EN 15022-4-2011 en Copper and copper alloys - Determination of tin content - Part 4 Medium tin content - Flame atomic absorption spectrometric method (FAAS)《铜和铜合金锡含量测定 第4部分 中锡含量-火焰.pdf

1、raising standards worldwideNO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAWBSI Standards PublicationBS EN 15022-4:2011Copper and copper alloys Determination of tin contentPart 4: Medium tin content Flame atomicabsorption spectrometric method (FAAS)BS EN 15022-4:2011 BRITISH STA

2、NDARDNational forewordThis British Standard is the UK implementation of EN 15022-4:2011.It supersedes DD CEN/TS 15022-4:2006 which is withdrawn.The UK participation in its preparation was entrusted to TechnicalCommittee NFE/34, Copper and copper alloys.A list of organizations represented on this com

3、mittee can beobtained on request to its secretary.This publication does not purport to include all the necessaryprovisions of a contract. Users are responsible for its correctapplication. BSI 2011ISBN 978 0 580 71096 4ICS 77.120.30Compliance with a British Standard cannot confer immunity fromlegal o

4、bligations.This British Standard was published under the authority of theStandards Policy and Strategy Committee on 30 November 2011.Amendments issued since publicationDate Text affectedBS EN 15022-4:2011EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 15022-4 November 2011 ICS 77.120.30 Superse

5、des CEN/TS 15022-4:2006English Version Copper and copper alloys - Determination of tin content - Part 4: Medium tin content - Flame atomic absorption spectrometric method (FAAS) Cuivre et alliages de cuivre - Dtermination de la teneur en tain - Partie 4: tain en moyenne teneur - Mthode par spectromt

6、rie dabsorption atomique dans la flamme (SAAF) Kupfer und Kupferlegierungen - Bestimmung des Zinngehaltes - Teil 4: Mittlerer Zinngehalt - Flammenatomabsorptionsspektrometrisches Verfahren (FAAS) This European Standard was approved by CEN on 24 September 2011. CEN members are bound to comply with th

7、e 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 Managemen

8、t 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 status

9、as the official versions. CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, R

10、omania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG Management Centre: Avenue Marnix 17, B-1000 Brussels 2011 CEN All rights of exploitation in any form and by any means reserv

11、ed worldwide for CEN national Members. Ref. No. EN 15022-4:2011: EBS EN 15022-4:2011EN 15022-4:2011 (E) 2 Contents Page Foreword 31 Scope 42 Normative references 43 Principle 44 Reagents .45 Apparatus .56 Sampling .57 Procedure .57.1 Preparation of the test portion solution 57.1.1 Test portion 57.1.

12、2 Test portion solution .57.2 Blank test 57.3 Check test .57.4 Establishment of the calibration curve .67.4.1 Preparation of the calibration solutions 67.4.2 Adjustment of the atomic absorption spectrometer 67.4.3 Spectrometric measurement of the calibration solutions .77.4.4 Calibration curve77.5 D

13、etermination .77.5.1 General 77.5.2 Preliminary spectrometric measurement 77.5.3 Spectrometric measurements 78 Expression of results 88.1 Use of calibration curve 88.2 Use of bracketing method .89 Precision .810 Test report 9Bibliography . 11BS EN 15022-4:2011EN 15022-4:2011 (E) 3 Foreword This docu

14、ment (EN 15022-4:2011) 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

15、2012, and conflicting national standards shall be withdrawn at the latest by May 2012. 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.

16、 This document supersedes CEN/TS 15022-4:2006. Within its programme of work, Technical Committee CEN/TC 133 requested CEN/TC 133/WG 10 “Methods of analysis“ to prepare the revision of the following document: CEN/TS 15022-4:2006, Copper and copper alloys Determination of tin content Part 4: Medium ti

17、n content Flame atomic absorption spectrometry method (FAAS). In comparison with the first edition of CEN/TS 15022-4:2006, the following significant technical changes were made: a) conversion into a European Standard; b) Clause 9 completely revised and the results of the precision test included. Thi

18、s is one of four parts of the standard for the determination of tin content in copper and copper alloys. The other parts are: prEN 15022-1, Copper and copper alloys Determination of tin content Part 1: Titrimetric method (Part 1 will be the subject of a future work); CEN/TS 15022-2, Copper and coppe

19、r alloys Determination of tin content Part 2: Spectrophotometric method; EN 15022-3, Copper and copper alloys Determination of tin content Part 3: Low tin content Flame atomic absorption spectrometry method (FAAS). According to the CEN/CENELEC Internal Regulations, the national standards organizatio

20、ns of the following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal,

21、 Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and the United Kingdom. BS EN 15022-4:2011EN 15022-4:2011 (E) 4 1 Scope This European Standard specifies a flame atomic absorption spectrometric method (FAAS) for the determination of the tin content of copper and copper alloys in the form of

22、unwrought, wrought and cast products. The method is applicable to products having medium tin mass fractions between 0,2 % and 3,0 %. 2 Normative references The following referenced documents are indispensable for the application of this document. For dated references, only the edition cited applies.

