EN 16117-2-2012 en Copper and copper alloys - Determination of copper content - Part 2 Electrolytic determination of copper in materials with copper content higher than 99 80 %《铜和铜.pdf

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1、raising standards worldwideNO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAWBSI Standards PublicationBS EN 16117-2:2012Copper and copper alloys Determination of copper contentPart 2: Electrolytic determination of copper in materials with copper content higher than 99,80 %BS EN 1

2、6117-2:2012 BRITISH STANDARDNational forewordThis British Standard is the UK implementation of EN 16117-2:2012. The UK participation in its preparation was entrusted to T e c h n i c a l Committee NFE/34, Copper and copper alloys.A list of organizations represented on this committee can be obtained

3、on request to its secretary.This publication does not purport to include all the necessary provisions of a contract. Users are responsible for its correct application. The British Standards Institution 2013. Published by BSI Standards Limited 2013.ISBN 978 0 580 75025 0 ICS 77.120.30 Compliance with

4、 a British Standard cannot confer immunityfrom legal obligations.This British Standard was published under the authority of the Standards Policy and Strategy Committee on 31 January 2013.Amendments issued since publicationDate T e x t a f f e c t e dBS EN 16117-2:2012EUROPEAN STANDARD NORME EUROPENN

5、E EUROPISCHE NORM EN 16117-2 November 2012 ICS 77.120.30 English Version Copper and copper alloys - Determination of copper content - Part 2: Electrolytic determination of copper in materials with copper content higher than 99,80 % Cuivre et alliages de cuivre - Dtermination de la teneur en cuivre -

6、 Partie 2 : Dtermination par lectrogravimtrie du cuivre dans les matriaux ayant une teneur en cuivre suprieure 99,80 % Kupfer und Kupferlegierungen - Bestimmung des Kupfergehaltes - Teil 2: Elektrolytische Bestimmung von Kupfer in Werkstoffen mit einem Kupfergehalt grer als 99,80 % This European Sta

7、ndard was approved by CEN on 20 October 2012. CEN members are bound to comply with 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 concernin

8、g such national standards may be obtained on application to the CEN-CENELEC Management 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 it

9、s own language and notified to the CEN-CENELEC Management Centre has the same status 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, Germa

10、ny, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, 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

11、NORMUNG Management Centre: Avenue Marnix 17, B-1000 Brussels 2012 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 16117-2:2012: EBS EN 16117-2:2012EN 16117-2:2012 (E) 2 Contents Page Foreword 31 Scope 42 Normative references 43 Pri

12、nciple 44 Reagents .45 Apparatus .56 Sampling .57 Procedure .58 Expression of results 69 Precision .610 Test report 7Annex A (normative) Spent electrolyte Determination of residual copper Flame atomic absorption spectrometric method (FAAS) 8Bibliography . 11BS EN 16117-2:2012EN 16117-2:2012 (E) 3 Fo

13、reword This document (EN 16117-2:2012) has been prepared by Technical Committee CEN/TC 133 “Copper and copper alloys”, the secretariat of which is held by DIN. This European Standard shall be given the status of a national standard, either by publication of an identical text or by endorsement, at th

14、e 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 be the subject of patent rights. CEN and/or CENELEC shall not be held responsible for identifying any or all suc

15、h patent rights. Within its programme of work, Technical Committee CEN/TC 133 requested CEN/TC 133/WG 10 “Methods of analysis“ to prepare the following standard: EN 16117-2, Copper and copper alloys Determination of copper content Part 2: Electrolytic determination of copper in materials with copper

16、 content higher than 99,80 %. This is one of two parts of the standard for the determination of the copper content of copper and copper alloys. The other part is: EN 16117-1, Copper and copper alloys Determination of copper content Part 1: Electrolytic determination of copper in materials with coppe

17、r content less than 99,85 %. 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 Repub

18、lic 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 16117-2:2012EN 16117-2:2012 (E) 4 1 Scope This Europ

19、ean Standard specifies an electrolytic method for the determination of the copper content of unalloyed copper materials with a copper content higher than 99,80 % (mass fraction) in the form of castings, wrought and unwrought products. Silver, if present, is co-deposited and is reported as copper. Ap

20、proximately one-half of any selenium and tellurium present will co-deposit. Bismuth, if present, also interferes. 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

