1、BSI Standards PublicationPD CEN/TS 15656:2015Copper and copper alloys Determination of phosphoruscontent SpectrophotometricmethodPD CEN/TS 15656:2015 PUBLISHED DOCUMENTNational forewordThis Published Document is the UK implementation of CEN/TS 15656:2015. It supersedes DD CEN/TS 15656:2009 which is
2、withdrawn.The UK participation in its preparation was entrusted to TechnicalCommittee NFE/34/1, Wrought and unwrought copper and copperalloys.A list of organizations represented on this committee can beobtained on request to its secretary.This publication does not purport to include all the necessar
3、yprovisions of a contract. Users are responsible for its correctapplication. The British Standards Institution 2015.Published by BSI Standards Limited 2015ISBN 978 0 580 87644 8ICS 77.120.30Compliance with a British Standard cannot confer immunity fromlegal obligations.This Published Document was pu
4、blished under the authority of theStandards Policy and Strategy Committee on 30 April 2015.Amendments/corrigenda issued since publicationDate Text affectedPD CEN/TS 15656:2015TECHNICAL SPECIFICATION SPCIFICATION TECHNIQUE TECHNISCHE SPEZIFIKATION CEN/TS 15656 April 2015 ICS 77.120.30 Supersedes CEN/
5、TS 15656:2009English Version Copper and copper alloys - Determination of phosphorus content - Spectrophotometric method Cuivre et alliages de cuivre - Dtermination du phosphore -Mthode spectrophotomtrique Kupfer und Kupferlegierungen - Bestimmung des Phosphorgehaltes - Spektrophotometrisches Verfahr
6、en This Technical Specification (CEN/TS) was approved by CEN on 24 February 2015 for provisional application. The period of validity of this CEN/TS is limited initially to three years. After two years the members of CEN will be requested to submit their comments, particularly on the question whether
7、 the CEN/TS can be converted into a European Standard. CEN members are required to announce the existence of this CEN/TS in the same way as for an EN and to make the CEN/TS available promptly at national level in an appropriate form. It is permissible to keep conflicting national standards in force
8、(in parallel to the CEN/TS) until the final decision about the possible conversion of the CEN/TS into an EN is reached. CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, Fran
9、ce, Germany, 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 KO
10、MITEE FR NORMUNG CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels 2015 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. CEN/TS 15656:2015 EPD CEN/TS 15656:2015CEN/TS 15656:2015 (E) 2 Contents Page Foreword 3 1 Scope 4 2
11、 Normative references 4 3 Principle 4 4 Reagents .4 5 Apparatus .6 6 Sampling .6 7 Procedure .6 7.1 Preparation of the test portion solution 6 7.2 Blank test 6 7.3 Check test .7 7.4 Establishment of the calibration curve .7 7.5 Determination 10 8 Expression of results . 11 9 Precision 11 10 Test rep
12、ort . 12 Bibliography . 13 PD CEN/TS 15656:2015CEN/TS 15656:2015 (E) 3 Foreword This document (CEN/TS 15656:2015) has been prepared by Technical Committee CEN/TC 133 “Copper and copper alloys”, the secretariat of which is held by DIN. Attention is drawn to the possibility that some of the elements o
13、f this document may 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 15656:2009. Within its programme of work, Technical Committee CEN/TC 133 requested CEN/TC 133/WG 10 “Methods of analysi
14、s“ to prepare the revision of the following document: CEN/TS 15656:2009, Copper and copper alloys Determination of phosphorus content Spectrophotometric method. In comparison with CEN/TS 15656:2009 only editorial modifications have been made. According to the CEN-CENELEC Internal Regulations, the na
15、tional standards organizations of the following countries are bound to announce this Technical Specification: Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latv
16、ia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom. PD CEN/TS 15656:2015CEN/TS 15656:2015 (E) 4 1 Scope This Technical Specification specifies a molybdovanadate spectrophotometric method for
17、the determination of phosphorus in copper and copper alloys in the form of castings or unwrought or wrought products. The method is applicable to products having phosphorus mass fractions between 0,001 % and 0,5 %. 2 Normative references The following documents, in whole or in part, are normatively
18、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 any amendments) applies. ISO 1811-1, Copper and copper alloys Selection and preparation of sam
19、ples 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 and castings 3 Principle Dissolution of a test portion in nitric acid. Elimination of interferin
20、g elements by fuming with perchloric, hydrofluoric and hydrobromic acids. Decomposition of insoluble phosphates by fusion with sodium carbonate. For contents below 0,01 % mass fraction, extraction of phosphorus as phosphomolybdic acid and spectrophotometric determination as molybdenum blue; for cont
21、ents between 0,005 % and 0,05 % mass fraction, extraction and spectrophotometric determination as phosphovanadomolybdic acid. 4 Reagents During the analysis, use only reagents of recognized analytical grade and only distilled water or water of equivalent purity. 4.1 Nitric acid, HNO3( = 1,40 g/ml) 4
22、.2 Nitric acid solution, 1 + 1 Add 500 ml of nitric acid (4.1) to 500 ml of water. 4.3 Hydrofluoric acid, HF ( = 1,13 g/ml) 4.4 Perchloric acid, HClO4( = 1,67 g/ml) 4.5 Hydrobromic acid, HBr ( = 1,50 g/ml) 4.6 Isobutanol 4.7 Sodium carbonate, Na2CO34.8 Methanol 4.9 Methyl isobutyl ketone PD CEN/TS 1
23、5656:2015CEN/TS 15656:2015 (E) 5 4.10 Ammonium molybdate solution, 50 g/l Dissolve 50 g of ammonium molybdate tetrahydrate (NH4)6Mo7O24 4H2O in 250 ml of water. Add a solution of 115 ml of the perchloric acid (4.4) and 500 ml of water at room temperature. Dilute to 1 000 ml with water. After prolong
24、ed storage, a white precipitate may form. While this residue will not affect the analysis, care should be taken to prevent its contamination of the aliquot used in the analysis. Immediately before use, the aliquot used in the analysis should be purified by shaking with 10 ml of the isobutanol (4.6).