23、 For undated references, the latest edition of the referenced document (including any amendments) applies. ISO 1811-1, Copper and copper alloys Selection and preparation of samples for chemical analysis Part 1: Sampling of cast unwrought products ISO 1811-2, Copper and copper alloys Selection and pr

24、eparation of samples for chemical analysis Part 2: Sampling of wrought products and castings 3 Principle Dissolution of a test portion in hydrochloric acid and hydrogen peroxide followed, after suitable dilution, by aspiration into a nitrous oxide/acetylene flame of an atomic absorption spectrometer

25、. Measurement of the absorption of the 286,3 nm line emitted by a tin hollow-cathode lamp. 4 Reagents Use only reagents of recognized analytical grade and only distilled water or water of equivalent purity. 4.1 Hydrochloric acid, HCl ( = 1,19 g/ml). 4.2 Hydrochloric acid solution, 7 + 3. Add 700 ml

26、of hydrochloric acid (4.1) to 300 ml of water. 4.3 Hydrogen peroxide, H2O230 % (mass fraction) solution, free from tin base stabilizers. Hydrogen peroxide may be stabilized by products containing some tin. It is therefore necessary to use exactly the same volume of hydrogen peroxide for the dissolut

27、ion of the test sample as for the preparation of the corresponding blank test. 4.4 Tin stock solution, 1 g/ l Sn. Weigh (1 0,001) g of tin (Sn 99 %) and transfer it into a 250 ml beaker. Dissolve it in 100 ml hydrochloric acid (4.1) and several drops of hydrogen peroxide (4.3) and cover with a watch

28、 glass. Heat gently until the metal is dissolved. Cool to room temperature and transfer the solution quantitatively into a 1 000 ml one-mark volumetric flask. Dilute to the mark with water and mix. 1 ml of this solution contains 1 mg of Sn. BS EN 15022-4:2011EN 15022-4:2011 (E) 5 4.5 Copper base sol

29、ution, 20 g/ l Cu. Weigh 10,0 g of electrolytic copper (Cu 99,95 %) into a 600 ml beaker. Add 250 ml of the hydrochloric acid solution (4.2) and cover with a watch glass. Cool to room temperature and add successively 5 ml hydrogen peroxide portions (4.3) until dissolution is complete, waiting after

30、each addition until all effervescence ceases. Heat to eliminate the excess of hydrogen peroxide. Cool to room temperature and transfer this solution quantitatively into a 500 ml one-mark volumetric flask. Dilute to the mark with water and mix. 5 Apparatus 5.1 Atomic absorption spectrometer, fitted w

31、ith a nitrous oxide/acetylene burner. 5.2 Tin hollow-cathode lamp. 6 Sampling Sampling shall be carried out in accordance with ISO 1811-1 or ISO 1811-2, as appropriate. Test samples shall be in the form of fine drillings, chips or millings, with a maximum thickness of 0,5 mm. 7 Procedure 7.1 Prepara

32、tion of the test portion solution 7.1.1 Test portion Weigh (1 0,001) g of the test sample. 7.1.2 Test portion solution Transfer the test portion (7.1.1) into a 250 ml beaker and cover with a watch glass. Add 25 ml of hydrochloric acid solution (4.2), cool and add 5 ml of hydrogen peroxide (4.3). Coo

33、l until the violent reaction has ceased and add, if necessary, 2 ml of hydrogen peroxide to continue the dissolution. Repeat this addition several times as necessary to complete the dissolution of the test portion. Heat to eliminate the excess of hydrogen peroxide and cool to room temperature. Trans

34、fer the dissolved test portion into a 100 ml one-mark volumetric flask. Add 3,5 ml of hydrochloric acid (4.1). Dilute to the mark with water and mix. 7.2 Blank test Carry out a blank test simultaneously with the determination, following the same procedure and using the same quantities of all reagent

