CEN/TR 10261:2008

SLOVENSKI STANDARD
01-oktober-2008
1DGRPHãþD
SIST CR 10261:1998
äHOH]RLQMHNOR3UHJOHGUD]SRORåOMLYLKPHWRG]DNHPLþQRDQDOL]R
Iron and steel - Review of available methods of chemical analysis
Eisen und Stahl - Übersicht über verfügbare Verfahren der chemischen Analyse
Aciers et fontes - Méthodes d´analyse chimique disponibles
Ta slovenski standard je istoveten z: CEN/TR 10261:2008
ICS:
77.040.30 Kemijska analiza kovin Chemical analysis of metals
77.080.01 Železne kovine na splošno Ferrous metals in general
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

TECHNICAL REPORT
CEN/TR 10261
RAPPORT TECHNIQUE
TECHNISCHER BERICHT
July 2008
ICS 77.040.30 Supersedes CR 10261:1995
English Version
Iron and steel - Review of available methods of chemical
analysis
Aciers et fontes - Méthodes d´analyse chimique disponibles Eisen und Stahl - Übersicht über verfügbare Verfahren der
chemischen Analyse
This Technical Report was approved by CEN on 9 April 2007. It has been drawn up by the Technical Committee ECISS/TC 20.
CEN members are the national standards bodies of Austria, Belgium, Bulgaria, 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 STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION
EUROPÄISCHES KOMITEE FÜR NORMUNG
Management Centre: rue de Stassart, 36  B-1050 Brussels
© 2008 CEN All rights of exploitation in any form and by any means reserved Ref. No. CEN/TR 10261:2008: E
worldwide for CEN national Members.

Contents Page
Foreword.3
1 Scope .4
2 Normative references .4
2.1 Mono-elemental methods .4
2.2 Multi-elemental methods.7
3 Range of application and method principle.7
3.1 Mono-elemental methods .7
3.2 Multi-elemental methods.18
Annex A (informative) List of Standards, CEN reports and ECISS Information Circulars relevant
for chemical analysis of ferrous materials.21
Annex B (informative) List of withdrawn Euronorms in the field of chemical analysis of ferrous
materials .22
Annex C (informative) Graphical presentation of the concentration ranges for the methods
presented in this technical report.25

Foreword
This document CEN/TR 10261:2008 has been prepared by Technical Committee ECISS/TC 20 “Methods of
chemical analysis of ferrous products”, the secretariat of which is held by SIS.
This document supersedes CEN/CR 10261:1995.
This report is a review of European standards methods of chemical analysis of steel and iron. Principles and
fields of application for the methods are also indicated.

1 Scope
This CEN Technical Report lists, under Clause 2, the European Standards which are currently available for
the chemical analysis of steel and iron. In Clause 3, it also provides details of range of application and method
principle for each standard.
Items which are under preparation as European Standards or as CEN Technical Reports by ECISS/TC 20 are
available on the webpage of CEN, through the link
http://www.cen.eu/CENORM/Sectors/TechnicalCommitteesWorkshops/CENTechnicalCommittees/WP.asp?pa
ram=6357&title=ECISS%2FTC+20.
Annex A contains a list of European Standards, CEN Technical Reports and ECISS Information Circulars
relevant for chemical analysis of ferrous materials.
Annex B contains a list of withdrawn Euronorms, together with the corresponding replacement European
Standards.
Annex C is a graphical presentation of the concentration ranges for the methods presented in this Technical
Report.
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.