25、 4.11 Ammonium molybdate solution, 150 g/l Dissolve 150 g of ammonium molybdate tetrahydrate (NH4)6Mo7O24 4H2O in 1 000 ml of water. 4.12 Hydrochloric acid, HCl ( = 1,19 g/l) 4.13 Tin(II) chloride solution, 400 g/l Dissolve 10 g of tin(II) chloride dihydrate (SnCl2 2H2O) in 25 ml of hydrochloric aci
26、d (4.12). Prepare this solution fresh before use. 4.14 Sulphuric acid, H2SO4( = 1,84 g/l) 4.15 Sulphuric acid solution, 10 mol/l To 100 ml of water add 56 ml of sulphuric acid (4.14) while cooling. 4.16 Tin(II) chloride solution, 2 g/l Dilute 1 ml of the tin(II) chloride stock solution (4.13) with 1
27、0 ml of sulphuric acid solution (4.15) and make up to 200 ml with water. Prepare this solution fresh before use. 4.17 Ammonium vanadate solution, 2,5 g/l Dissolve 2,5 g of ammonium vanadate (NH4VO3) in 1 000 ml of water. 4.18 Citric acid solution, 500 g/l Dissolve 500 g of citric acid (C6H8O7) in 1
28、000 ml of water. 4.19 Phosphorus stock solution, 100 mg/l Dissolve 0,439 3 g of potassium dihydrogen orthophosphate (KH2PO4), freshly dried at 105 C, with water into a 1 000 ml one-mark volumetric flask, dilute to the mark with water and mix well. 1 ml of this stock solution contains 0,1 mg of phosp
29、horus. 4.20 Phosphorus standard solution, 10 mg/l Transfer 20 ml of the phosphorus stock solution (4.19) into a 200 ml one-mark volumetric flask, dilute to the mark with water and mix well. 1 ml of this standard solution contains 0,01 mg of phosphorus. PD CEN/TS 15656:2015CEN/TS 15656:2015 (E) 6 5 A
30、pparatus All vessels shall be free of contamination by phosphorus. Cleaning with hot hydrochloric acid (4.12), is recommended. 5.1 PTFE beakers, capacity 100 ml 5.2 Spectrophotometer, fitted with cells of optical path lengths 1 cm and 4 cm 6 Sampling Sampling shall be carried out in accordance with
31、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 7.1.1 Test portion Weigh (1 0,001) g of the test sample. 7.1.2 Test portion solution 7.1.2.1 D
32、issolve the test portion (7.1.1) in a PTFE beaker (5.1) with 10,0 ml of nitric acid solution (4.2). Heat gently, if necessary. To eliminate silicon, add 0,50 ml of hydrofluoric acid (4.3) and 10,0 ml of perchloric acid (4.4) and heat until fuming begins. 7.1.2.2 Dilute the solution with 10 ml of wat
33、er and add 10,0 ml of hydrobromic acid (4.5). To eliminate interference from arsenic, antimony and tin, heat gently until fuming begins again. If tin content is 1 % (mass fraction), repeat the fuming step with 10,0 ml of hydrobromic acid (4.5). 7.1.2.3 Dissolve the copper bromide formed during the f
34、uming steps by adding several millilitres of nitric acid solution (4.2) and bring to fuming. Dilute with 30 ml of water. Heat to boiling for 10 min, then cool to room temperature. Filter the solution through a fine pored filter. Wash the filter with hot water until it is free of acid, then dry and i
35、gnite the filter in a small platinum crucible covered with a platinum cover. The temperature has to be increased slowly. Mix the residue with about 0,3 g of sodium carbonate and fuse. NOTE If the test sample contains zirconium, titanium, niobium and/or tantalum, phosphorus can be found totally or pa
36、rtially as insoluble phosphates. The procedure for dissolving these residues is described below. After cooling, dissolve the melt with a small amount of water. Filter off any insoluble residue and wash with hot water, adding the washings to the filtrate. Neutralize the combined filtrate and washings
37、 with perchloric acid (4.4). Add the neutralized solution of the original copper-containing filtrate. The total volume should not exceed 50 ml; if necessary, the volume should be reduced by evaporating. 7.2 Blank test Carry out a blank test simultaneously with the determination, following the same p