35、s as used for the determination, but substituting pure copper for the test portion. 7.3 Check test Make a preliminary check of the apparatus by preparing a solution of a reference material or a synthetic sample containing a known amount of tin and of a composition similar to the material to be analy

36、sed. Carry out the procedure specified in 7.5. BS EN 15022-4:2011EN 15022-4:2011 (E) 6 7.4 Establishment of the calibration curve 7.4.1 Preparation of the calibration solutions 7.4.1.1 General In all cases, copper and chloride concentrations, and acidity in the calibration solutions shall be similar

37、 to those of the test portion solutions. The presence of copper in the calibration solutions compensates for chemical interaction effects of copper in the test portion solution. Normally no similar additions are required to compensate for the effect of alloying elements. If an alloying element is pr

38、esent in the material to be analysed in mass fraction 10 %, an appropriate mass of this element shall be added to the calibration solutions. The volumes of copper base solution added (4.5) have been calculated to compensate for chemical interaction effects of copper in test solutions of copper or hi

39、gh-copper alloys. Overcompensation may occur if the same volumes are added when the test samples are copper-based alloys where the percentage of copper is lower. In these cases the volumes of copper base solution shall be decreased to match the copper content of the test sample in solution. The tin

40、concentration of the calibration solutions shall be adjusted to suit the sensitivity of the spectrometer used, so that the curve of absorbance as a function of concentration is a straight line. 7.4.1.2 Tin mass fractions between 0,2 % and 3,0 % Into each of a series of eight 100 ml one-mark volumetr

41、ic flasks, introduce the volumes of the tin stock solution (4.4), the copper base solution (4.5) and hydrochloric acid (4.1) shown in Table 1. Dilute to the mark with water and mix. Table 1 Calibration for tin mass fractions between 0,2 % and 3,0 % Tin stock solution volume Correspondingtin mass Cor

42、respondingtin concentration after final dilution Copper base solution volume Correspondingcopper mass Hydrochloric acid volume Correspondingtin mass fractionof sample (4.4) (4.5) (4.1) ml mg mg/ml ml g ml %0 a0 0 50 1 3,5 0 2 2 0,02 50 1 3,3 0,20 5 5 0,05 50 1 3,0 0,50 10 10 0,10 50 1 2,5 1,0015 15

43、0,15 50 1 2,0 1,50 20 20 0,20 50 1 1,5 2,0025 25 0,25 50 1 1,0 2,50 30 30 0,30 50 1 0,5 3,00aBlank test on reagents for calibration curve. 7.4.2 Adjustment of the atomic absorption spectrometer Fit the tin hollow-cathode lamp (5.2) into the atomic absorption spectrometer (5.1), switch on the current

44、 and allow it to stabilize. Adjust the wavelength in the region of 286,3 nm to minimum absorbance. Following the BS EN 15022-4:2011EN 15022-4:2011 (E) 7 manufacturers instructions, fit the correct burner, light the flame and allow the burner temperature to stabilize. The flame shall be set up on oxi

45、dising conditions. Taking careful note of the manufacturers instructions regarding the minimum flow rate of acetylene, aspirate the calibration solution of highest concentration of analyte and adjust the burner configuration and gas flows to obtain maximum absorbance. NOTE The wavelength 286,3 nm wa

46、s chosen because of its stability, linearity of calibration curve, sensitivity and lack of interference. Similar sensitivity can be obtained by using the 235,5 nm wavelength. Use of other lines is not advised. 7.4.3 Spectrometric measurement of the calibration solutions Aspirate the series of calibr

47、ation solutions (7.4.1) in succession into the flame and measure the absorbance for each. Take care to keep the aspiration rate constant throughout the preparation of the calibration curve. Spray water through the burner after each measurement, see NOTE. NOTE For certain types of apparatus, instead

48、of water it is preferable to use a solution containing the attack reagents, in the same concentrations as in the test portion solutions. 7.4.4 Calibration curve Establish the calibration curve using measured absorbances and corresponding analyte amounts. Use appropriate spectrometer software or an o

49、ff-line computer for regression calculations or prepare a graphical representation. 7.5 Determination 7.5.1 General The analyses shall be carried out independently, in duplicate. 7.5.2 Preliminary spectrometric measurement Carry out a preliminary measurement on the test portion solution (7.1.2) following the same procedure specified in 7.4.2 and 7.4.3 at the same time as the spectrometric measurements are carried out