BS EN 14936-1-2006 Copper and copper alloys - Determination of aluminium content - Titrimetric method《铜和铜合金 铝含量的测定 滴定法》.pdf

1、 g49g50g3g38g50g51g60g44g49g42g3g58g44g55g43g50g56g55g3g37g54g44g3g51g40g53g48g44g54g54g44g50g49g3g40g59g38g40g51g55g3g36g54g3g51g40g53g48g44g55g55g40g39g3g37g60g3g38g50g51g60g53g44g42g43g55g3g47g36g58Part 1: Titrimetric methodThe European Standard EN 14936-1:2006 has the status of a British Standar

2、dICS 77.120.30Copper and copper alloys Determination of aluminium content BRITISH STANDARDBS EN14936-1:2006BS EN 14936-1:2006This British Standard was published under the authority of the Standards Policy and Strategy Committee on 31 August 2006 BSI 2006ISBN 0 580 49078 5Cross-referencesThe British

3、Standards which implement international or European publications referred to in this document may be found in the BSI Catalogue under the section entitled “International Standards Correspondence Index”, or by using the “Search” facility of the BSI Electronic Catalogue or of British Standards Online.

4、This publication does not purport to include all the necessary provisions of a contract. Users are responsible for its correct application. Compliance with a British Standard does not of itself confer immunity from legal obligations.Summary of pagesThis document comprises a front cover, an inside fr

5、ont cover, the EN title page, pages 2 to 9 and a back cover.The BSI copyright notice displayed in this document indicates when the document was last issued.Amendments issued since publicationAmd. No. Date CommentsA list of organizations represented on this committee can be obtained on request to its

6、 secretary. present to the responsible international/European committee any enquiries on the interpretation, or proposals for change, and keep UK interests informed; monitor related international and European developments and promulgate them in the UK.National forewordThis British Standard is the of

7、ficial English language version of EN 14936-1:2006. The UK participation in its preparation was entrusted to Technical Committee NFE/34, Copper and copper alloys, which has the responsibility to: aid enquirers to understand the text;EUROPEAN STANDARDNORME EUROPENNEEUROPISCHE NORMEN 14936-1June 2006I

8、CS 77.120.30English VersionCopper and copper alloys - Determination of aluminium content -Part 1: Titrimetric methodCuivre et alliages de cuivre - Dosage de laluminium -Partie 1 : Mthode titrimtriqueKupfer und Kupferlegierungen - Bestimmung desAluminiumgehaltes - Teil 1: Titrimetrisches VerfahrenThi

9、s European Standard was approved by CEN on 15 May 2006.CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this EuropeanStandard the status of a national standard without any alteration. Up-to-date lists and bibliographical references c

10、oncerning such nationalstandards may be obtained on application to the Central Secretariat or to any CEN member.This European Standard exists in three official versions (English, French, German). A version in any other language made by translationunder the responsibility of a CEN member into its own

11、 language and notified to the Central Secretariat has the same status as the officialversions.CEN members are the national standards bodies of Austria, Belgium, Cyprus, Czech Republic, Denmark, Estonia, Finland, France,Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg,

12、 Malta, Netherlands, Norway, Poland, Portugal, Romania,Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom.EUROPEAN COMMITTEE FOR STANDARDIZATIONCOMIT EUROPEN DE NORMALISATIONEUROPISCHES KOMITEE FR NORMUNGManagement Centre: rue de Stassart, 36 B-1050 Brussels 2006 CEN All rights of exp

13、loitation in any form and by any means reservedworldwide for CEN national Members.Ref. No. EN 14936-1:2006: EEN 14936-1:2006 (E) 2 Contents Page Foreword3 1 Scope 4 2 Normative references 4 3 Principle4 4 Reagents and materials 4 5 Apparatus .5 6 Sampling.5 7 Procedure .5 8 Expression of results 7 9

14、 Precision.7 10 Test report 8 Bibliography9 EN 14936-1:2006 (E) 3 Foreword This document (EN 14936-1:2006) 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,

15、 either by publication of an identical text or by endorsement, at the latest by December 2006, and conflicting national standards shall be withdrawn at the latest by December 2006. Within its programme of work, Technical Committee CEN/TC 133 requested CEN/TC 133/WG 10 “Methods of analysis” to prepar

16、e the following standard: EN 14936-1, Copper and copper alloys Determination of aluminium content Part 1: Titrimetric method This is one of two parts of the standard for the determination of aluminium content in copper and copper alloys. The other part is: EN 14936-2, Copper and copper alloys Determ

17、ination of aluminium content Part 2: FAAS method According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following coun-tries are bound to implement this European Standard: Austria, Belgium, Cyprus, Czech Republic, Denmark, Esto-nia, Finland, France, Germany, G

