilés et barres pour usages généraux
La présente Norme européenne fournit des lignes directrices sur les concepts et les procédures d’étalonnage et d’analyse du cuivre et des alliages de cuivre par la spectrométrie de fluorescence X à dispersion en longueur d’onde.
Baker in bakrove zlitine – Določevanje glavnih sestavin in nečistoč z rentgensko fluorescenčno spektrometrijo (XRF) – 1. del: Smernice za rutinsko metodo
Standards Content (Sample)
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.Copper and copper alloys - Determination of main constituents and impurities by wavelength dispersive X-ray fluorescence spectrometry (XRF) - Part 1: Guidelines to the routine methodCuivre et alliages de cuivre - Détermination des éléments principaux et des impuretés par analyse spectrométrique de fluorescence X a dispersion en longueur d'onde (XRF) - Partie 1: Lignes directrices pour la méthode de routineKupfer und Kupferlegierungen - Bestimmung von Hauptbestandteilen und Verunreinigungen durch wellenlängendispersive Röntgenfluoreszenzanalyse (RFA) - Teil 1: Anleitungen für das RoutineverfahrenTa slovenski standard je istoveten z:EN 15063-1:2006SIST EN 15063-1:2007en77.120.30Baker in bakrove zlitineCopper and copper alloysICS:SLOVENSKI
STANDARDSIST EN 15063-1:200701-januar-2007
EUROPEAN STANDARDNORME EUROPÉENNEEUROPÄISCHE NORMEN 15063-1November 2006ICS 77.040.20 English VersionCopper and copper alloys - Determination of main constituentsand impurities by wavelength dispersive X-ray fluorescencespectrometry (XRF) - Part 1: Guidelines to the routine methodCuivre et alliages de cuivre - Détermination des élémentsprincipaux et des impuretés par analyse spectrométriquede fluorescence X à dispersion en longueur d'onde (XRF) -Partie 1: Lignes directrices pour la méthode de routineKupfer und Kupferlegierungen - Bestimmung vonHauptbestandteilen und Verunreinigungen durchwellenlängendispersive Röntgenfluoreszenzanalyse (RFA) -Teil 1: Anleitungen für das RoutineverfahrenThis European Standard was approved by CEN on 22 September 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 bibliographical 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 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, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania,Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom.EUROPEAN COMMITTEE FOR STANDARDIZATIONCOMITÉ EUROPÉEN DE NORMALISATIONEUROPÄISCHES KOMITEE FÜR NORMUNGManagement Centre: rue de Stassart, 36
B-1050 Brussels© 2006 CENAll rights of exploitation in any form and by any means reservedworldwide for CEN national Members.Ref. No. EN 15063-1:2006: E
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Contents Page Foreword.3 Introduction.4 1 Scope.5 2 Principle.5 3 Terms and definitions.5 4 Instrumentation.7 5 Sampling and test sample preparation.12 6 Evaluation methods.12 7 Calibration strategy.15 8 Method validation (accuracy and precision).17 9 Performance criteria.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 (informative)
Example of performance criteria obtained in a precision test.22 Bibliography.23
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3 Foreword This European Standard (EN 15063-1:2006) has been prepared by Technical Committee CEN/TC 133 “Copper and copper alloys”, the secretariat of which is held by DIN. 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 May 2007, and conflicting national standards shall be withdrawn at the latest by May 2007. Within its programme of work, Technical Committee CEN/TC 133 requested CEN/TC 133/WG 10 "Methods of analysis" to prepare the following standard: EN 15063-1, 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 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 According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Cyprus, Czech Republic, Den-mark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxem-bourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzer-land and United Kingdom.
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Introduction Wavelength dispersive X-ray fluorescence spectrometry (XRF) has been used for several decades as an im-portant analytical tool for production analysis. XRF is characterised by its speed and high precision 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 primarily intended to be used for the analysis of metal alloys but it is also applicable to other
materials although the test specimen preparation techniques differ.
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5 1 Scope This part of 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 fluorescence spectrometry.