2.1 Mono-elemental methods
Aluminium, Al
EN 29658:1991, Steel — Determination of aluminium content — Flame atomic absorption spectrometric
method (ISO 9658:1990)
Arsenic, As
EN 10212:1995, Chemical analysis of ferrous materials — Determination of arsenic in steel and iron —
Spectrophotometric method
Boron, B
EN 10200:1991, Chemical analysis of ferrous materials — Determination of boron in steel —
Spectrophotometric method
EN ISO 13900:2002, Steel — Determination of boron content — Curcumin spectrophotometric method after
distillation (ISO 13900:1997)
Calcium, Ca
EN 10177:1989, Chemical analysis of ferrous materials — Determination of calcium in steels — Flame atomic
absorption spectrometric method
Carbon, C
EN 10036:1989, Chemical analysis of ferrous materials — Determination of total carbon in steels and irons —
Gravimetric method after combustion in a stream of oxygen
EN ISO 15349-2:2003, Unalloyed steel — Determination of low carbon content — Part 2: Infrared absorption
method after combustion in an induction furnace (with preheating) (ISO 15349-2:1999)
EN ISO 9556:2001, Steel and iron — Determination of total carbon content — Infrared absorption method
after combustion in an induction furnace (ISO 9556:1989)
Chromium, Cr
EN 10188:1989, Chemical analysis of ferrous materials — Determination of chromium in steels and irons —
Flame atomic absorption spectrometric method
EN 24937:1990, Steel and iron — Determination of chromium content — Potentiometric or visual method
(ISO 4937:1986)
EN 24937:1990/AC 1991, Steel and iron — Determination of chromium content — Potentiometric or visual
method
Copper, Cu
EN 24946:1990, Determination of copper content in steel and cast iron
EN 24946:1990/AC 1991 (Editorial correction), Steel and cast iron — Determination of copper content — 2,2'
diquinolyl spectrophotometric method (ISO 4946:1984)
EN 24943:1990, Chemical analysis of ferrous metal — Determination of copper content — Flame atomic
absorption spectrometric method (ISO 4943:1985)
EN 24943:1990/AC 1991 (Editorial correction), Steel and cast iron — Determination of copper content —
Flame atomic absorption spectrometric method (ISO 4943:1985)
Lead, Pb
EN 10181:1989, Chemical analysis of ferrous materials — Determination of lead in steels — Flame atomic
absorption spectrometric method
Manganese, Mn
EN 10071:1989, Chemical analysis of ferrous materials — Determination of manganese in steels and irons —
Electrometric titration method
EN 24159:1989, Ferromanganese and ferrosilicomanganese — Determination of manganese content —
Potentiometric method (ISO 4159:1978, ed .1)
EN 24159:1989/AC 1:1989 (Editorial correction), Ferromanganese and ferrosilicomanganese —
Determination of manganese content — Potentiometric method (ISO 4159:1978, ed. 1)
EN ISO 10700:1995, Steel and iron — Determination of manganese content — Flame atomic spectrometric
method (ISO 10700:1994)
Nickel, Ni
EN 10136:1989, Chemical analysis of ferrous materials — Determination of nickel in steels and irons —
Flame atomic absorption spectrometric method
EN 24938:1990, Steel and iron — Determination of nickel content — Gravimetric or titrimetric method
(ISO 4938:1988)
EN 24938:1990/AC 1991 (Editorial correction), Steel and iron — Determination of nickel content —
Gravimetric or titrimetric method (ISO 4938:1988)
Niobium, Nb
EN 10178:1989, Chemical analysis of ferrous materials — Determination of niobium in steels —
Spectrophotometric method
Nitrogen, N
EN 10179:1989, Chemical analysis of ferrous materials — Determination of nitrogen (trace amounts) in
steel — Spectrophotometric method
EN ISO 10720:2007, Steel and iron - Determination of nitrogen content – Thermal conductimetric method after
fusion in a current of inert gas (ISO 10720:1997)
Oxygen, O
EN 10276-1:2000, Chemical analysis of ferrous materials — Determination of oxygen in steel and iron —
Part 1: Sampling and preparation of steel samples for oxygen determination
EN 10276-2:2003, Chemical analysis of ferrous materials — Determination of oxygen content in steel and
iron — Part 2: Infrared method after fusion under inert gas
