1、BRITISH STANDARDBS EN14937-1:2006Copper and copper alloys Determination of antimony content Part 1: Spectrophotometric methodThe European Standard EN 14937-1:2006 has the status of a British StandardICS 77.120.30g49g50g3g38g50g51g60g44g49g42g3g58g44g55g43g50g56g55g3g37g54g44g3g51g40g53g48g44g54g54g4
2、4g50g49g3g40g59g38g40g51g55g3g36g54g3g51g40g53g48g44g55g55g40g39g3g37g60g3g38g50g51g60g53g44g42g43g55g3g47g36g58BS EN 14937-1:2006This British Standard was published under the authority of the Standards Policy and Strategy Committee on 31 August 2006 BSI 2006ISBN 0 580 49077 7National forewordThis B
3、ritish Standard is the official English language version of EN 14937-1:2006. The UK participation in its preparation was entrusted to Technical Committee NFE/34, Copper and copper alloys, which has the responsibility to: A list of organizations represented on this committee can be obtained on reques
4、t to its secretary.Cross-referencesThe British 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 Elect
5、ronic Catalogue or of British Standards Online.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. aid enquirers to un
6、derstand the text; 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.Summary of pagesThis document comprises a
7、 front cover, an inside front 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 CommentsEUROPEAN STANDARDNORME EUROPENNEEUROPISCHE NORMEN 14937-1June
8、 2006ICS 77.120.30English VersionCopper and copper alloys - Determination of antimony content -Part 1: Spectrophotometric methodCuivre et alliages de cuivre - Dosage de lantimoine - Partie1 : Mthode spectrophotomtriqueKupfer und Kupferlegierungen - Bestimmung desAntimongehaltes - Teil 1: Spektrophot
9、ometrischesVerfahrenThis 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 bibli
10、ographical references concerning 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
11、CEN member into its own 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,
12、 Lithuania, Luxembourg, 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 200
13、6 CEN All rights of exploitation in any form and by any means reservedworldwide for CEN national Members.Ref. No. EN 14937-1:2006: EEN 14937-1:2006 (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 Ex
14、pression of results 7 9 Precision.7 10 Test report 8 Bibliography9 EN 14937-1:2006 (E) 3 Foreword This document (EN 14937-1:2006) 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
15、of a national standard, 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
16、 of analysis“ to prepare the following standard: EN 14937-1, Copper and copper alloys Determination of antimony content Part 1: Spectrophotometric method This is one of two parts of the standard for the determination of antimony content in copper and copper alloys. The other part is: EN 14937-2, Cop
17、per and copper alloys Determination of antimony content Part 2: FAAS method According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Cyprus, Czech Republic, Denmark, Estonia, Fi
18、nland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom. EN 14937-1:2006 (E) 4 1 Scope This part of this European Standard specifies a Rho
19、damine B spectrophotometric method for the determination of the antimony content of copper and copper alloys in the form of unwrought, wrought and cast products. The method is applicable to products having antimony mass fractions in the range between 0,001 % and 0,1 %, or greater by appropriate modi
20、fication of the mass of the test portion, the volume of the test portion solution to be taken for the extraction and the cell path length. 2 Normative references The following referenced documents are indispensable for the application of this document. For dated references, only the edition cited ap
21、plies. 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
22、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 text, are listed in the Bibliography. 3 Principle Extraction of pentavalent
23、 antimony into isopropyl ether and spectrophotometric determination of the chloro-antimonate-Rhodamine B complex. 4 Reagents and materials 4.1 General During the analysis, use only reagents of recognized analytical grade and only distilled water or water of equivalent purity. 4.2 Isopropyl ether, (C
24、H2)2CHOCH(CH2)2. 4.3 Hydrochloric acid, HCl ( = 1,19 g/ml). 4.4 Hydrochloric acid solution, 7 + 3 Dilute 700 ml of hydrochloric acid (4.3) in 300 ml of water. 4.5 Hydrochloric acid solution, 1 mol/l Dilute 83 ml of hydrochloric acid (4.3) in 500 ml of water and make up to 1 000 ml with water. EN 149
25、37-1:2006 (E) 5 4.6 Hydrogen peroxide solution, H2O230 % (mass fraction). 4.7 Cerium(IV) sulfate solution Dissolve 4 g of cerium(IV) sulfate tetrahydrate Ce(SO4)2 4H2O in 50 ml of 0,5 mol/l sulfuric acid solution and dilute to 100 ml with the same acid. 4.8 Hydroxylammonium chloride solution Dissolv
26、e 1 g of hydroxylammonium chloride NH2OH HCl in water and dilute to 100 ml. Prepare this solution immediately prior to use. 4.9 Rhodamine B solution Dissolve 0,01 g of Rhodamine B and dilute to 100 ml with hydrochloric acid solution (4.5). Filter the solution before use. 4.10 Antimony stock solution
27、, 1,000 g/l Sb Dissolve 0,274 3 g of potassium antimonyl tartrate hemihydrate K(SbO)C4H4O6 0,5H2O and make up to volume with the hydrochloric acid solution (4.4) in a 100 ml one-mark volumetric flask. 1 ml of this solution contains 1,000 mg of Sb. 4.11 Antimony standard solution, 100 mg/l Sb Dilute
28、10 ml of the antimony stock solution (4.10) to the mark with the hydrochloric acid solution (4.4) in a 100 ml one-mark volumetric flask. 1 ml of this solution contains 100 g of Sb. 5 Apparatus 5.1 Ordinary laboratory apparatus. 5.2 Refrigerator. 5.3 Spectrophotometer. 6 Sampling Sampling shall be ca
