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 concentration range and since the technique in most cases is used as an relative method the limitations are often connected to the quality of the calibration samples. The technique is well established and most of its physical properties are well known.

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This document lists, under Clause 4, the European Standards which are currently available for the determination of the chemical composition of steels and cast irons.
In Clause 5, this document provides details on the range of application and gives the principle of the method described in each standard.
Items which are under preparation as European Standards or as CEN Technical Reports by ECISS/TC 102 are available on the webpage of CEN, through the  following link: https://standards.cen.eu/dyn/www/f?p=204:22:0::::FSP_ORG_ID:733643&cs=123E58BF77E3DE921F548B80C5FF2E5D4.
Annex A gives a list of other European Standards and CEN Technical Reports applicable for the determination of the chemical composition of steels and cast irons.
Annex B gives a list of withdrawn Euronorms, together with the corresponding replacement European Standards, if any.
Annex C shows graphical representations of the content ranges of the methods listed in this document. Figure C.1 gives the content ranges of the referee methods, Figure C.2 gives the content ranges of the routine methods and Figure C.3 represents the fields of application of all the methods described.
Annex D provides a trilingual key of the abbreviations used in the Figures given in Annex C.
NOTE   Three methods applicable for the analysis of some ferro-alloys are listed in Annex A.

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This document specifies methods for sampling and sample preparation for the determination of the chemical composition of pig irons, cast irons and steels.
Methods are specified for both liquid and solid metal.

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This International Standard specifies a flame atomic absorption spectrometric method for the
determination of the cobalt content in steel and iron.
The method is applicable to cobalt contents between 0,003 % (m/m) and 5,0 % (m/m).

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This document specifies a flame atomic absorption spectrometric method (FAAS) for the determination of the vanadium content in steel.
The method is applicable to vanadium contents between 0,01 % (mass fraction) and 0,80 % (mass fraction), provided that the tungsten content in a 1,0 g test portion is not higher than 1,0 % and/or the titanium content is not higher than 0,5 %.

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This document specifies a flame atomic absorption spectrometric method for the determination of copper in steel and cast iron.
The method is applicable to copper contents in the range of 0,003 % (mass fraction) to 3,0 % (mass fraction).

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This document specifies an infrared absorption method after combustion in an induction furnace for the determination of the low carbon content in unalloyed steel.
The method is applicable to carbon contents between 0,000 3 % (mass fraction) and 0,009 % (mass fraction).

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This document specifies a potentiometric titration method for the determination of vanadium in steel and cast iron.
The method is applicable to vanadium contents between 0,04 % (mass fraction) and 2 % (mass fraction).

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This document specifies a gravimetric method for the determination of the silicon content in steel and cast iron.
The method is applicable to silicon contents between 0,10 % (mass fraction) and 5,0 % {mass fraction).
NOTE    For samples containing molybdenum, niobium, tantalum, titanium, tungsten, zirconium or high levels of chromium, the results are less accurate than for unalloyed matrixes.

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This document describes the classification, method of sample preparation, certification main rules and certificate content of the EURONORM-CRMs.
It also details the sample presentation of the various producers' organizations and the distributing sources.

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This document specifies a flame atomic absorption spectrometric method (FAAS) for the determination of nickel content in steels and cast irons.
The method is applicable to nickel contents between 0,004 % (weight percent) and 2,0 % (weight percent).
The method can be adapted to lower or higher nickel contents by changing the test portion or the dilution process, provided the criteria in 6.2.2 and 6.2.3 are still met.

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This document specifies a flame atomic absorption spectrometric method (FAAS) for the determination of lead content in non-alloy and low alloy steels.
The method is applicable to lead contents between 0,005 % (weight percent) and 0,5 % (weight percent).
The method can be adapted to lower or higher lead contents by changing the test portion or the dilution process, provided the criteria in 6.2.2 and 6.2.3 are still met.

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This document specifies a flame atomic absorption spectrometric method (FAAS) for the determination of calcium content in non-alloy and low alloy steels.
The method is applicable to calcium contents between 4 µg/g and 120 µg/g.
The method can be adapted to higher calcium contents by changing the test portion or the dilution process, provided the criteria in 6.2.2 and 6.2.3 are still met.

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This document specifies an inductively coupled plasma optical emission spectrometric method for the determination of the chromium content (mass fraction) between 5,0 % (m/m) and 27,0 % (m/m) in alloyed steels.
The method doesn't apply to alloyed steels having carbon contents higher than 1 % and niobium and/or tungsten contents higher than 0,1 %.