Phosphorus, P
EN 10184:2006, Chemical analysis of ferrous materials — Determination of phosphorus in non-alloyed steels
and irons — Molybdenum blue spectrophotometric method
EN ISO 10714:2002, Steel and iron — Determination of phosphorus content — Phosphovanadomolybdate
spectrophotometric method (ISO 10714:2002)
Silicon, Si
EN 24829-1:1990, Steel and cast iron – Determination of total silicon content — Reduced molybdosilicate
spectrophotometric method — Part 1: Silicon content between 0,05 and 1 % (ISO 4829-1:1986)
EN 24829-1:1990/AC 1991(Editorial correction), Determination of total silicon content — Reduced
molybdosilicate spectrophotometric method — Part 1: Silicon content between 0,05 and 1,0 % (ISO 4829-
1:1986)
EN 24829-2:1990, Steel and cast iron — Determination of total silicon content — Reduced molybdosilicate
spectrophotometric method — Part 2: Silicon content between 0,01 and 0,05 % (ISO 4829-2:1988)
EN 24829-2:1990/AC 1991 (Editorial correction), Steel and cast iron — Determination of total silicon
content — Reduced molybdosilicate spectrophotometric method — Part 2: Silicon content between 0,01 and
0,05 % (ISO 4829-2:1988)
Sulphur, S
EN 24935:1991, Steel and iron — Determination of sulphur content — Infrared absorption method after
combustion in an induction furnace (ISO 4935:1989)
EN ISO 4934:2003, Steel and iron — Determination of sulphur content — Gravimetric method
(ISO 4934:2003)
Titanium, Ti
EN ISO 10280:1995, Steel and iron — Determination of titanium content — Diantipyrylmethane
spectrophotometric method (ISO 10280:1991)

Vanadium, V
EN 24947:1991, Steel and cast iron — Determination of vanadium content — Potentiometric titration method
(ISO 4947:1986)
2.2 Multi-elemental methods
Aluminium, Al; Lead, Pb; Nickel, Ni; Silicon, Si and Zinc, Zn
EN 10318:2005, Determination of thickness and chemical composition of zinc- and aluminium-based metallic
coatings — Routine method
Silicon, Si; Manganese, Mn; Phosphorus, P; Chromium, Cr; Nickel, Ni; Molybdenum, Mo; Copper, Cu;
Cobalt, Co; Vanadium, V; Titanium, Ti and Niobium, Nb
EN 10315:2006, Routine method for analysis of high alloy steel by X-ray Fluorescence Spectrometry (XRF) by
using a near by technique
Carbon, C; Silicon, Si; Sulphur, S; Phosphorus, P; Manganese, Mn; Chromium, Cr; Nickel, Ni and
Copper, Cu
CR 10320:2004, Optical emission analysis of low alloy steels (routine method) - Method for determination of C,
Si, S, P, Mn, Cr, Ni and Cu
3 Range of application and method principle
3.1 Mono-elemental methods
3.1.1 Aluminium, Al
3.1.1.1 EN 29658:1991, Steel — Determination of aluminium content — Flame atomic absorption
spectrometric method (ISO 9658:1990)
Range of application:
 determination of aluminium contents between 0,005 % (m/m) and 0,20 % (m/m) in non-alloyed steel.
Method principle:
a) dissolution of a test portion in dilute hydrochloric and nitric acids;
b) fusion of the acid-insoluble material with a mixture of orthoboric acid and potassium carbonate;
c) spraying of the solution into a dinitrogen monoxide-acetylene flame;
d) spectrometric measurement of the atomic absorption of the 309,3 nm spectral line emitted by an
aluminium hollow cathode lamp.
3.1.2 Arsenic, As
3.1.2.1 EN 10212:1995, Chemical analysis of ferrous materials — Determination of arsenic in steel
and iron — Spectrophotometric method
Range of application:
 determination of arsenic contents from 0,001 % to 0,08 % (m/m) in all types of steel and iron.
Method principle:
a) dissolution of a test portion in a mixture of nitric and hydrochloric acids followed by evaporation to dryness
and prolonged heating of the dried residue;
b) extraction of the residue with acid, reduction of the arsenic (As V to As III) by addition of potassium iodine,
ascorbic acid and tin (II) chloride. Conversion of the arsenic to arsenic hydride (arsine) with zinc;
c) absorption of the evolved arsine in a solution of silver diethyldithiocarbamate and l-ephedrin in
trichloromethane;
d) spectrophotometric measurement of the reddish-violet coloured colloid at a wavelength between 500 nm
and 520 nm.