38、rocedure and using the same quantities of all reagents and of pure copper as used for the determination, but omitting the test portion. Correct the result obtained from the determination in accordance with the result for the blank. PD CEN/TS 15656:2015CEN/TS 15656:2015 (E) 7 7.3 Check test Make a pr
39、eliminary check of the apparatus by preparing a solution of reference material or a synthetic sample containing a known amount of phosphorus and of composition similar to the material to be analysed. Carry out the procedure specified in 7.1 and 7.5. 7.4 Establishment of the calibration curve 7.4.1 P
40、reparation of the calibration solutions 7.4.1.1 General In all cases, copper concentration and acidity in the calibration solutions shall be similar to those of the test portion solutions. The phosphorus concentration of the calibration solutions shall be adjusted to suit the sensitivity of the spec
41、trophotometer used, so that the curve of absorbance as a function of concentration is a straight line. 7.4.1.2 Phosphorus mass fraction between 0,001 % and 0,005 % Into each of a series of five PTFE beakers (5.1) introduce in each beaker (1 0,001) g of electrolytic tough pitch copper (P 0,000 1 %).
42、Follow exactly the procedure described in 7.1.2. Add the volumes of phosphorus standard solution (4.20) as shown in Table 1, just before heating for fuming with perchloric acid (4.4). Follow the procedure as described in 7.1.2.2, 7.1.2.3 and 7.5.2.1. Table 1 Calibration for phosphorus mass fractions
43、 between 0,001 % and 0,005 % Phosphorus standard solution volume (4.20) Corresponding phosphorus mass Corresponding phosphorus concentration after final dilution Corresponding phosphorus mass fraction of test sample ml mg mg/ml % 0a0 0 0 1 0,01 0,000 2 0,001 2 0,02 0,000 4 0,002 4 0,04 0,000 8 0,004
44、 5 0,05 0,001 0 0,005 aBlank test on reagents for calibration curve. PD CEN/TS 15656:2015CEN/TS 15656:2015 (E) 8 7.4.1.3 Phosphorus mass fraction between 0,005 % and 0,01 % Into each of a series of seven PTFE beakers (5.1) introduce in each beaker (1 0,001) g of electrolytic tough pitch copper (P 0,
45、000 1 %). Follow exactly the procedure described in 7.1.2. Add the volumes of phosphorus standard solution (4.20) as shown in Table 2, just before heating for fuming with perchloric acid (4.4). Follow the procedure as described in 7.1.2.2, 7.1.2.3 and 7.5.2.2. Table 2 Calibration for phosphorus mass
46、 fractions between 0,005 % and 0,01 % Phosphorus standard solution volume (4.20) Corresponding phosphorus mass Corresponding phosphorus concentration after final dilution Corresponding phosphorus mass fraction of test sample ml mg mg/ml % 0a0 0 0 5 0,05 0,000 5 0,005 6 0,06 0,000 6 0,006 7 0,07 0,00
47、0 7 0,007 8 0,08 0,000 8 0,008 9 0,09 0,000 9 0,009 10 0,10 0,001 0 0,010 aBlank test on reagents for calibration curve. 7.4.1.4 Phosphorus mass fraction between 0,01 % and 0,10 % Into each of a series of six PTFE beakers (5.1) introduce in each beaker (1 0,001) g of electrolytic tough pitch copper
48、(P 0,000 1 %). Follow exactly the procedure described in 7.1.2. Add the volumes of phosphorus stock solution (4.19) as shown in Table 3, just before heating for fuming with perchloric acid (4.4). Follow the procedure as described in 7.1.2.2, 7.1.2.3 and 7.5.2.3. Table 3 Calibration for phosphorus ma
49、ss fractions between 0,01 % and 0,10 % Phosphorus stock solution volume (4.19) Corresponding phosphorus mass Corresponding phosphorus concentration after final dilution Corresponding phosphorus mass fraction of test sample ml mg mg/ml % 0a0 0 0 1 0,1 0,002 0,010 4 0,4 0,008 0,040 6 0,6 0,012 0,060 8 0,8 0,016 0,080 10 1,0 0,020 0,10 aBlank test on reagents for calibration curve. PD CEN/TS 15656:2015CEN/TS 15656:2015 (E) 9 7.4.1.5 Phosphorus mass fraction between 0,10 % and 0,50 % Into each of a series of six PTFE beakers (5.1) introduce i
