1、BSI Standards Publication PD CEN/TS 15656:2015 Copper and copper alloys Determination of phosphorus content Spectrophotometric methodPD CEN/TS 15656:2015 PUBLISHED DOCUMENT National foreword This Published Document is the UK implementation of CEN/TS 15656:2015. It supersedes DD CEN/TS 15656:2009 whi
2、ch is withdrawn. The UK participation in its preparation was entrusted to Technical Committee NFE/34/1, Wrought and unwrought copper and copper alloys. A list of organizations represented on this committee can be obtained on request to its secretary. This publication does not purport to include all
3、the necessary provisions of a contract. Users are responsible for its correct application. The British Standards Institution 2015. Published by BSI Standards Limited 2015 ISBN 978 0 580 87644 8 ICS 77.120.30 Compliance with a British Standard cannot confer immunity from legal obligations. This Publi
4、shed Document was published under the authority of the Standards Policy and Strategy Committee on 30 April 2015. Amendments/corrigenda issued since publication Date Text affectedPD CEN/TS 15656:2015TECHNICAL SPECIFICATION SPCIFICATION TECHNIQUE TECHNISCHE SPEZIFIKATION CEN/TS 15656 April 2015 ICS 77
5、.120.30 Supersedes CEN/TS 15656:2009 English 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 - Spekt
6、rophotometrisches Verfahren 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, particularl
7、y on the question whether 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 nat
8、ional standards in force (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 Re
9、public 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 United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NOR
10、MALISATION EUROPISCHES KOMITEE 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 15656:2015 CEN/TS 15656:2015 (E) 2 Contents P
11、age Foreword 3 1 Scope 4 2 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
12、9 Precision 11 10 Test report . 12 Bibliography . 13 PD CEN/TS 15656:2015 CEN/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
13、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 such patent rights. This document supersedes CEN/TS 15656:2009. Within its programme of work, Technical Committee CEN/TC 133 requested CEN/TC 13
14、3/WG 10 “Methods of analysis“ 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 I
15、nternal Regulations, the national 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, Ic
16、eland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom. PD CEN/TS 15656:2015 CEN/TS 15656:2015 (E) 4 1 Scope This Technical Specification specifies a molybdovanadate sp
17、ectrophotometric method for 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
18、or in part, are normatively 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 Sele
19、ction 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 Part 2: Sampling of wrought products and castings 3 Principle Dissolution of a test portion in nitric aci
20、d. Elimination of interfering 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
21、as molybdenum blue; for contents 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 Nitri
22、c acid, HNO 3( = 1,40 g/ml) 4.2 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, HClO 4( = 1,67 g/ml) 4.5 Hydrobromic acid, HBr ( = 1,50 g/ml) 4.6 Isobutanol 4.7 Sodium carbonate, Na 2 CO 34.8 Methanol 4.9 M
23、ethyl isobutyl ketone PD CEN/TS 15656:2015 CEN/TS 15656:2015 (E) 5 4.10 Ammonium molybdate solution, 50 g/l Dissolve 50 g of ammonium molybdate tetrahydrate (NH 4 ) 6 Mo 7 O 24 4H 2 O 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. D
24、ilute to 1 000 ml with water. After prolonged 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
25、shaking with 10 ml of the isobutanol (4.6). 4.11 Ammonium molybdate solution, 150 g/l Dissolve 150 g of ammonium molybdate tetrahydrate (NH 4 ) 6 Mo 7 O 24 4H 2 O 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
26、 dihydrate (SnCl 2 2H 2 O) in 25 ml of hydrochloric acid (4.12). Prepare this solution fresh before use. 4.14 Sulphuric acid, H 2 SO 4( = 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
27、 1 ml of the tin(II) chloride stock solution (4.13) with 10 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 (NH 4 VO 3 ) in 1 000 ml of water. 4.18 Citric acid
28、solution, 500 g/l Dissolve 500 g of citric acid (C 6 H 8 O 7 ) in 1 000 ml of water. 4.19 Phosphorus stock solution, 100 mg/l Dissolve 0,439 3 g of potassium dihydrogen orthophosphate (KH 2 PO 4 ), freshly dried at 105 C, with water into a 1 000 ml one-mark volumetric flask, dilute to the mark with
29、water and mix well. 1 ml of this stock solution contains 0,1 mg of phosphorus. 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 contain
30、s 0,01 mg of phosphorus. PD CEN/TS 15656:2015 CEN/TS 15656:2015 (E) 6 5 Apparatus 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
31、 cm and 4 cm 6 Sampling Sampling shall be carried 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 7.1.1 Test portion We
32、igh (1 0,001) g of the test sample. 7.1.2 Test portion solution 7.1.2.1 Dissolve 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) an
33、d heat until fuming begins. 7.1.2.2 Dilute the solution with 10 ml of water 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 hydrob
34、romic acid (4.5). 7.1.2.3 Dissolve the copper bromide formed during the fuming 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
35、. Wash the filter with hot water until it is free of acid, then dry and ignite 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,
36、 titanium, niobium and/or tantalum, phosphorus can be found totally or partially 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 th
37、e washings to the filtrate. Neutralize the combined filtrate and washings 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
38、 a blank test simultaneously with the determination, following the same procedure 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 bl
39、ank. PD CEN/TS 15656:2015 CEN/TS 15656:2015 (E) 7 7.3 Check test Make a preliminary 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 sp
40、ecified in 7.1 and 7.5. 7.4 Establishment of the calibration curve 7.4.1 Preparation 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 c
41、alibration solutions shall be adjusted to suit the sensitivity of the spectrophotometer 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
42、each beaker (1 0,001) g of electrolytic tough pitch copper (P 0,000 1 %). 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
43、.2, 7.1.2.3 and 7.5.2.1. Table 1 Calibration for phosphorus mass fractions 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/m
44、l % 0 a0 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 5 0,05 0,001 0 0,005 aBlank test on reagents for calibration curve. PD CEN/TS 15656:2015 CEN/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) i
45、ntroduce in each beaker (1 0,001) g of electrolytic tough pitch copper (P 0,000 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 descri
46、bed in 7.1.2.2, 7.1.2.3 and 7.5.2.2. Table 2 Calibration for phosphorus mass 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
47、 ml mg mg/ml % 0 a0 0 0 5 0,05 0,000 5 0,005 6 0,06 0,000 6 0,006 7 0,07 0,000 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 (
48、5.1) introduce in each beaker (1 0,001) g of electrolytic tough pitch copper (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 des
49、cribed in 7.1.2.2, 7.1.2.3 and 7.5.2.3. Table 3 Calibration for phosphorus mass 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 % 0 a0 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 15656:2015 CEN/TS 15656:2015 (E) 9 7.4.1.5 Phosphorus mass fractio