18、reece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom. EN 14936-1:2006 (E) 4 1 Scope This part of this European Standard specifies a titrimetric method for the d

19、etermination of the aluminium content of copper and copper alloys in the form of unwrought, wrought and cast products. The method is applicable to products having aluminium mass fractions between 0,5 % and 12 %. 2 Normative references The following referenced documents are indispensable for the appl

20、ication of this document. For dated references, only the 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 o

21、f cast unwrought products ISO 1811-2, Copper and copper alloys Selection and preparation of samples for chemical analysis Part 2: Sampling of wrought products and castings NOTE Informative references to documents used in the preparation of this standard, and cited at the appropriate places in the te

22、xt, are listed in the Bibliography. 3 Principle Determination of aluminium by chelatometric titration at pH about 6, following a sodium fluoride demasking procedure, and using a voltametric indication. 4 Reagents and materials 4.1 General During the analysis, use only reagents of recognized analytic

23、al grade and only distilled water or water of equivalent purity. 4.2 Hexamethylenetetramine, (CH2)6N4. 4.3 Chloroform, CHCl3. 4.4 Perchloric acid, HClO4( = 1,68 g/ml). WARNING Perchloric acid, concentrated and hot, reacts rapidly, often with violently explosive force, with oxidizable materials. Spec

24、ially designed hoods are specified for handling perchloric acid fumes and any hood in which perchloric acid is fumed should not be used for other operations that permit easily oxi-dizable materials to collect in the ducts and blower. 4.5 Nitric acid, HNO3( = 1,40 g/ml). 4.6 Nitric acid solution, 1 +

25、 1 Dilute 50 ml of nitric acid (4.5) in 50 ml of water. 4.7 Hydrochloric acid, HCl ( = 1,19 g/ml). EN 14936-1:2006 (E) 5 4.8 Hydrochloric acid solution, 1 + 1 Dilute 50 ml of hydrochloric acid (4.7) in 50 ml of water. 4.9 Disodium salt of ethylenediaminetetra-acetic acid (EDTA), C10H14N2Na2O8 2 H2O,

26、 0,2 mol/l Dissolve 74,448 g Disodium-ethylenediaminetetra-acetic acid dihydrate in water and dilute to 1 000 ml. 4.10 Hydrogen peroxide, H2O230 % (mass fraction) solution 4.11 Cupferron solution Dissolve 10 g of cupferron in 100 ml water. 4.12 Manganese solution, 4,55 g/l of Mn(NO3)2 4H2O. 4.13 Cop

27、per base solution, 0,05 mol/l solution Weigh 3,177 g of copper, (Cu 99,9 %) and transfer it into a 250 ml beaker. Add 20 ml of nitric acid (4.5). Heat gently until the copper is dissolved, and then bring to the boiling point until the nitrous fumes have been expelled. Cool to room temperature, trans

28、fer the solution quantitatively into a 1 000 ml one-mark volumetric flask, dilute to the mark with water and mix well. 4.14 Sodium fluoride solution, NaF 25 g/l. 5 Apparatus 5.1 Ordinary laboratory apparatus 5.2 Potentiometer in connection with a device for a voltametric indication, i.e. for polaris

29、ing the elec-trodes with a constant current of 2 A to 10 A. This attachment can be made in a simple way using, for example, an accumulator or a storage battery of 2 V in series with a 1 M resistor and the electrodes. The potentiometer shall be in parallel with the electrodes. 5.3 Double platinum ele

30、ctrode, made of 1 mm diameter platinum wire, sealed in a glass tube directly or af-ter welding on a copper wire in such a way that each wire electrode is about 4 mm long with a free geometric sur-face of about 10 mm2. 6 Sampling Sampling shall be carried out in accordance with ISO 1811-1 or ISO 1811

31、-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 Preparation of the test portion solution 7.1.1 General Prepare test portion solutions, ready for titration, in accordance with one of the procedures in 7.1.2

32、 to 7.1.5 depending on the expected aluminium content of the sample and whether it is free from or containing titanium and zirconium. EN 14936-1:2006 (E) 6 7.1.2 Alloys free from titanium and zirconium, having aluminium mass fractions between 0,5 % and 4,0 % Weigh (0,5 0,001) g of the sample. Transf

33、er the test portion into a 250 ml tall-form beaker. Add 5 ml of water and 5 ml of the nitric acid solution (4.6). Heat gently until the test portion is completely dissolved. Evaporate the solution obtained to about 1 ml to 2 ml and di-lute with 25 ml of water. Add 1 ml of the manganese solution (4.1

34、2), 42 ml of the EDTA solution (4.9) and sufficient hexamethylenetetramine (4.2) to give a pH value 6,0 to 6,2. (The manganese solution may be omitted if the sample contains 0,5 % or more of manganese). Boil for 5 min and cool to room temperature. 7.1.3 Alloys free from titanium and zirconium, havin