29、rried 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 Preparation of the test portion solution Depending on the expected antimony content of the sample, weigh a
30、 test portion in accordance with Table 1 and transfer it into a 250 ml conical flask. EN 14937-1:2006 (E) 6 Table 1 Antimony contents Expected antimony content Mass of test portion Volume of HCl (4.3) Volume of test portion solution to be taken w (Sb) m0V1V0% g ml ml 0,001 to 0,004 2 0,001 10 5 0,00
31、5 to 0,02 1 0,001 15 2 0,03 to 0,1 0,5 0,001 15 1 Dissolve the test portion in 15 ml of the hydrochloric acid solution (4.4) and add 5 ml to 10 ml of the hydrogen peroxide solution (4.6), in small portions. Cool until the violent reaction has ceased. When the test portion is completely dissolved, he
32、at the solution to boiling for several minutes to decompose the excess hydrogen peroxide. Cool to room temperature. Transfer the test portion solution into a 100 ml one-mark volumetric flask. Dilute to the mark with the hydrochloric acid solution (4.4) and mix well. NOTE In the case of high content
33、of Si, Cr, Zr, contained in the relevant Master Alloys, the dissolution of the test portion might be incomplete. 7.2 Blank test Carry out a blank test simultaneously with the determination, following the same procedure and using the same quantities of all reagents as used for the determination, but
34、omitting the test portion. Correct the result obtained from the determination in accordance with the result for the blank. 7.3 Check test Make a preliminary check of the apparatus by preparing a solution of a standard material or a synthetic sample containing a known amount of antimony and of compos
35、ition similar to the material to be analysed. Carry out the procedure specified in 7.1 and 7.5. 7.4 Preparation of the calibration Into each of a series of at least four 250 ml conical flasks transfer 1 g of pure antimony-free copper (Cu 99,95 %) and 0 ml to 6 ml of antimony standard solution (4.11)
36、. Dissolve the copper in accordance with 7.1. Using 15 ml of hydrochloric acid (4.3) and 1 ml of the calibration solutions, proceed to 7.5. The solutions for spectrophotometric measurements thus prepared will contain 0 g to 6 g of Sb. 7.5 Determination In accordance with Table 1, transfer into a sep
37、arating funnel V1ml of hydrochloric acid (4.3) previously cooled to 5 C or below in the refrigerator (5.2) and V0ml of the test portion solution. Carry out the following operations without interruption. Add 6 drops of the cerium (IV) sulfate solution (4.7) and mix well. After 2 min add 3 drops of th
38、e hydroxylammonium chloride solution (4.8) and mix again. Add 10 ml of the isopropyl ether (4.2) at a maximum temperature of 20 C. Shake for 30 s. Add 75 ml of water previously cooled to 5 C or below and shake for 15 s. Allow to stand for 5 min. Discard the aqueous layer and wash the organic layer t
39、wice with 3 ml of the hydrochloric acid solution (4.5). Add 20 ml of the Rhodamine B solution (4.9), shake for 30 s and allow to stand for 2 min. Drain the aqueous layer together with a small amount of the organic layer. Collect the remaining organic layer in a small, dry, stoppered flask. Swirl the
40、 flask to collect water droplets on the bottom. Transfer the organic phase into a 1 cm cell and immediately measure the absorbance against water at about 550 nm. EN 14937-1:2006 (E) 7 8 Expression of results Calculate the antimony mass fraction, in per cent (%), as follows: Antimony mass fraction =
41、100001 mVm(1) where m0is the mass of the test portion, in gram (g) (7.1); m1is the mass of antimony determined in the volume V0, in microgram (g); V0is the volume of the test portion solution taken, in millilitre (ml). 9 Precision Eight laboratories co-operated in validating this method and obtained
42、 the results summarized in Table 2 and Figure 1 respectively. These data conform to the method given in ISO 5725 including the Cochrans Test and Grubbs Test. Table 2 Statistical information Levels Reference value % Found % Repeatibility r Reproducibility R 1 0,033 0,033 0,001 4 0,002 5 2 0,008 4 0,0
43、08 3 0,000 44 0,001 2 3 0,002 6 0,002 6 0,000 26 0,000 3 lg R = 0,825 lg M 1,3248 lg r = 0,668 lg M 1,8962 Figure 1 lg relationship between Antimony concentration (lg M) and r and R EN 14937-1:2006 (E) 8 10 Test report The test report shall contain the following information: a) identification of the
44、 sample; b) test method used; c) results; d) any unusual characteristics noted during the determination; e) any operation not included in this European Standard or in the document to which reference is made or regarded as optional; f) date of the test and/or date of preparation or signature of the t
45、est report; g) signature of the responsible person. EN 14937-1:2006 (E) 9 Bibliography In the preparation of this European Standard, use was made of a number of documents for reference purposes. The relevant publications are listed hereafter. 1 ISO 5725-1, Accuracy (trueness and precision) of measur
46、ement methods and results Part 1: General principles and definitions 2 ISO 5725-2, Accuracy (trueness and precision) of measurement methods and results Part 2: Basic method for the determination of repeatability and reproducibility of a standard measurement method 3 ISO 5725-3, Accuracy (trueness an
47、d precision) of measurement methods and results Part 3: Intermediate measures of the precision of a standard measurement method 4 ISO 5956, Copper and copper alloys Determination of antimony content Rhodamine B spectrometric method BS EN 14937-1:2006BSI389 Chiswick High RoadLondonW4 4ALBSI British S
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