3.1.3 Boron, B
3.1.3.1 EN 10200:1991, Chemical analysis of ferrous materials — Determination of boron in steel —
Spectrophotometric method
Range of application:
 determination of boron content from 0,0004 % to 0,0120 % (m/m) in non-alloyed and alloyed steels.
Method principle:
a) dissolution of a test portion with hydrochloric and nitric acids;
b) decomposition of boron compounds (nitrides, etc.) with orthophosphoric and sulphuric acids at 290 °C.
Spectrophotometric measurement at a wavelength of 543 nm of the complex formed between boric acid
and curcumin in buffered acetic medium.
3.1.3.2 EN ISO 13900:2002, Steel — Determination of boron content — Curcumin
spectrophotometric method after distillation (ISO 13900:1997)
Range of application:
 determination of boron content from 0,00005 % to 0,0010 % (m/m) in steel.
Method principle:
a) dissolution of a test portion in hydrochloric and nitric acids. Decomposition of boron compounds (nitrides,
etc.) with orthophosphoric and sulphuric acids at a temperature of 290 °C;
b) distillation of the solution after the addition of methanol and collection of methylborate in a receiver
containing sodium hydroxide solution;
c) evaporation of the solution to dryness. Formation of a coloured complex between orthoboric acid and
curcumin in a methanol medium;
d) spectrophotometric measurements at a wavelength of about 550 nm.
3.1.4 Calcium, Ca
3.1.4.1 EN 10177:1989, Chemical analysis of ferrous materials — Determination of calcium in
steels — Flame atomic absorption spectrometric method
Range of application:
 determination of calcium contents greater than 0,0002 % (m/m) in non-alloyed and low-alloy steels.
Method principle:
a) dissolution of a test portion with hydrochloric acid followed by oxidation with nitric acid;
b) addition of potassium chloride solution and spraying of the solution into an acetylene-nitrous oxide flame.
Determination of the calcium by means of the spectrometric measurement of the atomic absorption of the
422,67 nm line emitted by a calcium hollow cathode lamp.
NOTE Potassium chloride is added to suppress ionization of calcium and the instrument is calibrated by addition of a
calcium standard solution to a similar matrix to that of the test solution.
3.1.5 Carbon, C
3.1.5.1 EN 10036:1989, Chemical analysis of ferrous materials — Determination of total carbon in
steels and irons — Gravimetric method after combustion in a stream of oxygen
Range of application:
 determination of carbon content equal to or greater than 0,1 % (m/m) in steels and irons.
Method principle:
a) combustion of a test portion in a stream of oxygen in a high temperature furnace iron (1 200 °C –
1 400 °C), with the addition of a fluxing agent to assist combustion;
b) absorption of the evolved carbon dioxide in soda asbestos contained in a weighed absorption bulb;
c) calculation of the carbon content from the increase in mass of the absorption bulb.
3.1.5.2 EN ISO 15349-2:2003, Unalloyed steel — Determination of low carbon content — Part 2:
Infrared absorption method after combustion in an induction furnace (with preheating) (ISO 15349-
2:1999)
Range of application:
 carbon contents between 0,0003 % (m/m) and 0,010 % (m/m) in unalloyed steel.
Method principle:
a) preheating of a test portion at low temperature and combustion of a test portion with accelerator at a high
temperature in an induction furnace in a current of pure oxygen;
b) transformation of carbon into carbon dioxide and/or carbon monoxide;
c) measurement of infrared absorption of the carbon dioxide or carbon dioxide/carbon monoxide evolved
from steel and carried by a current of pure oxygen;
d) calibration graph is established using sucrose or calcium carbonate.
