BS EN 16117-1-2011 Copper and copper alloys Determination of copper content Electrolytic determination of copper in materials with copper content less than 99 85 %《铜和铜合金 含铜量的测定 含铜量.pdf

1、raising standards worldwideNO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAWBSI Standards PublicationBS EN 16117-1:2011Copper and copper alloys Determination of coppercontentPart 1: Electrolytic determination of copperin materials with copper content less than99,85 %BS EN 16117-

2、1:2011 BRITISH STANDARDNational forewordThis British Standard is the UK implementation of EN 16117-1:2011.The UK participation in its preparation was entrusted to TechnicalCommittee NFE/34, Copper and copper alloys.A list of organizations represented on this committee can beobtained on request to it

3、s 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 71094 0ICS 77.120.30Compliance with a British Standard cannot confer immunity fromlegal obligations.This British Standard was p

4、ublished under the authority of theStandards Policy and Strategy Committee on 31 October 2011.Amendments issued since publicationDate Text affectedBS EN 16117-1:2011EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 16117-1 October 2011 ICS 77.120.30 English Version Copper and copper alloys - Dete

5、rmination of copper content - Part 1: Electrolytic determination of copper in materials with copper content less than 99,85 % Cuivre et alliages de cuivre - Dtermination de la teneur en cuivre - Partie 1: Dtermination par lectrogravimtrie de la teneur en cuivre dans les alliages ayant une teneur en

6、cuivre infrieure 99,85 % Kupfer und Kupferlegierungen - Bestimmung des Kupfergehaltes - Teil 1: Elektrolytische Bestimmung von Kupfer in Werkstoffen mit einem Kupfergehalt kleiner als 99,85 % This European Standard was approved by CEN on 27 August 2011. CEN members are bound to comply with the CEN/C

7、ENELEC 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 Centr

8、e 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

9、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, Romania,

10、 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 reserved worl

11、dwide for CEN national Members. Ref. No. EN 16117-1:2011: EBS EN 16117-1:2011EN 16117-1:2011 (E) 2 Contents Page Foreword 31 Scope 42 Normative references 43 Principle 44 Reagents .45 Apparatus .56 Sampling .57 Procedure .57.1 Test portion 57.2 Determination .58 Expression of results 69 Precision .6

12、10 Test report 7Annex A (normative) Spent electrolyte Determination of residual copper Flame atomic absorption spectrometric method (FAAS) 8A.1 General 8A.2 Principle 8A.3 Reagents .8A.4 Apparatus .9A.5 Procedure .9A.6 Expression of results . 10Bibliography . 12BS EN 16117-1:2011EN 16117-1:2011 (E)

13、3 Foreword This document (EN 16117-1:2011) 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, a

14、t the latest by April 2012, and conflicting national standards shall be withdrawn at the latest by April 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

15、 all such 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 16117-1, Copper and copper alloys Determination of copper content Part 1: Electrolytic determination of copper in materials wit

16、h copper content less than 99,85 %. 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: prEN 16117-2, Copper and copper alloys Determination of copper content Part 2: Electrolytic determination of copper in materials wi

17、th copper content higher than 99,80 %. According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Ger

18、many, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and the United Kingdom. BS EN 16117-1:2011EN 16117-1:2011 (E) 4 1 Scope This European Standard specifies an electrolyti

19、c method for the determination of the copper content in copper materials with a copper content less than 99,85 % (mass fraction) in the form of unwrought, wrought and cast products. Silver, if present, is co-deposited and is reported as copper. Approximately one-half of any selenium and tellurium pr

20、esent will co-deposit. Arsenic, antimony, bismuth and tin, if present, also interfere. 2 Normative references The following referenced documents are indispensable for the application of this document. For dated references, only the edition cited applies. For undated references, the latest edition of

21、 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 preparation of samples for chemical analysis Par

22、t 2: Sampling of wrought products and castings 3 Principle Dissolution of a test portion in a fluoroboric and nitric acid mixture. Electrolytic deposition of the copper on a platinum cathode of known weight. Determination of residual copper in the spent electrolyte by atomic absorption spectrometry.

