BS EN 15616-2012 Copper and copper alloys Determination of cadmium content Flame atomic absorption spectrometric method (FAAS)《铜和铜合金 镉含量的测定 火焰原子吸收光谱法(FAAS)》.pdf

1、raising standards worldwideNO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAWBSI Standards PublicationBS EN 15616:2012Copper and copper alloys Determination of cadmiumcontent Flame atomicabsorption spectrometricmethod (FAAS)Copyright European Committee for Standardization Provide

2、d by IHS under license with CENNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-BS EN 15616:2012 BRITISH STANDARDNational forewordThis British Standard is the UK implementation of EN 15616:2012. It supersedes DD CEN/TS 15616:2009 which is withdrawn.The UK participat

3、ion in its preparation was entrusted to Technical Committee NFE/34, Copper and copper alloys.A list of organizations represented on this committee can be obtained on request to its secretary.This publication does not purport to include all the necessary provisions of a contract. Users are responsibl

4、e for its correct application. The British Standards Institution 2013. Published by BSI Standards Limited 2013ISBN 978 0 580 75026 7 ICS 77.120.30 Compliance with a British Standard cannot confer immunity from legal obligations.This British Standard was published under the authority of the Standards

5、 Policy and Strategy Committee on 28 February 2013.Amendments issued since publicationDate T e x t a f f e c t e dCopyright European Committee for Standardization Provided by IHS under license with CENNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-BS EN 15616:2012

6、EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 15616 November 2012 ICS 77.120.30 Supersedes CEN/TS 15616:2009English Version Copper and copper alloys - Determination of cadmium content -Flame atomic absorption spectrometric method (FAAS) Cuivre et alliages de cuivre - Dtermination du cadmium -

7、 Mthode par spectromtrie dabsorption atomique dans la flamme (SAAF) Kupfer und Kupferlegierungen - Bestimmung des Cadmiumgehaltes - Flammenatomabsorptionsspektrometrisches Verfahren (FAAS) This European Standard was approved by CEN on 20 October 2012. CEN members are bound to comply with the CEN/CEN

8、ELEC 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 Management Centre

9、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 as the of

10、ficial 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, Netherland

11、s, 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 Management Centre: Avenue Marnix 17, B-1000 Brussels 2012 CEN All rights of exploitati

12、on in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 15616:2012: ECopyright European Committee for Standardization Provided by IHS under license with CENNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-BS EN 15616:2012EN 15616:201

13、2 (E) 2 Contents Page Foreword 31 Scope 42 Normative references 43 Principle 44 Reagents .45 Apparatus .56 Sampling .57 Procedure .58 Expression of results 89 Precision 1010 Test report . 11Bibliography . 12Copyright European Committee for Standardization Provided by IHS under license with CENNot fo

14、r ResaleNo reproduction or networking permitted without license from IHS-,-,-BS EN 15616:2012EN 15616:2012 (E) 3 Foreword This document (EN 15616:2012) has been prepared by Technical Committee CEN/TC 133 “Copper and copper alloys”, the secretariat of which is held by DIN. This European Standard shal

15、l be given the status of a national standard, either by publication of an identical text or by endorsement, at the latest by May 2013, and conflicting national standards shall be withdrawn at the latest by May 2013. Attention is drawn to the possibility that some of the elements of this document may

16、 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 supersedes CEN/TS 15616:2009. Within its programme of work, Technical Committee CEN/TC 133 requested CEN/TC 133/WG 10 “Methods of analysis“ to revise the fo

17、llowing document: CEN/TS 15616:2009, Copper and copper alloys Determination of cadmium content Flame atomic absorption spectrometric method (FAAS) In comparison with CEN/TS 15616:2009, the following significant technical changes were made: a) Conversion into a European Standard; b) Scope (Clause 1)

18、revised; c) Principle (Clause 3) completely revised, dissolution process changed; d) Precision (Clause 9) completely revised and the results of the precision test included. According to the CEN/CENELEC Internal Regulations, the national standards organisations of the following countries are bound to

19、 implement this European Standard: 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, Ro

20、mania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom. Copyright European Committee for Standardization Provided by IHS under license with CENNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-BS EN 15616:2012EN 15616:2012 (E) 4 1 Scope

21、This European Standard specifies a flame atomic absorption spectrometric method (FAAS) for the determination of the cadmium content of copper and copper alloys in the form of unwrought, wrought and cast products. The method is applicable to products having cadmium mass fractions between 0,000 5 % an

22、d 0,1 %. 2 Normative references The following documents, 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

23、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 preparation of samples for chemical analysis Part 2: Sampling of wrought products an

24、d castings 3 Principle Dissolution of a test portion in hydrochloric acid and nitric acid solution followed, after suitable dilution, by aspiration of the test solution into an air/acetylene flame of an atomic absorption spectrometer. Measurement of the absorption of the 228,8 nm line emitted by a c

25、admium hollow-cathode lamp. 4 Reagents During the analysis use only reagents of recognised analytical grade and only distilled water or water of equivalent purity. 4.1 Hydrochloric acid, HCl ( = 1,19 g/ml) 4.2 Nitric acid, HNO3( = 1,40 g/ml) 4.3 Nitric acid solution, 1 + 1 Add 500 ml of nitric acid

26、(4.2) to 500 ml of water. 4.4 Cadmium stock solution, 1,0 g/l Cd Weigh (1 0,001) g of cadmium (Cd 99,8 %) and transfer it into a 250 ml beaker. Add 10 ml of nitric acid (4.2). Cover with a watch glass and, if necessary, heat gently to assist dissolution. When dissolution is complete, allow to cool a

27、nd 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 1,0 mg of Cd. 4.5 Cadmium standard solution, 0,005 g/l Cd Transfer 2,5 ml of cadmium stock solution (4.4) into a 500 ml one-mark volumetric flask.

