DIN EN 10211-2014 Chemical analysis of ferrous materials - Determination of titanium in steels and cast irons - Flame atomic absorption spectrometric method German version EN 10211.pdf

1、March 2014 Translation by DIN-Sprachendienst.English price group 11No 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、77.040.30!%,4“2099317www.din.deDDIN EN 10211Chemical analysis of ferrous materials Determination of titanium in steels and cast irons Flame atomic absorption spectrometric method;English version EN 10211:2013,English translation of DIN EN 10211:2014-03Chemische Analyse von Eisenwerkstoffen Bestimmun

3、g des Titananteils in Stahl und Eisen Flammenatomabsorptionspektrometrisches Verfahren;Englische Fassung EN 10211:2013,Englische bersetzung von DIN EN 10211:2014-03Analyse chimique des produits ferreux Dtermination du titane dans les aciers et les fontes Mthode par spectromtrie dabsorption atomique

4、dans la flamme;Version anglaise EN 10211:2013,Traduction anglaise de DIN EN 10211:2014-03SupersedesDIN EN 10211:1996-02www.beuth.deDocument comprises 20 pagesIn case of doubt, the German-language original shall be considered authoritative.02.14 DIN EN 10211:2014-03 2 A comma is used as the decimal m

5、arker. National foreword This document (EN 10211:2013) has been prepared by Technical Committee ECISS/TC 102 “Methods of chemical analysis for iron and steel” (Secretariat: SIS, Sweden). The responsible German body involved in its preparation was the Normenausschuss Eisen und Stahl (Iron and Steel S

6、tandards Committee), Working Committee NA 021-00-30 AA Analysenverfahren. Amendments This standard differs from DIN EN 10211:1996-02 as follows: a) in Clause 1, “steel and iron” has been replaced by “non-alloyed and alloyed steels and cast irons”; b) in Clause 3, the use of aluminium chloride within

7、 both dissolutions described has been clarified; c) Subclause 5.2.3 has been added (information on the linearity criteria); d) in Table 1, terms corresponding to 0,025 % and 0,075 % titanium have been added; e) Subclause 7.6 has been merged in Subclause 7.5; f) Clause 8, formula: the notation has be

8、en changed; g) in Annex A, the notes have been included in the text and the correlation coefficients have been corrected; h) Annex B has been added (procedures for the determination of instrumental criteria). Previous editions DIN EN 10211: 1996-02 EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM E

9、N 10211 November 2013 ICS 77.040.30 Supersedes EN 10211:1995 English Version Chemical analysis of ferrous materials Determination of titanium in steels and cast irons Flame atomic absorption spectrometric method Analyse chimique des produits ferreux Dtermination du titane dans les aciers et les font

10、es Mthode par spectromtrie dabsorption atomique dans la flamme Chemische Analyse von Eisenwerkstoffen Bestimmung des Titananteils in Stahl und Eisen Flammenatomabsorptionsspektrometrisches Verfahren This European Standard was approved by CEN on 29 September 2013. CEN members are bound to comply with

11、 the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this European Standard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such national standards may be obtained on application to the CEN-CENELEC Manage

12、ment Centre or to any CEN member. This European Standard exists in three official versions (English, French, German). A version 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 stat

13、us as the official versions. CEN members are the national standards bodies of 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

14、, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels 2013 CEN

15、All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 10211:2013 E 2 Contents Page Foreword 3 1 Scope 4 2 Normative references 4 3 Principle 4 4 Reagents .4 5 Apparatus .6 6 Sampling .7 7 Procedure .7 8 Expression of results . 10 9 Test repo

16、rt . 11 Annex A (informative) Precision data . 12 A.1 General . 12 A.2 Information on repeatability and reproducibilities 15 A.2.1 Repeatability, r 15 A.2.2 Within-laboratory reproducibility, Rw. 15 A.2.3 Reproducibility, R . 15 Annex B (normative) Procedures for the determination of instrumental cr

17、iteria 16 B.1 Determination of minimum precision . 16 B.2 Determination of limit of detection . 16 B.3 Linearity of calibration . 16 B.4 Determination of characteristic concentration, cTi,cc17 Bibliography . 18 DIN EN 10211:2014-03 EN 10211:2013 (E) 3 Foreword This document (EN 10211:2013) has been