21、 edition cited applies. 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

22、 alloys Selection and preparation of samples for chemical analysis Part 2: Sampling of wrought products and castings. 3 Principle Dissolution of a test portion in a nitric and sulphuric acid mixture. Electrolytic deposition of the copper on a platinum cathode of known weight with subsequent weighing

23、 of the cathode together with the electrodeposited copper. Determination of residual copper in the spent electrolyte by atomic absorption spectrometry. 4 Reagents During the analysis use only reagents of recognised analytical grade and only distilled water or water of equivalent purity. 4.1 Sulphuri

24、c acid, H2SO4( = 1,84 g/ml) 4.2 Nitric acid, HNO3( = 1,40 g/ml) 4.3 Sulphuric acid-nitric acid mixture While stirring, slowly add 300 ml of sulphuric acid (4.1) to 750 ml of water. Cool to ambient temperature. While stirring, cautiously add 210 ml of nitric acid (4.2). 4.4 Sulphamic acid, H(NH2)SO34

25、.5 Sulphamic acid solution, 100 g/l H(NH2)SO3Dissolve 10 g of sulphamic acid (4.4) in water and dilute to 100 ml. Prepare freshly before using. 4.6 Alcohol Ethanol: 95 % 0,2 %, methanol: min. 99,9 %, other alcohols: higher than 99,9 %. BS EN 16117-2:2012EN 16117-2:2012 (E) 5 5 Apparatus 5.1 Current

26、source Preferably use a 6 V accumulator. If a rectifier is to be used, an additional buffer battery is recommended. 5.2 Electrolysis equipment 5.2.1 Platinum cathode, Winkler type1), made preferably from gauze containing approximately 400 meshes per square centimetre, woven from wire of diameter app

27、roximately 0,2 mm. The cathode shall be stiffened by doubling the gauze for about 3 mm at the top and the bottom of the cylinder or by reinforcing the gauze at the top and bottom with a platinum band or ring. The diameter of the cylinder shall be 30 mm to 50 mm and the height 40 mm to 60 mm. The ste

28、m shall be made from a platinum alloy wire such as platinum-iridium, platinum-rhodium or platinum-ruthenium, having a diameter of approximately 1,3 mm, flattened and welded the entire length of the gauze. The overall height of the cathode shall be approximately 130 mm. The cathode shall be sandblast

29、ed. 5.2.2 Spiral anode, made of platinum alloy wire of minimum diameter 1 mm, formed into a spiral of seven turns, having a height of approximately 50 mm and a diameter of 12 mm, the overall height being approximately 130 mm. The spiral section shall be sandblasted. 6 Sampling Sampling shall be carr

30、ied 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 Test portion Weigh (5,0 0,001) g of the test sample. 7.2 Determination 7.2.1 Transfer the test portion (7.1)

31、 to a 400 ml tall-form beaker. Add 45 ml of the sulphuric acid-nitric acid mixture (4.3) by small portions and then cover with a watch glass. Cool if required to prevent the reaction from becoming violent. When the reaction has subsided, heat moderately (80 C to 90 C) until dissolution is complete.

32、Continue heating at approximately 90 C, without boiling, to completely expel the oxides of nitrogen (more than 1 h may be necessary). Cool slightly and carefully wash down the watch glass and the sides of the beaker with water. Add 10 ml of the sulphamic acid solution (4.5), stir and dilute to 175 m

33、l to 200 ml. 7.2.2 Weigh the cathode (5.2.1) to the nearest 0,1 mg. 7.2.3 Position the electrodes (5.2.1 and 5.2.2) in the solution and add water so that the gauze is completely immersed. Cover the beaker with two halves of a watch glass, one of which has two indentations through which the electrode

34、 stems may pass. Electrolyze at a current of about 1 A to 3 A, slowly stirring the electrolyte by a magnetic stirrer, avoiding turbulence (see Note). When the solution becomes colourless, wash the cover, the electrode stem and the sides of the beaker. Add 10 ml of sulphamic acid solution (4.5) and c

35、ontinue the electrolysis until deposition is essentially complete, as indicated by failure to plate on a new surface of the cathode stem, when the level of the solution is raised. NOTE When a current of 1 A to 3 A is used, the electrolysis requires less than 10 h. Avoid extended electrolysis times.