28、Dilute to the mark with water and mix. Prepare this solution immediately prior to use. 1 ml of this solution contains 0,005 mg of Cd. Copyright European Committee for Standardization Provided by IHS under license with CENNot for ResaleNo reproduction or networking permitted without license from IHS-

29、,-,-BS EN 15616:2012EN 15616:2012 (E) 5 4.6 Copper base solution, 50 g/l Cu Transfer 25,0 g of cadmium-free copper (Cu 99,95 %) into a 1 000 ml beaker. Add 250 ml of hydrochloric acid (4.1) and, cautiously, 125 ml of nitric acid (4.2). Cover with a watch glass and heat gently until the copper has be

30、en completely dissolved, then heat up to the boiling point until the nitrous fumes have been expelled. Allow to cool and transfer the solution quantitatively into a 500 ml one-mark volumetric flask, dilute to the mark with water and mix. 4.7 Copper base solution, 5 g/l Cu Transfer 50,0 ml of copper

31、base solution (4.6) into a 500 ml one-mark volumetric flask. Dilute to the mark with water and mix. 5 Apparatus 5.1 Atomic absorption spectrometer, fitted with an air/acetylene burner 5.2 Cadmium hollow-cathode lamp 6 Sampling Sampling shall be carried out in accordance with ISO 1811-1 or ISO 1811-2

32、, 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 Preparation of the test portion solution 7.1.1 General Prepare test portion solutions in accordance with 7.1.2 or 7.1.3 depending on the expected cadmium cont

33、ent of the test sample. 7.1.2 Cadmium mass fractions between 0,000 5 % and 0,010 % Weigh (1 0,001) g of the test sample. Transfer the test portion into a 250 ml beaker. Add 10 ml of hydrochloric acid (4.1) and 10 ml of the nitric acid solution (4.3). Cover with a watch glass and heat gently until th

34、e test portion is completely dissolved and then bring to boiling point until the nitrous fumes have been expelled. Cool to room temperature, and wash the beaker cover and the sides of the beaker with water. Transfer the dissolved test portion quantitatively into a 100 ml one-mark volumetric flask. D

35、ilute to the mark with water and mix. NOTE The validation test of this method showed that for cadmium mass fractions until and including 0,01 %, the results are better when the determination is carried out following 7.1.2. 7.1.3 Cadmium mass fractions between 0,01 % and 0,10 % Weigh (1 0,001) g of t

36、he test sample. Transfer the test portion into a 250 ml beaker. Add 10 ml of hydrochloric acid (4.1) and 10 ml of the nitric acid solution (4.3). Cover with a watch glass and heat gently until the test portion is completely dissolved and then bring to the boiling point until the nitrous fumes have b

37、een expelled. Cool to room temperature, and wash the beaker cover and the sides of the beaker with water. Copyright European Committee for Standardization Provided by IHS under license with CENNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-BS EN 15616:2012EN 15616

38、:2012 (E) 6 Transfer the dissolved test portion quantitatively into a 100 ml one-mark volumetric flask. Dilute to the mark with water and mix. Transfer 5,0 ml of this solution into a 100 ml one-mark volumetric flask. Dilute to the mark with water and mix. 7.2 Blank test Carry out a blank test simult

39、aneously with the determination, following the same procedure and using the same quantities of all reagents 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

40、synthetic sample containing a known amount of cadmium and of a composition similar to the material to be analysed. Carry out the procedure specified in 7.5. 7.4 Establishment of the calibration curve 7.4.1 Preparation of the calibration solutions 7.4.1.1 General In all cases, copper, chloride and ni

41、trate concentrations, and acidity in the calibration solutions shall be similar 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

42、to compensate for the effect of alloying elements. If an alloying element is present 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 (4.6 or 4.7) have been calculated to c

43、ompensate for chemical interaction effects of copper in test solutions of copper or high-copper alloys. Over-compensation 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

44、 shall be decreased to match the copper content of the test sample in solution. The cadmium 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 Cadmiu

45、m mass fractions between 0,000 5 % and 0,010 % Into each of a series of five 100 ml one-mark volumetric flasks, introduce the volumes of cadmium standard solution (4.5) and copper base solution (4.6) shown in Table 1. Dilute to the mark with water and mix. Copyright European Committee for Standardiz

46、ation Provided by IHS under license with CENNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-BS EN 15616:2012EN 15616:2012 (E) 7 Table 1 Calibration for cadmium mass fractions between 0,000 5 % and 0,010 % Cadmium Corresponding Corresponding Copper Corresponding Cor

47、respondingstandard cadmium cadmium base copper cadmiumsolution volume mass concentration solution volume mass mass fraction(4.5) after final dilution (4.6) of sampleml mg g/ml ml g % 0a0 0 20 1 0 1 0,005 0,05 20 1 0,000 5 4 0,020 0,20 20 1 0,002 010 0,050 0,50 20 1 0,005 0 20 0,100 1,00 20 1 0,010 0

48、aBlank test on reagents for calibration curve. 7.4.1.3 Cadmium mass fractions between 0,01 % and 0,10 % Into each of a series of five 100 ml one-mark volumetric flasks, introduce the volumes of cadmium standard solution (4.5) and copper base solution (4.7) shown in Table 2. Dilute to the mark with water and mix. Table 2 Calibration for cadmium mass fractions between 0,01 % and 0,10 % Cadmium Corresponding Corresponding Copper Corresponding Correspondingstandard cadmium cadmium base copper cadmiumsolution volume mass concentration solution volume mass mass fraction(4.5)