18、prepared by Technical Committee ECISS/TC 102 “Methods of chemical analysis for iron and steel”, the secretariat of which is held by SIS. 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 2014, a

19、nd conflicting national standards shall be withdrawn at the latest by May 2014. Attention is drawn to the possibility that some of the 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 d

20、ocument supersedes EN 10211:1995. In comparison with the previous edition of EN 10211, the following technical changes were made: Clause 1, “steel and iron” replaced by “non-alloyed and alloyed steels and cast irons”; Clause 3, clarification regarding the use of aluminium chloride within both dissol

21、utions described; Addition of 5.2.3 (information on the linearity criteria); Table 1, addition of terms corresponding to 0,025 % and 0,075 % titanium; Subclause 7.6 was merged in Subclause 7.5; Clause 8, formula: notation changed; Annex A, the notes were included in the text and the correlation coef

22、ficients corrected; Annex B: added. According to the CEN-CENELEC Internal Regulations, the national standards organisations of the following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugosla

23、v 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 the United Kingdom. DIN EN 10211:2014-03 EN 10211:2013 (E) 4 1 Scope Th

24、is 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). 2 Normative references The following do

25、cuments, in whole or in part, are normatively referenced in this document and are indispensable for its application. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies. EN ISO 648, Laboratory

26、glassware - Single-volume pipettes (ISO 648) EN ISO 1042, Laboratory glassware - One-mark volumetric flasks (ISO 1042) EN ISO 14284, Steel and iron - Sampling and preparation of samples for the determination of chemical composition (ISO 14284) 3 Principle Two dissolution procedures are possible and

27、described: a) The first one is specific to cast irons and is based on dissolution of the test portion with nitric and perchloric acids, followed by evaporation with perchloric acid to dryness. The further steps being a separation of the insolubilised silica by filtration and collection of the filtra

28、te. b) The second one, which can be used for steels as well as for cast irons is based on dissolution of the test portion with hydrochloric and nitric acid. This dissolution is followed by: 1) filtration and ignition of the acid insoluble residue and removal of silica with hydrofluoric acid; 2) fusi

29、on of the residue with a mixture of boric acid and sodium carbonate, dissolution of the melt with acid and addition of this solution to the reserved filtrate. Addition of aluminium chloride as interaction buffer, in both cases. Nebulisation of the test solution into a slightly fuel rich nitrous oxid

30、e/acetylene flame, of an atomic absorption spectrometer. Spectrometric measurement of the atomic absorption of the 365,3 nm (or 364,3 nm) spectral line emitted by a titanium hollow-cathode lamp. 4 Reagents During the analysis, use only reagents of recognised analytical grade and only distilled water

31、 or water of equivalent purity. 4.1 Nitric acid, HNO3(20= 1,40 g/ml). 4.2 Hydrochloric acid, HCl (20= 1,19 g/ml). DIN EN 10211:2014-03 EN 10211:2013 (E) 5 4.3 Perchloric acid, HClO4(20= 1,67 g/ml). 4.4 Sulphuric acid, H2SO4(20= 1,84 g/ml). 4.5 Hydrofluoric acid, HF (20= 1,15 g/ml). 4.6 Nitric acid s

32、olution, 1 + 1. Add 100 ml of nitric acid (4.1) to 100 ml water 4.7 Hydrochloric acid solution, 1 + 1. Add 100 ml of hydrochloric acid (4.2) to 100 ml water 4.8 Aluminium chloride solution, equivalent to 10 g/l Al. Dissolve 90 g of hydrated aluminium chloride (ALCl3. 6H2O) in a 600 ml beaker with wa

33、ter and transfer the solution into a 1 000 ml one-mark volumetric flask. Dilute to the mark with water and mix well. 4.9 Fusion mixture. Mix one part by mass of boric acid, H3BO3and one part of sodium carbonate anhydrous, Na2CO3. Store in a stoppered polyethylene container. 4.10 Iron-perchloric matr

34、ix solution, 20 g/l Fe. Weigh, to the nearest 0,01 g, 10,00 g of pure iron free of titanium or of known low titanium content. Transfer into a 600 ml beaker and cover with a watch glass. Add in small portions, 150 ml of nitric acid (4.6). When effervescence ceases, add 200 ml of perchloric acid (4.3)