23、 4 Reagents During the analysis use only reagents of recognized analytical grade and only distilled water or water of equivalent purity. 4.1 Boric acid, H3BO3. 4.2 Boric acid solution, 40 g/l H3BO3. Dissolve 40 g of boric acid (4.1) in a 1 000 ml one-mark flask with water, dilute to the mark with wa

24、ter and mix. 4.3 Hydrofluoric acid, HF ( = 1,13 g/ml). 4.4 Nitric acid, HNO3( = 1,40 g/ml). 4.5 Nitric acid solution, 1 + 1. Add 500 ml of nitric acid (4.4) to 500 ml of water. 4.6 Ammonia solution, NH4OH ( 0,91 g/ml). 4.7 Hydrochloric acid, HCl, ( = 1,19 g/ml). 4.8 Alcohol. Ethanol: 95 % 0,2 %, met

25、hanol: min. 99,9 %, other alcohols: higher than 99,9 %. 4.9 Hydrogen Peroxide, H2O2(30 % (mass fraction) solution, = 1,2 g/ml). BS EN 16117-1:2011EN 16117-1:2011 (E) 5 5 Apparatus 5.1 Current source. Preferably, use a 6 V accumulator. If a rectifier is to be used, an additional buffer battery is rec

26、ommended. 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 approximately 0,2 mm. The cathode shall be stiffened by doubling the gauze for about 3 mm at the top and the

27、 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 stem shall be made from a platinum alloy wire such as platinum-iridium, platinum-rhodium or platinum-rutheni

28、um, 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 sandblasted. 5.2.2 Spiral anode, made of platinum alloy wire of minimum diameter 1 mm, formed into a spiral of sev

29、en 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. In the case of an analysis of alloys containing lead, gauze anodes shall be used. 6 Sampling Sampling shall be carried out in accordance w

30、ith 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 (2,5 0,001) g of the test sample. 7.2 Determination 7.2.1 Transfer the test portion (7.1) to a 400 ml tall-form

31、beaker. Add 15 ml of the boric acid solution (4.2), 2 ml of the hydrofluoric acid (4.3) and 30 ml of the nitric acid solution (4.5). Cover with a watch glass and allow to stand until the reaction has nearly ceased. 7.2.2 Wash the watch glass and the walls of the beaker and boil the solution, or alte

32、rnatively heat the solution in a boiling water bath for about one hour, to completely expel the oxides of nitrogen. Cool to ambient temperature and dilute the solution with 50 ml of cold water. NOTE In cases of copper alloys having a lead content 0,5 %, addition of 2,5 ml of a 5 g/l lead standard so

33、lution may advantageously increase the kinetic of the copper deposition. This standard solution is prepared by dissolution of 2,5 g of pure lead (Pb 99,99 % mass fraction) in 50 ml of nitric acid solution (4.5) and, after boiling in order to expel the oxides of nitrogen, is transferred into a 500 ml

34、 one-mark volumetric flask, made up to the mark with water and mixed. Neutralize with ammonia solution (4.6) until a precipitate appears. Re-acidify with the nitric acid solution (4.5) until the precipitate is dissolved. Add 20 ml of the nitric acid solution (4.5) and dilute the solution with water

35、to 300 ml. Add one drop of hydrochloric acid (4.7). 7.2.3 Weigh the cathode (5.2.1) to the nearest 0,1 mg. 1) Platinum cathodes formed from plain or perforated sheets may also be used. BS EN 16117-1:2011EN 16117-1:2011 (E) 6 7.2.4 Position the electrodes (5.2.1 and 5.2.2) in the solution and cover t