3.1.5.3 EN ISO 9556:2001, Steel and iron — Determination of total carbon content — Infrared
absorption method after combustion in an induction furnace (ISO 9556: 1989)
Range of application:
 determination of carbon contents between 0,003 % (m/m) and 4,5 % (m/m) in steel and iron.
Method principle:
a) combustion of a test portion with accelerator at a high temperature in a high-frequency induction furnace
in a current of pure oxygen. Transformation of carbon into carbon dioxide and/or carbon monoxide;
b) measurement by infrared absorption of the carbon dioxide and/or carbon monoxide carried by a current of
oxygen.
3.1.6 Chromium, Cr
3.1.6.1 EN 10188:1989, Chemical analysis of ferrous materials — Determination of chromium in
steels and irons — Flame atomic absorption spectrometric method
Range of application:
 determination of chromium contents of 0,002 % to 2,0 % (m/m) in non-alloy and low-alloy steels and irons.
Method principle:
a) dissolution of a test portion with hydrochloric acid followed by oxidation with nitric acid. Filtration and
ignition of the acid insoluble residue. Removal of silica with hydrofluoric acid. Fusion of the residue with
potassium hydrogen sulphate, extraction of the melt in acid and addition of the extract to the reserved
filtrate;
b) determination of the chromium by means of the spectrometric measurement of the atomic absorption of
the 357,87 nm line emitted by a chromium hollow cathode lamp when the solution is nebulized into a
nitrous oxide acetylene flame.
3.1.6.2 EN 24937:1990, Steel and iron — Determination of chromium content — Potentiometric or
visual titration method (ISO 4937:1986)
Range of application:
 determination of chromium contents between 0,25 % and 35 % (m/m) in steel and iron.
Method principle:
a) dissolution of a test portion with appropriate acids;
b) oxidation of chromium in an acid medium to chromium (VI) by ammonium peroxydisulphate in the
presence of silver sulphate. Reduction of manganese (VII) by hydrochloric acid;
c) reduction of chromium (VI) by ammonium iron (II) sulphate standard solution;
d) in the case of potentiometric detection, determination of the equivalence point by measurement of the
potential variation when the ammonium iron (II) sulphate standard solution is being added;
e) in the case of visual detection, titration of the excess ammonium iron (II) sulphate by potassium
permanganate standard solution which also acts as the indicator.
3.1.7 Copper, Cu
3.1.7.1 EN 24943:1990, Chemical analysis of ferrous metal — Determination of copper content —
Flame atomic absorption spectrometric method (ISO 4943:1985)
Range of application:
 determination of copper content between 0,004 % (m/m) and 0,5 % (m/m) in steel and cast iron.
Method principle:
a) dissolution of a test portion in mixture of hydrochloric, nitric and perchloric acids. Spraying of the solution
into an air-acetylene flame. Spectrometric measurement of the atomic absorption of the 324,7 nm
spectral line emitted by a copper hollow cathode lamp.
3.1.7.2 EN 24946:1990, Determination of copper content in steel and cast iron
Range of application:
 determination of copper contents between 0,02 % and 5 % (m/m) in steel and cast irons.
Method principle:
a) dissolution of a test portion with appropriate acids;
b) fuming with perchloric acid to remove hydrochloric and nitric acids and dehydrate silicic acid;
c) reduction of copper (II) to copper (I) in hydrochloric acid solution by means of ascorbic acid. Formation of
a coloured compound of copper (I) with 2,2-diquinolyl;
d) spectrophotometric measurement at a wavelength of about 545 nm.
3.1.8 Lead, Pb
3.1.8.1 EN 10181:1989, Chemical analysis of ferrous materials — Determination of lead in steels —
Flame atomic absorption spectrometric method
Range of application:
 determination of lead contents of 0,003 % to 0,5 % (m/m) in non-alloy and low-alloy steels.
Method principle:
a) dissolution of a test portion with hydrochloric acid followed by oxidation with nitric acid;
b) spraying of the solution into an air-acetylene flame. Determination of the lead by means of the
spectrometric measurement of the atomic absorption of the 283,3 nm line emitted by a lead radiation
source;
c) the instrument is calibrated by addition of a lead standard solution to a similar matrix to that of the test
solution.