2 Principle An appropriately cleaned test specimen 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 are determined by relating the measured intensities of unknown test specimens to analytical curves prepared from reference materials of known concentrations. 3 Terms and definitions For the purposes of this European Standard, the following terms and definitions apply. 3.1 reference material material, one or more of whose property values are sufficiently homogeneous and well established to be used for calibrating an apparatus, assessing a measurement method, or for assigning values to materials 3.2 certified reference material reference material, accompanied by a certificate, one or more of whose property values are certified by a pro-cedure which establishes traceability to an accurate realisation of the unit in which the property values are expressed, and for which each certified value is accompanied by an uncertainty at a stated level of confidence 3.3 test sample representative quantity of material 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 high points of the calibration range for each element; used to detect variations over time in these points NOTE 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 recalibrate the spectrometer NOTE 1 These samples are measured during the calibration procedure and the intensities obtained are stored in the computer according to the manufacturer's instructions. NOTE 2 No chemical analyses are necessary, but the homogeneity of the 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 con-centrations of a number of calibration samples
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3.8 recalibration adjusting instrumental output to conform to the calibration NOTE To compensate for day to day instrumental variation, a set of recalibration samples are measured at the mini-mum low concentration and at a high concentration for each element (two-points recalibration). The measured intensities are compared to the 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 ratios of intensities for unknown reference materials NOTE Initial intensities for 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 di-rectly related to the desired observation NOTE 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 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 See Annex A. 3.13 lower limit of detection calculated minimum concentration based 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 See Annex A. 3.14 limit of quantification smallest concentration that can be determined with a specified confidence level related to the limit of detection by a factor dependent on the method NOTE See Annex A.
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7 3.15 sensitivity rate of change of signal with change in concentration NOTE See Annex A. Sensitivity is expressed as counts per second 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 concepts are shown in Figures 1 and 2. Each detail is described in the following sub-clauses.
Key 1 Crystal 2 Primary collimator 3 X-ray tube 4 Test specimen
5 Spinner 6 Counter 7 Secondary collimator Figure 1 — Plane crystal spectrometer geometry, used in sequential instruments
Key 1 Crystal 2 Source slit 3 X-ray tube 4 Test specimen
5 Spinner 6 Counter 7 Detector slit Figure 2 — Curved crystal spectrometer geometry, used in simultaneous instruments
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4.2 X-ray tubes Two different types of X-ray tubes are used: side-window tubes or end-window tubes. Table 1 compares 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 determined. Table 1 — Comparison between end-window and side-window tubes Feature 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 5 000 h
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9 The applicability of common anode materials is summarised in Table 2. Table 2 — Anode materials for X-ray tubes and relative fields of application Anode material Application
Rh Good excitation conditions for elements with a low or high atomic number.
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 applications according to the anode materials.
The X-ray tube produces a continuous spectrum and characteristic spectra depending on the selected anode material. For optimum excitation, a maximum excitation energy lying at least two to three times above the cor-responding absorption edge of the element line to be measured, is recommended. Equipment is available which may be operated with acceleration voltages up to 100 kV and with a maximum power of 3 kW. The applicability of the apparatus is derived from either the high-voltage supply or the X-ray tube used. Using acceleration voltages above 60 kV is only advantageous in a few cases, e.g. to determine traces of elements with a high atomic number. The fluorescence arising inside a test specimen is emitted uniformly in all directions. Only a fraction reaches the test specimen surface. The proportion of the fluorescence measured depends on the angle between the test specimen surface and the spectrometer. The nearer to perpendicular the beam of radiation is to the test specimen, the deeper the layers of the test specimens that are measured. 4.3 Vacuum system The test specimen is placed in the spectrometer chamber to be measured. To analyse copper and copper al-loys it is recommended, for all elements, to measure under vacuum, to maintain stable conditions in the in-strument. A pressure of 13 Pa or less, controlled to ± 3 Pa is required. 4.4 Test specimen spinner Most instruments are equipped with a test specimen spinner to avoid effects of inhomogeneities, e. g. grinding striations. If not, the test specimen shall be orientated so that the relation between the X-ray beam and the inhomogeneities is always the same from measurement to measurement. 4.5 Filters If the element to be determined is the same as the anode material, a filter has to be put in front of the exit win-dow of the tube to eliminate the characteristic lines. The efficiency of a filter depends on its material and thick-ness. A filter made of titanium or aluminium is often used to eliminate the characteristic lines from a chromium anode. When a filter is used, the sensitivity for the element of interest will significantly decrease. Sometimes a filter can be used to increase the peak to background ratio for low concentrations of elements with a high atomic number. Many instruments are supplied with a filter changer containing filters of different materials and thicknesses.