36、he beaker with two halves of a watch glass, one of which has two indentations through which the electrode stems may pass. Electrolyse at a current of about 1 A to 3 A while slowly stirring the electrolyte. When the solution becomes colourless, wash the watch glass, the electrode stem and the sides o

37、f the beaker. Continue the electrolysis until the deposition of the copper is complete, as indicated by failure to plate on a new surface of the cathode stem, when the level of the solution is raised. NOTE If manganese is present in the sample and it is oxidized to MnO4during electrolysis, drops of

38、hydrogen peroxide solution (4.9) need to be added until the colour due to the oxidized form of manganese disappears. 7.2.5 Without switching off the current, wash the cathode with a stream of water as it is being removed from the spent solution. Remove the cathode and dip it in ethanol, methanol or

39、other alcohols (4.8). 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. 7.2.6 Determine the residual copper in the spent electrolyte by a convenient spectrometric technique such as atom

40、ic absorption spectrometry or Inductively coupled plasma optical emission spectrometry. The flame atomic absorption spectrometry method is described in Annex A. 8 Expression of results Calculate the copper mass fraction, in percent (%),using Equation (1): wCu= 100)(0321+mmmm(1) where wCuis the coppe

41、r mass fraction in per cent (%); m0is the mass of the test portion (7.1), in grams (g); m1 is the mass of the cathode plus the electro-deposited copper, in grams (g); m2is the mass of the cathode (5.2.1), in grams (g); m3is the mass of residual copper found in the spent electrolyte (Annex A), in gra

42、ms (g). 9 Precision Twelve laboratories co-operated in testing this method and obtained the results summarized in Table 1 and Figure 1 respectively. Table 1 Statistical information Level Reference value % Found % Repeatability r Reproducibility R 1 58,5 58,494 0,095 0,1442 95,0 94,977 0,132 0,167 BS

43、 EN 16117-1:2011EN 16117-1:2011 (E) 7 lg R = 0,309 8 lg wCu 1,390 8 lg r = 0,688 7 lg wCu 2,240 5 Figure 1 lg relationship between copper concentration wCuand r and R 10 Test report The test report shall contain the following information: a) identification of the test sample; b) reference to this Eu

44、ropean Standard (EN 16117-1); 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 optional; g) date of the test and/or date of preparation or si

45、gnature of the test report; h) signature of the responsible person. BS EN 16117-1:2011EN 16117-1:2011 (E) 8 Annex A (normative) Spent electrolyte Determination of residual copper Flame atomic absorption spectrometric method (FAAS) A.1 General This Annex specifies a flame atomic absorption spectromet

46、ric method (FAAS) for the determination of the copper content of spent electrolyte after the deposition of copper on the electrode as described in 7.2.4 and 7.2.5. NOTE Elements and reagents ordinarily present in the spent electrolyte do not interfere. A.2 Principle Aspiration of the test solution i

47、nto 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 Reagents During the analysis use only reagents of recognized analy

48、tical grade and only distilled water or water of equivalent purity. A.3.1 Nitric acid, HNO3( = 1,40 g/ml). A.3.2 Nitric acid solution, 1 + 1. Add 500 ml of nitric acid (A.3.1) to 500 ml of water. A.3.3 Boric acid, H3BO3. A.3.4 Boric acid solution, 40 g/l H3BO3. Dissolve 10 g boric acid (A.3.3) in a

49、250 ml one-mark flask in water, dilute to the mark with water and mix. A.3.5 Hydrofluoric acid, HF ( = 1,13 g/ml). A.3.6 Acid mixture solution. In a 500 ml one-mark volumetric flask introduce: 150 ml of boric acid solution (A.3.4); 20 ml of hydrofluoric acid (A.3.5); 300 ml of nitric acid solution (A.3.2); add water up to the mark and mix. A.3.7 Ammonia solution, NH4OH ( 0,91 g/ml). A.3.8 Copper stock solution, 1,0 g/l Cu. BS EN 16117-1: