1、DD CEN/TS15703-1:2009ICS 77.040.30; 77.120.30NO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAWDRAFT FOR DEVELOPMENTCopper and copperalloys Determinationof manganese contentPart 1: Spectrophotometric methodThis Draft for Developmentwas published under theauthority of the Standard
2、sPolicy and StrategyCommittee on 30 June2009. BSI 2009ISBN 978 0 580 58980 5Amendments/corrigenda issued since publicationDate CommentsDD CEN/TS 15703-1:2009National forewordThis Draft for Development is the UK implementation of CEN/TS15703-1:2009.This publication is not to be regarded as a British
3、Standard.It is being issued in the Draft for Development series of publications andis of a provisional nature. It should be applied on this provisional basis,so that information and experience of its practical application can beobtained.Comments arising from the use of this Draft for Development are
4、requested so that UK experience can be reported to the internationalorganization responsible for its conversion to an international standard.A review of this publication will be initiated not later than 3 years afterits publication by the international organization so that a decision can betaken on
5、its status. Notification of the start of the review period will bemade in an announcement in the appropriate issue of Update Standards.According to the replies received by the end of the review period,the responsible BSI Committee will decide whether to support theconversion into an international St
6、andard, to extend the life of theTechnical Specification or to withdraw it. Comments should be sent tothe Secretary of the responsible BSI Technical Committee at BritishStandards House, 389 Chiswick High Road, London W4 4AL.The UK participation in its preparation was entrusted to TechnicalCommittee
7、NFE/34, Copper and copper alloys.A list of organizations represented on this committee can be obtained onrequest to its secretary.This publication does not purport to include all the necessary provisionsof a contract. Users are responsible for its correct application.Compliance with a British Standa
8、rd cannot confer immunityfrom legal obligations.DD CEN/TS 15703-1:2009TECHNICAL SPECIFICATIONSPCIFICATION TECHNIQUETECHNISCHE SPEZIFIKATIONCEN/TS 15703-1April 2009ICS 77.040.30; 77.120.30English VersionCopper and copper alloys - Determination of manganesecontent - Part 1: Spectrophotometric methodCu
9、ivre et alliages de cuivre - Dosage du manganse -Partie 1: Mthode spectrophotomtriqueKupfer und Kupferlegierungen - Bestimmung desMangangehaltes - Teil 1: SpektrophotometrischesVerfahrenThis Technical Specification (CEN/TS) was approved by CEN on 1 March 2009 for provisional application.The period o
10、f validity of this CEN/TS is limited initially to three years. After two years the members of CEN will be requested to submit theircomments, particularly 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
11、the same way as for an EN and to make the CEN/TS availablepromptly at national level in an appropriate form. It is permissible to keep conflicting national 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 mem
12、bers are the national standards bodies of Austria, Belgium, Bulgaria, Cyprus, Czech Republic, Denmark, Estonia, Finland,France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal,Romania, Slovakia, Slovenia, Spain, Sweden, S
13、witzerland and United Kingdom.EUROPEAN COMMITTEE FOR STANDARDIZATIONCOMIT EUROPEN DE NORMALISATIONEUROPISCHES KOMITEE FR NORMUNGManagement Centre: Avenue Marnix 17, B-1000 Brussels 2009 CEN All rights of exploitation in any form and by any means reservedworldwide for CEN national Members.Ref. No. CE
14、N/TS 15703-1:2009: EDD CEN/TS 15703-1:2009CEN/TS 15703-1:2009 (E) 2 Contents Page Foreword 3 1 Scope 4 2 Normative references 4 3 Principle 4 4 Reagents and materials 4 5 Apparatus .6 6 Sampling .6 7 Procedure .6 8 Expression of results 8 9 Precision .9 10 Test report 9 DD CEN/TS 15703-1:2009CEN/TS
15、15703-1:2009 (E) 3 Foreword This document (CEN/TS 15703-1:2009) 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 of this document may be the subject of patent right
16、s. CEN and/or CENELEC shall not be held responsible for identifying any or all such patent rights. This is one of two parts of the standard/technical specification for the determination of manganese content in copper and copper alloys. The other part is: prEN 15703-2, Copper and copper alloys Determ