36、1)Platinum cathodes formed from plain or perforated sheets may also be used.BS EN 16117-2:2012EN 16117-2:2012 (E) 6 7.2.4 Without switching off the current, wash the cathode with a stream of water as it is being removed from the spent solution. Immediately wash successively in two baths of water and

37、 two baths of ethanol, methanol or other alcohols (4.6). Dry at 110 C for 3 min to 5 min and cool to ambient temperature in a desiccator. Determine the mass of the metallic copper deposited. Reserve the spent electrolyte. 7.2.5 Determine the residual copper in the spent electrolyte by a convenient s

38、pectrometric technique such as atomic absorption spectrometry or inductively coupled plasma optical emission spectrometry. The flame atomic absorption spectrometry method is described in the Annex A. 8 Expression of results Calculate the copper mass fraction, in percent (%), using Formula (1): wCu=

39、100)(0321+mmmm(1) where: wCuis the copper mass fraction in per cent (%); m0is the mass of the test portion (7.1), in grams (g); m1is the mass of the cathode plus the electrodeposited copper, in grams (g); m2is the mass of the cathode (5.2.1), in grams (g); m3is the mass of residual copper found in t

40、he spent electrolyte (Annex A), in grams (g). 9 Precision Twelve laboratories co-operated in testing this method and obtained the results summarised in Table 1. Table 1 Statistical information Level Reference value % Found % Repeatability r Reproducibility R 1 99,89 99,837 0,074 0,106 2 99,99 99,988

41、 0,013 0,032 NOTE Taking into account the narrowness of the scope (99,80 % to 100 %) and the discrepancy in the relation between the level of content and the r and R levels (r and R for the lowest level of content are higher than those for the highest level), the lg relationship between copper mass

42、fraction (wCu) and r and R is irrelevant. Therefore, it is suitable to take 0,074 % and 0,106 % as the representative values for r and R respectively, for the whole scope of the method. BS EN 16117-2:2012EN 16117-2:2012 (E) 7 10 Test report The test report shall contain the following information: a)

43、 identification of the test sample; b) reference to this European Standard (EN 16117-2); c) method used; d) results; e) any unusual characteristics noted during the determination; f) any operation not included in this European Standard or in the document to which reference is made or regarded as opt

44、ional; g) date of the test and/or date of preparation or signature of the test report; h) signature of the responsible person. BS EN 16117-2:2012EN 16117-2:2012 (E) 8 Annex A (normative) Spent electrolyte Determination of residual copper Flame atomic absorption spectrometric method (FAAS) A.1 Genera

45、l This Annex specifies a flame atomic absorption spectrometric method (FAAS) for the determination of the copper content of spent electrolyte after the deposition of copper on the electrode as described in 7.2.3 and 7.2.4. NOTE Elements and reagents ordinarily present in the spent electrolyte do not

46、 interfere. A.2 Principle Aspiration of the test solution into an air-acetylene flame of an atomic absorption spectrometer and determination of the copper content by measurement of the absorption of the most convenient lines (324,8 nm or 327,4 nm) emitted by a copper hollow-cathode lamp. A.3 Reagent

47、s During the analysis use only reagents of recognised analytical grade and only distilled water or water of equivalent purity. A.3.1 Sulphuric acid, H2SO4( = 1,84 g/ml) A.3.2 Sulphuric acid solution, 1 + 1 Carefully, while stirring, add 100 ml of sulphuric acid (A.3.1) to 100 ml of water. A.3.3 Nitr

48、ic acid, HNO3( = 1,40 g/ml) A.3.4 Nitric acid solution, 1 + 1 Add 100 ml of nitric acid (A.3.3) to 100 ml of water. A.3.5 Copper stock solution, 1,0 g/l Cu Weigh (1 0,001) g of pure copper (Cu 99,9 %) and transfer it into a 250 ml beaker. Add 10 ml of nitric acid solution (A.3.4) and cover with a wa

49、tch glass. After dissolution, warm the solution to expel nitrous fumes. Cool to room temperature and transfer 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 Cu. A.3.6 Copper standard solution, 0,02 g/l Cu Transfer 5 ml of the copper stock solution (A.3.5) into a 250 ml one-mark volumetric flask. Dilute to the mark with water and mix. 1 ml of this solution contains 20 g Cu. BS EN 16117-2:2012EN 16117-2:20