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This document specifies a spectrophotometric method for the determination of nitrogen in steel.
The method is applicable to the determination of nitrogen mass fraction between 0,000 6 % and 0,050 % in low alloy steels and between 0,010 % and 0,050 % in high alloy steels.
The method does not apply to samples containing silicon nitrides or having silicon contents higher than 0,6 %.

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ISO 4829-1:2018 specifies a spectrophotometric method for the determination of total silicon in steel and cast iron using reduced molybdosilicate.
The method is applicable to the determination of silicon mass fraction between 0,05 % and 1,0 %.

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The present Technical Report gives guidance regarding the chemical composition controls of steels (except chrome plated products) and cast irons in respect of the European legislation, namely Directives 2011/65/EU (RoHS) [1], repealing 2002/95/EU, the Commission Delegated Directive EU 2015/863 amending Annex II to Directive 2011/65/EU [10] and 2000/53/EC (ELV) [2].
These Directives require the characterization of these materials for Cadmium (Cd), hexavalent chromium (Cr (VI)), mercury (Hg), Lead (Pb), polybrominated biphenyls (PBB), polybrominated diphenyl ethers (PBDE) and the four phthalates DEHP, BBP DBP and DIBP. Nevertheless, the Directives do not reflect the correspondence between these elements/compounds and the normal composition of each material concerned. In other words, for every material there is an obligation to determine all the compounds listed, independently of the relevance of such controls.

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ISO 4829-2:2016 specifies a spectrophotometric method for the determination of total silicon in steels using reduced molybdosilicate.
The method is applicable to silicon contents between 0,01 % and 0,05 % (mass fraction) in steels.

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ISO 4946:2016 specifies a spectrophotometric method for the determination of copper in steel and cast iron by 2,2'-biquinoline.
The method is applicable to the determination of copper mass fraction in the range of 0,02 % and 5 %.

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ISO 4938:2016 specifies a method for the determination of nickel in steel and iron by gravimetry or titrimetry.
The method is applicable to nickel contents from 1 % to 30 % (mass fraction).

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This European Standard specifies an inductively coupled plasma optical emission spectrometric method for the determination of nickel content (mass fraction) between 5,0 % and 25,0 % in alloyed steels.
The method does not apply to alloyed steels having niobium and/or tungsten contents higher than 0,1 %.

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This Technical Report specifies an electrothermal atomic absorption spectrometric method for the determination of selenium in steels.
The method is applicable to selenium contents between 0,000 4 % (m/m) and 0,02 % (m/m).

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This European Standard specifies a flame atomic absorption spectrometric method for the determination of titanium in steels and cast irons. The method is applicable to non-alloyed and alloyed steels and cast irons with titanium contents of 0,01 % to 1,0 % (m/m).

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This European Standard specifies an inductively coupled plasma optical emission spectrometry routine method for the analysis of unalloyed and low alloyed steels, whose iron content shall be at least 95 %. This standard differs from the similar standard EN 10351:2011 in that it is optimised for the determination of silicon.
This method is applicable to the elements listed in Table 1 within the ranges shown.
The sample preparation described may not completely dissolve samples having a combination of high chromium and substantial carbon. Incomplete dissolution may also affect the determination of manganese and molybdenum in these samples. For this reason, the scope of the method is limited to chromium contents = 0,9 %, whereas the scope of EN 10351 covers a range of up to 1,6 % chromium.
Table 1 - Application ranges
Element   Mass fraction %
   min.   max.
Si   0,020   0,45
Mn   0,005   1,40
P   0,005   0,10
Cu   0,005   0,60
Ni   0,010   2,00
Cr   0,010   0,90
Mo   0,005   0,60
Sn   0,010   0,10
NOTE   For tin, see NOTE 2 under Clause 11.
In all cases, the ranges specified can be extended or adapted (after validation) for the determination of other mass fractions, provided that the iron content in the samples under concern is above 95 %.
Other elements may be included. However such elements and their mass fractions should be carefully checked, taking into account the possible interferences, the sensitivity, the resolution and the linearity criteria of each instrument and each wavelength.
Depending also on the sensitivity of each instrument, suitable dilutions of the calibration and the test sample solutions may be necessary.
Moreover, even if the method described is "multi elemental", it is not absolutely necessary to carry out the determination of all the elements of its scope simultaneously. The measurement conditions have to be optimised by each laboratory, depending on the performances of each apparatus available.