35、. Heat gently, until the iron is completely dissolved. Continue heating at a temperature at which a steady reflux of white perchloric acid fumes is maintained on the walls of the beaker. Continue heating until there are no perchloric acid fumes visible inside the beaker and the iron perchlorate crys

36、tallises. Allow to cool, add 150 ml of water, swirl and boil gently to dissolve the salts. Transfer quantitatively into a 500 ml one-mark volumetric flask. Dilute to the mark with water and mix. 4.11 Ironchloro nitric matrix solution, 20 g/l Fe. Weigh, to the nearest 0,01 g, 20,00 g of pure iron fre

37、e of titanium or of known low titanium content. Transfer into a 600 ml beaker, add 200 ml of water and then 220 ml of hydrochloric acid (4.2), in small portions. Cover with a watch glass and heat gently until effervescence ceases. Add gradually 60 ml of nitric acid (4.1). Heat for about 10 min at ab

38、out 80 C, to expel nitrous fumes. Allow to cool and transfer quantitatively into a 1 000 ml one-mark volumetric flask. Add water until about 600 ml and add 20 g of fusion mixture (4.9). Dissolve, dilute to the mark with water and mix. 4.12 Titanium, 1 g/l standard solution. Weigh (1 0,001) g of tita

39、nium (99,99 % purity), transfer into a 400 ml beaker and cover with a watch glass. Dissolve it in 200 ml of hydrochloric acid solution (4.7) and add two drops of hydrofluoric acid (4.5). Heat gently until the metal is dissolved. After cooling, transfer the solution quantitatively into a 1 000 ml one

40、-mark volumetric flask, dilute to the mark with water and mix well. DIN EN 10211:2014-03 EN 10211:2013 (E) 6 1 ml of this solution contains 1 mg of titanium. 4.13 Titanium, 0,5 g/l standard solution freshly prepared. Transfer 50,0 ml of titanium standard solution (4.12) into a 100 ml one-mark volume

41、tric flask. Dilute to the mark with water and mix well. 1 ml of this standard solution contains 0,5 mg of titanium. 4.14 Titanium, 0,05 g/l standard solution freshly prepared. Transfer 10,0 ml of titanium standard solution (4.12) into a 200 ml one-mark volumetric flask. Dilute to the mark with water

42、 and mix well. 1 ml of this standard solution contains 0,05 mg of titanium. 5 Apparatus All volumetric glassware shall be Class A and calibrated, in accordance with EN ISO 648 or EN ISO 1042 as appropriate. 5.1 30 ml platinum crucibles. 5.2 Atomic absorption spectrometer. This shall be equipped with

43、 a titanium hollow-cathode lamp and supplied with nitrous oxide and acetylene sufficiently pure to give a a clear, steady slightly fuel-rich flame, free from water and oil, and free from titanium. The atomic absorption spectrometer used will be satisfactory if, after optimisation according to 7.5, t

44、he limit of detection and characteristic concentration are in reasonable agreement with the values given by the manufacturer and it meets the precision criteria given in 5.2.1 to 5.2.3. It is also recommended that the instrument should conform to the additional performance requirements given in 5.2.

45、4. 5.2.1 Minimum precision. Calculate the standard deviation of 10 measurements of the absorbance of the most concentrated calibration solution. The standard deviation shall not exceed 1,5 % of the mean absorbance of this solution. Calculate the standard deviation of 10 measurements of the absorbanc

46、e of the least concentrated calibration solution (excluding the zero member). The standard deviation shall not exceed 0,5 % of the mean absorbance of the most concentrated calibration solution. 5.2.2 Limit of detection. The limit of detection is a number, expressed in units of concentration (or amou

47、nt) that describes the lowest concentration level (or amount) of an element that can be determined to be statistically different from an analytical blank. The limit of detection of titanium in a matrix similar to that of the final test portion solution shall be better than 0,2 g/ml for the 365,3 nm

48、line and better than 0,1 g/ml for the 364,3 nm line. DIN EN 10211:2014-03 EN 10211:2013 (E) 7 5.2.3 Linearity of calibration. The value of the slope of the calibration graph covering the top 20 % of the concentration range (expressed as a change in absorbance) shall not be less than 0,7 times the value of the slope for the bottom 20 % of the concentration range (expressed as a change in absorbance) determined in the same way. For instruments with automatic calibration using two or more standa