17、ination of manganese content Part 2: Flame atomic absorption spectrometric method (FAAS) According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are bound to announce this Technical Specification: Austria, Belgium, Bulgaria, Cyprus, Czech Re
18、public, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and the United Kingdom. DD CEN/TS 15703-1:2009CEN/TS 15703-1:2009 (E) 4 1
19、 Scope This part of this Technical Specification specifies a spectrophotometric method for the determination of the manganese content of copper and copper alloys in the form of castings or unwrought or wrought products. The method is applicable to products having manganese mass fractions between 0,0
20、25 % and 6,25 %. 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 the referenced document (including any amendments) applies. ISO 1811-
21、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 Part 2: Sampling of wrought products and castings 3 Principle Dissolution
22、 of a test portion in fluoroboric-nitric acid mixture. Oxidation of manganese to permanganic acid by potassium periodate. Spectrophotometric determination in comparison with a background colour prepared by selective reduction of permanganic acid by sodium nitrite. 4 Reagents and materials During the
23、 analysis, use only reagents of recognized analytical grade and only distilled water or water of equivalent purity. 4.1 Boric acid, H3BO3(40 g/l solution) 4.2 Nitric acid, HNO3( = 1,40 g/ml) 4.3 Nitric acid solution (1 + 3) Add 25 ml of nitric acid (4.2) to 75 ml of water. 4.4 Hydrofluoric acid, HF
24、40 % ( = 1,14 g/ml) WARNING Hydrofluoric acid is a hazardous substance. Care shall be taken and it shall be used under an efficient fume hood. 4.5 Sulphuric acid, H2SO4( = 1,84 g/ml) 4.6 Sulphuric acid solution (1 + 3) Add 25 ml of sulphuric acid (4.5) to 75 ml of water. DD CEN/TS 15703-1:2009CEN/TS
25、 15703-1:2009 (E) 5 4.7 Potassium periodate, KIO4crystals 4.8 Potassium periodate solution, KIO450 g/l Dissolve 5 g of potassium periodate (4.7) in 100 ml of nitric acid solution (4.3). 4.9 Sodium nitrite, NaNO2solution, 20 g/l Dissolve 2,0 g of sodium nitrite in water. Transfer this solution into a
26、 100 ml volumetric flask. Make up to 100 ml and mix. The solution shall be freshly prepared. 4.10 Fluoroboric-nitric acid mixture Using a polypropylene stirrer in a 1 000 ml polypropylene tall form beaker, mix well: a) 150 ml of water; b) 300 ml of boric acid solution (4.1); c) 50 ml of nitric acid
27、(4.2); d) 30 ml of hydrofluoric acid (4.4). 4.11 Dilution solution To 1 000 ml of boric acid solution (4.1) add 5,5 ml of sulphuric acid (4.5). Bring to the boil and add a few crystals of potassium periodate (4.7). Cool and transfer the solution into a stoppered 1 000 ml conical flask. 4.12 Manganes
28、e stock solution, 1 g/l Mn Place a few grams of electrolytic manganese (Mn 99,9 %) in a 250 ml glass beaker containing 60 ml to 80 ml of sulphuric acid solution (4.6) and 100 ml of water. Stir, and after a few minutes, decant the acid solution and wash the metal with water several times, decanting t
29、he liquid each time. Place the metal in acetone and stir. Decant the acetone and dry the metal and allow it to cool in a desiccator. In a 600 ml tall form beaker, dissolve (1 0,001) g of the cleaned manganese in 40 ml of sulphuric acid solution (4.6) and about 80 ml of water. When dissolution is com
30、plete, boil the solution for several minutes. Cool and transfer the solution to a 1 000 ml volumetric flask. Dilute to the mark with water and mix well. 1 ml of this solution contains 1 mg of Mn. 4.13 Manganese standard solution, 0,1 g/l Mn Transfer 20 ml of the manganese stock solution (4.12) to a
31、200 ml volumetric flask. Dilute to the mark with water and mix well. 1 ml of this solution contains 0,1 mg of Mn. DD CEN/TS 15703-1:2009CEN/TS 15703-1:2009 (E) 6 5 Apparatus 5.1 Ordinary laboratory apparatus 5.2 Spectrophotometer, fitted with cells of optical path lengths of 1 cm, 2 cm and 4 cm 6 Sa
32、mpling 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 Weigh (0,4 0,001) g
33、 of the test sample into a 300 ml conical flask. 7.1.2 Test portion solution 7.1.2.1 General Dissolve the test portion (7.1.1) with 50 ml of the fluoroboric-nitric acid mixture (4.10). Warm, if necessary, to accelerate the attack. When dissolution is complete, add 20 ml of water. Boil for 5 min to r