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This Technical Report is a guideline to carry out the statistical evaluation of data from an inter laboratory test for method validation.
Its purpose is to detail the methodology of ISO 5725 1:1994, ISO 5725 2:1994 and ISO 5725 3:1994 for the treatment of the data collected under the conditions used within the ECISS/TC 102 working groups.
NOTE   The present document is not a simplification of the ISO 5725 standard, which is the only reference document.

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This European Standard specifies an electrometric titration method for the determination of manganese in steels and irons.
The method is applicable to unalloyed, low alloy or alloyed steels and to irons with manganese contents greater than or equal to 0,5 % (m/m).

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This European Standard specifies a spectrophotometric method for the determination of boron in steels. The method is applicable to non-alloyed and alloyed steels with boron contents of 0,000 4 to 0,012 0 % (m/m).

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The present statistical procedure describes how to check results for absence of bias by comparison of these analytical results with those obtained during the certification of CRMs.
If the resulting data confirm the absence of bias, the method may be considered accurate when applied to all steels and irons whose composition ranges are adequately covered or bounded by the CRMs used.
The resulting data give also an estimate of the repeatability and/or the intermediate precision ("intralaboratory reproducibility") for the CRMs used. The comparison of these analytical data with the repeatability data obtained during the certification may also be performed depending on the strict purpose of the method under consideration.
For the purpose of this Technical Report, the use of existing CRMs is essential for the assessment of the trueness, but it may be only indicative for the other statistical data.
NOTE   This Technical Report does not describe the use of CRMs as calibrants, this subject being treated in ISO Guide 32.

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This Technical Report describes a X-ray fluorescence (XRF) spectrometric method for the determination of Si and Al contents in Ferro Silicon materials.
The method is applicable to:
- Si content between 40 and 90 %;
- Al content between 0,5 and 6 %.
The Technical Report specifies the general requirements for analysis by X-ray fluorescence spectrometry and the preparation of the test sample.
The correction of the spectrometric measurement from spectral interferences on the analytical lines used is essential. This Technical Report is valid for the analytical lines:
- Si Kα 7.126 (for element contents between 45 and 90 %);
- Al Kα 8.339 (for element contents between 0,8 and 6 %);
- Fe Kα 1.937 (for element contents between 10 and 58 %).
NOTE   For matrix matching purposes, iron is included in the analytical program to be prepared.
Within the conditions here above, spectral interferences don’t need to be calculated.

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This Technical Report describes an inductively coupled plasma optical emission spectrometric method for the determination of Al, Ti and P contents in Ferro Silicon materials.
The method is applicable to:
- Al content between 0,2 and 2 %;
- Ti content between 0,02 and 0,25 %;
- P content between 0,005 and 0,05 %.
This Technical Report also describes the general requirements for analysis by inductively coupled plasma optical emission spectrometry, the preparation and dissolution of the test sample and the method of calculation of the results.
The procedure is valid for the analytical lines given in Table 1. This table also gives, for each line, the spectral interferences, which must be accurately corrected.
NOTE   The interferences extend as well as other possible interferences depend on the temperature in the plasma and on the optical resolution of the spectrometer used.
Table 1 - Spectral lines suggested together with the interferences which shall be corrected
Element   Wavelength (nm)   Interferences
Al   308,22   V
Ti   337,28   V, Ni
P   178,29   Mo

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This European Standard specifies an inductively coupled plasma optical emission spectrometry routine method for the analysis of unalloyed and low alloyed steels, whose iron content shall be at least 95 %.
This method is applicable to the elements listed in Table 1 within the ranges shown.
Table 1 - Application ranges
(...)
In all cases, the ranges specified can be extended or adapted (after validation) for the determination of other mass fractions, provided that the iron content in the samples under concern is above 95 %.
Other elements may be included. However such elements and their mass fractions should be carefully checked, taking into account the possible interferences, the sensitivity, the resolution and the linearity criteria of each instrument and each wavelength.
Depending also on the sensitivity of each instrument, suitable dilutions of the calibration and the test sample solutions may be necessary.
Moreover, even if the method described is "multi elemental", it is not absolutely necessary to carry out the determination of all the elements of its scope simultaneously: the measurement conditions have to be optimised by each laboratory, depending on the performances of each apparatus available.
NOTE 1   The accuracy of the method is unsatisfactory for phosphorus contents from 0,05 to 0,1 %.
NOTE 2   The trueness of the method couldn't be checked for vanadium contents below 0,05 %.
NOTE 3   The precision of the method is unsatisfactory for aluminium (total) contents below 0,02 %.