35、g aluminium mass fractions over 4,0 % up to and including 12,0 % Weigh (0,2 0,001) g of the sample. Transfer the test portion into a 250 ml tall-form beaker. Add 5 ml of water and 3 ml of the nitric acid solution (4.6). Heat gently until the test portion is completely dissolved. Evaporate the soluti

36、on obtained to about 1 ml to 2 ml and di-lute with 25 ml of water. Add 1 ml of the manganese solution (4.12), 22 ml of the EDTA solution (4.9) and sufficient hexamethylenetetramine (4.2) to give a pH value 6,0 to 6,2. (The manganese solution may be omitted if the sample contains 0,5 % or more of man

37、ganese.) Boil for 5 min and cool to room temperature. 7.1.4 Alloys containing titanium and zirconium, having aluminium mass fractions between 0,5 % and 4,0 % Weigh (0,5 0,001) g of the sample. Transfer the test portion into a 250 ml tall-form beaker and dissolve with 30 ml of the hydrochloric acid s

38、olution (4.8) by adding a total amount of 10 ml of the hydrogen peroxide (4.10) in several small portions. Cool the solution during this operation. Destroy the excess peroxide by boiling for about 5 min. After cooling to room temperature, transfer the solution into a separating funnel of approximate

39、ly 150 ml, using as little water as necessary for rinsing. The total vol-ume of the solution shall amount to approximately 50 ml. Depending on the amount of iron, titanium and zirconium present, add 2 ml to 5 ml of the cupferron solution (4.11) and 20 ml of the chloroform (4.3) and shake vigourously

40、 for about 1 min. After separation of the phases, draw off the organic phase and repeat the extraction of the aqueous phase using 1 ml of the cupferron solution and 10 ml of the chloroform. Repeat this extraction once more if the organic phase shows a yellowish colour at this step. Discard the chlor

41、oform phases. Transfer the aqueous solution, now free of iron, titanium and zirconium, into a 250 ml tall-form beaker and evaporate to about 5 ml. Add 5 ml of the perchloric acid (4.4) and 5 ml of the nitric acid (4.5) and destroy any organic matter which may be present by wet combustion. Fume the p

42、erchloric acid to about 1 ml, dilute with about 25 ml of water and filter off any insoluble matter. 7.1.5 Alloys containing titanium and zirconium, having aluminium mass fractions over 4,0 % up to and including 12,0 % Weigh (0,2 0,001) g of the sample. Transfer the test portion into a 250 ml tall-fo

43、rm beaker and dissolve with 25 ml of the hydrochloric acid solution (4.8) by adding a total amount of 5 ml of the hydrogen peroxide (4.10) in several small portions. Cool the solution during this operation. Destroy the excess peroxide by boiling for about 5 min. After cooling to room temperature, tr

44、ansfer the solution into a separating funnel of approximately 150 ml, using as little water as necessary for rinsing. The total volume of the solution shall amount to approximately 50 ml. Depending on the amount of iron, titanium and zirconium present, add 2 ml to 5 ml of the cupferron solution (4.1

45、1) and 20 ml of the chloroform (4.3) and shake vigourously for about 1 min. After separation of the phases, draw off the organic phase and repeat the extraction of the aqueous phase using 1 ml of the cupferron solution and 10 ml of the chloroform. Repeat this extraction once more if the organic phas

46、e shows a yellowish colour at this step. Discard the chloroform phases. Transfer the aqueous solution, now free of iron, titanium and zirconium, to a 250 ml tall-form beaker and evaporate into about 5 ml. Add 5 ml of the perchloric acid (4.4) and 5 ml of the nitric acid (4.5) and destroy any organic

47、 matter which may be present, by wet combustion. Fume the perchloric acid to about 1 ml, di-lute with about 25 ml of water and filter off any insoluble matter. EN 14936-1:2006 (E) 7 7.2 Blank test Carry out a blank test simultaneously with the determination, following the same procedure and using th

48、e same quan-tities of all the reagents as used for the determination, but omitting the test portion. 7.3 Check test Make a preliminary check of the apparatus by preparing a solution of a standard material or a synthetic sample con-taining a known amount of aluminium and of composition similar to the

49、 material to be analysed. Carry out the proce-dure specified in 7.4. 7.4 Determination Titrate the excess EDTA present in the test portion solution (see 7.1.2 to 7.1.5) with the copper base solution (4.13) employing voltametric indication using the polarised double platinum electrode (5.3). The copper solution shall be added drop by drop, rapidly at first, and near the end-point in 1 drop steps. The end-point is indicated by a sharp potential break of more than 100 mV per drop (note the volume used, V