3.1.9 Manganese, Mn
3.1.9.1 EN 10071:1989, Chemical analysis of ferrous materials — Determination of manganese in
steels and irons — Electrometric titration method
Range of application:
 determination of manganese contents greater than or equal to 0,5 % (m/m) in non-alloy or alloy steels
and iron.
Method of principle:
a) dissolution of the test portion by suitable acid and partial neutralization of the acid by sodium hydrogen
carbonate;
b) precipitation by zinc oxide of the cations which may interfere with the electrometric determination.
c) titration of the Mn (II) by means of potassium permanganate solution, in the presence of pyrophosphoric irons at
a pH value of about 6,5. The oxidation-reduction [oxidation of Mn (II) into Mn (III)] reaction is followed by an
electrometric measurement
3.1.9.2 EN 24159:1989, Ferromanganese and ferrosilicomanganese — Determination manganese
content — Potentiometric method (ISO 4159:1978, ed. 1)
Range of application:
 determination of manganese content of ferromanganese and ferrosilicomanganese alloys containing from
55 % to 95 % (m/m) of manganese.
Method principle:
a) dissolution of a test portion with hydrochloric, hydrofluoric and perchloric acids. Potentiometric
determination (see note) of manganese with potassium permanganate in a pyrophosphoric medium at a
controlled pH, according to the reaction:
2+ - + 2- 3-
4 Mn + MnO + 8 H + 15 (P O H ) → 5 Mn(P 0 H ) + 4 H O.
4 2 7 2 2 7 2 3 2
NOTE The method may be completed by any other electrometric method: amperometric titration, dead-stop, etc.
3.1.9.3 EN ISO 10700: 1995, Steel and iron — Determination of manganese content — Flame atomic
spectrometric method (ISO 10700:1994)
Range of application:
 determination of manganese contents between 0,002 % (m/m) and 2,0 % (m/m).
Method principle:
a) dissolution of a test portion in hydrochloric and nitric acids followed by evaporation with perchloric acid
until white fumes appear;
b) spraying of the solution into an air-acetylene flame;
c) spectrometric measurement of the atomic absorption of the 279,5 nm spectral line emitted by a
manganese hollow cathode lamp.
3.1.10 Nickel, Ni
3.1.10.1 EN 10136:1989, Chemical analysis of ferrous materials — Determination of nickel in steel
and irons — Flame atomic absorption spectrometric method
Range of application:
 determination of nickel contents of 0,003 % to 2 % (m/m) in steels and irons.
Method principle:
a) dissolution of a test portion in a mixture of appropriate acids and fuming with perchloric acid;
b) spraying of the solution into an air-acetylene flame. Determination of the nickel by means of the
spectrometric measurement of the atomic absorption of the 232,0 nm or 352,5 nm line emitted by a nickel
hollow cathode lamp;
c) the instrument is calibrated by addition of a nickel standard solution to a similar matrix to that of the test
solution.
NOTE At the wavelength of 352,5 nm the signal-to-noise ratio is higher than at a wavelength of 232,0 nm. Generally,
use of the 352,2 nm line will lead to a better reproducibility.
However, as the sensitivity of 352,5 nm is less than the sensitivity at 232,0 nm, with some instruments the use of the
longer wavelength will be impossible when analysing low nickel contents.
3.1.10.2 EN 24938:1990, Steel and iron — Determination of nickel content — Gravimetric or titrimetric
method (ISO 4938:1988)
Range of application:
 determination of nickel content between 0,5 % (m/m) and 30 % (m/m) in steel and iron.
Method of principle:
a) dissolution of a test portion with appropriate acids. Precipitation of the nickel as nickel dimethylglyoxime;
1) cobalt, if present, is oxidized by potassium hexacyanoferrate (III);
2) copper, if present with cobalt, preferably is removed by controlled-potential electrolysis;
b) acid dissolution of the precipitate followed by a second precipitation of the nickel as nickel dimethylglyoxime;
c) in the case of th
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