BS EN 10211-2013 Chemical analysis of ferrous materials Determination of titanium in steels and cast irons Flame atomic absorption spectrometric method《黑色金属材料的化学分析 钢和铸铁中钛含量的测定 火焰原子.pdf

1、BSI Standards PublicationBS EN 10211:2013Chemical analysis of ferrousmaterials Determination oftitanium in steels and cast irons Flame atomic absorptionspectrometric methodBS EN 10211:2013 BRITISH STANDARDNational forewordThis British Standard is the UK implementation of EN 10211:2013. Itsupersedes

2、BS EN 10211:1996 which is withdrawn.The UK participation in its preparation was entrusted to TechnicalCommittee ISE/102, Methods of Chemical Analysis for Iron and Steel.A list of organizations represented on this committee can beobtained on request to its secretary.This publication does not purport

3、to include all the necessaryprovisions of a contract. Users are responsible for its correctapplication. The British Standards Institution 2013. Published by BSI StandardsLimited 2013ISBN 978 0 580 81798 4ICS 77.040.30; 77.080.01Compliance with a British Standard cannot confer immunity fromlegal obli

4、gations.This British Standard was published under the authority of theStandards Policy and Strategy Committee on 30 November 2013.Amendments issued since publicationDate Text affectedBS EN 10211:2013EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 10211 November 2013 ICS 77.040.30 Supersedes EN

5、10211:1995English 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 fontes - Mthode par spectromtrie dabsorption atom

6、ique 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 the CEN/CENELEC Internal Regulations w

7、hich 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 Management Centre or to any CEN member. This

8、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 status as the official versions. CEN member

9、s 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, Netherlands, Norway, Poland, Portugal

10、, 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 All rights of exploitation in any form

11、and by any means reserved worldwide for CEN national Members. Ref. No. EN 10211:2013 EBS EN 10211:2013EN 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 report . 1

12、0 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 criteria

13、 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 BS EN 10211:2013EN 10211:2013 (E) 3 Foreword This document (EN 10211:2013) has been prepared by

14、 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, and conflict

15、ing 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 document sup

16、ersedes 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 dissolutions desc

17、ribed; 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 coefficients co

18、rrected; 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 Yugoslav Republic

19、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. BS EN 10211:2013EN 10211:2013 (E) 4 1 Scope This European Stan

20、dard 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 documents, in whol

21、e 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 glassware - Sing

22、le-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 described: a) Th

23、e 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 filtrate. b) The secon

24、d 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) fusion of the residu

25、e 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 oxide/acetylene flam

26、e, 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 or water of equ

27、ivalent purity. 4.1 Nitric acid, HNO3(20= 1,40 g/ml). 4.2 Hydrochloric acid, HCl (20= 1,19 g/ml). BS EN 10211:2013EN 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 solution, 1 + 1. Add 1

28、00 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 water and transfer the

29、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 matrix solution, 20 g/l F

30、e. 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). Heat gently, until

31、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 crystallises. Allow to co

32、ol, 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 free of titanium or of k

33、nown 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 about 80 C, to expel ni

34、trous 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 titanium (99,99 % purity)

35、, 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-mark volumetric flas

36、k, dilute to the mark with water and mix well. BS EN 10211:2013EN 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 volumetric flask. Dilute to the

37、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 and mix well. 1 ml of thi

38、s 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 a titanium hollow-cathode

39、 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, the limit of detection and

40、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 5.2.4. 5.2.1 Minimum precision

41、. 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 absorbance of the least concentrate

42、d 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 amount) that describes the low

43、est 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 line and better than 0,1 g

44、/ml for the 364,3 nm line. BS EN 10211:2013EN 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

45、 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 standard solutions, it shall be established prior to the analysis, by obtaining absorbance readings, that the above requirements for graph l

46、inearity are fulfilled. 5.2.4 Characteristic concentration. The characteristic concentration for titanium in a matrix similar to the final test portion solution shall be better than 1,9 g/ml for the 365,3 nm line and better than 1,4 g/ml for the 364,3 nm line. 5.3 Ancillary equipment. A system for a

47、cquisition of the measured values, data processing and evaluation is necessary. Usually data processing and evaluation is performed with the appropriate software of the computer, connected to the atomic absorption spectrometer. Scale expansion can be used until the noise observed is greater than the

48、 read-out error and is preferred for absorbances below 0,1. If scale expansion has to be used and the instrument does not have the means to read the value of the scale expansion factor, the value can be calculated by measuring the absorbances of a suitable solution with and without scale expansion a

49、nd using the ratio of the signals obtained. 6 Sampling Sampling shall be carried out in accordance with EN ISO 14284 or with an appropriate national standard for steels. 7 Procedure 7.1 Test portion Weigh, to the nearest 0,001 g, 1 g of the test sample. 7.2 Blank test In parallel with the determination and following the same procedure, carry out a blank test using the same quantities of all reagents as used for the determination in accordance with the chosen dissolution method, 7.3.1 or 7.3.2, including iron (solution 4.10 or 4.11 dep