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This International Standard specifies an infrared absorption method, after combustion in an induction furnace, for
the determination of the total carbon and sulfur content in steel and iron.
The method is applicable to carbon contents of mass fraction between 0,005 % and 4,3 % and to sulfur contents of
mass fraction between 0,000 5 % and 0,33 %.
This method is intended to be used in normal production operations and is intended to meet all generally accepted,
good laboratory practices of the type expected by recognized laboratory accreditation agencies. It uses
commercially available equipment, is calibrated and calibration verified using steel and iron certified reference
materials, and its performance is controlled using normal statistical process control (SPC) practices.
This method can be used in the single element mode, i.e., determination of carbon and sulfur independently or in
the simultaneous mode, i.e., determination of carbon and sulfur concurrently.

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This International Standard specifies a thermal conductimetric method after fusion under inert gas for the
determination of nitrogen in steel and iron.
The method is applicable to nitrogen contents between 0,002 % (m/m) and 0,6 % (m/m).

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Method for determination of nitrogen content between 0,0008 % and 0,5 % in steel and iron.

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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 (preferable 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) a
Si   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
a   The 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 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 high 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. A variety of computer programs for corrections is commonly used and included in the software package from the manufacturers.

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This European Standard specifies a method for the molybdenum blue spectrophotometric determination of phosphorus in non-alloyed steels and irons.
The method is applicable to non-alloyed steels and irons with phosphorus contents from 0,005 % to 0,25 % (m/m).

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This document specifies a glow discharge optical emission spectrometric method for the determination of the thickness and chemical composition of metallic surface coatings consisting of zinc and aluminium based alloys. The alloying elements considered are aluminium, nickel, silicon and lead.
This method is applicable to zinc contents between 40 % (m/m) and 100 % (m/m); aluminium contents between 0,01 % (m/m) and 60 % (m/m); nickel contents between 0,01 % (m/m) and 15 % (m/m); silicon contents between 0,01 % (m/m) and 3 % (m/m); lead contents between 0,005 % (m/m) and 0,1 % (m/m).

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This document specifies an optical emission spectrometry spark source routine standard method for multi-element analysis of unalloyed steel and iron.

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ISO 4934:2003 specifies a gravimetric method for the determination of the sulfur content in steels and iron, excluding steels containing selenium. The method is particularly suitable as a reference method for the standardization of samples on which certified standard values are to be established.
The method is applicable to a sulfur content between 0,003 % (mass fraction) and 0,35 %(mass fraction).

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This European Standard specifies an infrared method after fusion under inert gas for the determination of oxygen in steel and iron.
The method is applicable to oxygen contents between 0,0005 % (m/m) and 0,01 % (m/m).

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The method is applicable with the following limitations: phosphorus contents between 0,001 0 % (m/m) and 1,0 % (m/m), application ranges and test portions in table 1 depending on the concentration of the interfering elements (arsenic, hafnium, niobium, tantalum, titanium, tungsten).

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Method for determination of boron content between 0,00005 % and 0,001 % in steel.

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The purpose of this document is to describe concepts and procedures for calibration and analysis of the equipment based on spark source optical emission spectrometry. Optical emission spectrometers are equipments that provide a quality and quantity characterization of electromagnetic radiation which is emitted by a test sample when excited by a suitable source.

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The method is applicable to carbon contents between 0,003% (m/m) and 4,5 % (m/m). Specifies principle, reagents, apparatus, sampling, procedure, expression of results and test report. The annexes give additional information on the international co-operative tests, a graphical representation of precision data and features of induction furnaces and carbon analysers.

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This European Standard specifies two methods for the preparation of steel samples for oxygen determination. Both methods are suitable for preparing samples for the determination of oxygen content, especially for oxygen contents < 0,0050 %. This standard is applicable to steels having a hardness of < 400 HBW 10/3000.

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The principle of the method specified is dissolving a test portion in hydrochloric and nitric acids followed by evaporation with perchloric acid until white fumes appear, spraying the solution into an air-acetylene flame, spectrometrically measuring the atomic absorption of the 279,5 nm spectral line emitted by a manganese hollow cathode lamp. The method is applicable to manganese contents between 0,002 % (m/m) and 2,0 % (m/m).

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Migrated from Progress Sheet (TC Comment) (2000-07-10): Will be submitted to the UAP procedure to replace EU 182

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This European standard specifies a spectrophotometric method for the determination of arsenic in steel and iron. The method is applicable to all types of steel and iron with arsenic contents from 0,001% to 0,08% (m/m).

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