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4.6 Collimators of slits In a plane crystal geometry (Figure 1), only a portion of the secondary radiation is selected by a primary colli-mator and the parallel beam is allowed to penetrate the plane surface of the crystal. The resolution of the spectrometer is affected not only by the crystal used, but also by the collimation of the radiation. The finer the collimator selected, the better the resolution, but the intensity measured is lower. Most sequential spectrome-ters of this type are supplied with at least two collimators: coarse and fine. In a curved crystal geometry (Figure 2), using collimators is not necessary as the radiation is focussed on the detector by a slit system. 4.7 Analysing crystals Analysing crystals are flat or curved with optimised capability for diffraction of the wavelength of interest. In order to isolate individual characteristic lines emitted by the test specimen, large single crystals are used as dispersion media. To cover the usual wavelength range between 0,2 Å and 15 Å, crystals with different spaces between the atomic layers (d-value) are used. Commonly used analysing crystals are listed in Table 3 for measuring the Kα-lines of particular elements. To cover the whole wavelength range, a minimum of three crystals is required; LiF(200), PET and TlAP or a multi-layer crystal for elements with a low atomic number. Table 3 — Crystals and their fields of application Crystal Lattice planes 2 d-value (nm) Elements Lithium fluoride (LiF) 220 0,284 8 Ti, V, Cr, Mn, Fe, Co, Ni Lithium fluoride (LiF) 200 0,402 7 K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Sr, V Germanium (Ge) 111 0,653 2 P, S, Cl Pyrolitic graphite (PG) 002 0,671 5 P, S, Cl Pentaerythritol (PET) 002 0,874 2 Al, Si, P, S, Cl Ammonium dihydrogen phosphate (ADP) 101 1,064 2 Mg, Na Thallium hydrogen phtalate (TlAP) 100 2,575 F, Mg, Na, Al Multi-layer crystal — Variable Elements Za
< 11 a Atomic number.
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11 A typical set of crystals used for the analysis of copper and copper materials is shown in Table 4. Table 4 — Typical set of crystals for the analysis of copper and copper alloys Channel No. Line Crystal d-value nm 2 θ
degrees Counter FC/SCa
Foil thickness µm 1 CKα1, 2 OVO — C
48,02 FC 1,0 2 MgKα1, 2 OVO 55
20,70 FC 1,0 3 AlKα1, 2
144,92 FC 1,5 4 SiKα1, 2
109,12 FC 1,5 5 PKα1, 2
141,14 FC 1,5 6 SKα1, 2
110,74 FC 1,5 7 AgLα1
79,00 FC 6,0 8 CdLβ1
136,32 FC 6,0 9 SbLα1
117,31 FC 6,0 10 TeLα1
109,50 FC 6,0 11 CrKα1, 2
69,36 FC 6.0 12 MnKα1, 2
62,98 FC 6,0 13 FeKα1, 2
57,51 FC 6,0 14 NiKα1, 2
48,65 SC — 15 ZnKα1, 2
41,80 SC — 16 CuKβ1
40,45 SC — 17 PbLα1
33,93 SC — 18 BiLα1
33,01 SC — 19 SeKα1, 2
31,89 SC — 20 AsKβ1
30,44 SC — 21 ZrKα1
22,50 SC — 22 SnKα1
13,99 SC — a FC = flow counter and SC = scintillation counter.
4.8 Counters The selected fluorescent radiation in a spectrometer is recorded by means of appropriate counters (flow counter, sealed gas counter, scintillation counter). The sensitivity of the various counters is a function of the radiation energy measured. In simultaneous instruments the most suitable counter should be used for the par-ticular element line.
In sequential instruments, flow and scintillation counters are generally used at the same time and are connected in a series (tandem connection). For elements with atomic numbers below 25, the flow counter is used, and with atomic numbers above 30, the scintillation counter is used. For elements with atomic numbers between 25 and 30, both counters are used in tandem if possible. In simultaneous instru-ments, gas counters filled with Kr or Xe are often used for elements with atomic numbers between 20 and 40. All counters can record only a limited number of pulses per unit of time because the measuring process for each pulse requires a fixed amount of time, which is in the order of 1 µs to 100 µs. Other pulses cannot be detected in this time, which is defined as dead time τ. Therefore, care shall be taken to ensure that the maxi-mum pre-set pulse rate is not exceeded. This is possible, for example, by connecting attenuation filters (simul-taneous equipment) or decreasing the tube current. Otherwise, there will be no linearity between the intensity of the X-ray radiation and the pulse rate measured. NOTE Normally the number of pulses (counts) is indicated as kilocounts per second (Kc/s).
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The dead time of the counters may ha