34、emove the oxides of nitrogen. 7.1.2.2 Mass fractions less than 0,5 % Introduce 5 ml of potassium periodate solution (4.8) into the boiling solution (7.1.2.1). Maintain at boiling for 5 min, then immerse the conical flasks in a boiling water bath for 20 min. Cool and transfer the solution to a 100 ml
35、 volumetric flask. Use the dilution solution (4.11) for rinsing and making up to the mark and mix well. 7.1.2.3 Mass fractions between 0,5 % and 2,5 % Cool the solution (7.1.2.1) and transfer to a 100 ml volumetric flask. Dilute to the mark with water and mix well. Transfer a 20 ml aliquot to a 300
36、ml conical flask, then add 40 ml of fluoroboric-nitric acid mixture (4.10) and 10 ml of water in order to obtain the same condition of dilution as in the preceding case. Boil for 5 min and introduce 5 ml of potassium periodate solution (4.8) into the boiling solution. Maintain at boiling for 5 min,
37、then immerse the conical flasks in a boiling water bath for 20 min. Cool and transfer the solution to a 100 ml volumetric flask. Use the dilution solution (4.11) for rinsing and making up to the mark and mix well. 7.1.2.4 Mass fractions between 2 % and 6,25 % Cool the solution (7.1.2.1) and transfer
38、 to a 250 ml volumetric flask. Dilute to the mark with water and mix well. Transfer a 20 ml aliquot to a 300 ml conical flask, then add 46 ml of fluoroboric-nitric acid mixture (4.10) and 10 ml of water in order to obtain the same condition of dilution as in the preceding case. DD CEN/TS 15703-1:200
39、9CEN/TS 15703-1:2009 (E) 7 Boil for 5 min and introduce 5 ml of potassium periodate solution (4.8) into the boiling solution. Maintain at boiling for 5 min, then immerse the flasks in a boiling water bath for 20 min. Cool and transfer the solution to a 100 ml volumetric flask. Use the dilution solut
40、ion (4.11) for rinsing and making up to the mark and mix well. 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 omitting the test portion. Correct the result obta
41、ined from the determination in accordance with the result of the blank. 7.3 Check test Make a preliminary check of the apparatus by preparing a solution of a reference material or a synthetic sample containing a known amount of manganese and of composition similar to the material to be analysed. Car
42、ry out the procedure specified in 7.5. 7.4 Establishment of the calibration curve 7.4.1 Preparation of the calibration solutions Into each of a series of seven 300 ml conical flasks, introduce approximately the volume of water and exactly the volume of manganese standard solution (4.13) as shown in
43、Table 1. Add 50 ml of the fluoroboric-nitric acid mixture (4.10). Boil for 5 min in order to eliminate any oxides of nitrogen which may be present. Table 1 Calibration for manganese mass fraction between 0,025 % and 6,25 % Water volume Manganese standard solution(4.13) Corresponding manganese mass f
44、raction of test sample % Volume Mass of Mn contained For a test portion of ml ml mg 0,400 g 0,080 g 0,032 g 20 0a0 0 0 0 19 1 0,1 0,025 0,125 0,312 5 18 2 0,2 0,050 0,250 0,625 16 4 0,4 0,1 0,5 1,25 14 6 0,6 0,15 0,75 1,875 10 10 1 0,25 1,25 3,125 0 20 2 0,50 2,50 6,25 aBlank test on reagents for ca
45、libration curve. Introduce 5 ml of potassium periodate solution (4.8) into each of the boiling solutions. Maintain at boiling for 5 min, then immerse the conical flasks in a boiling water bath for 20 min. Cool and transfer to a 100 ml volumetric flask. Use the dilution solution (4.11) for rinsing an
46、d making up to the mark and mix well. DD CEN/TS 15703-1:2009CEN/TS 15703-1:2009 (E) 8 7.4.2 Spectrophotometric measurements of the calibration solutions Measure the absorbance immediately, using the spectrophotometer (5.2) set at 530 nm using 1 cm, 2 cm or 4 cm cells depending on the expected mangan
47、ese concentration after first adjusting the apparatus to zero absorbance against the blank test solution (term 0) of the reagents for calibration (7.4.1) as reference. 7.4.3 Calibration curve Establish the calibration curve using measured absorbances and corresponding analyte amounts. NOTE Recent wo
48、rk has demonstrated that the calibration curve may suffer from excessive curvature. A non-acceptable curvature would result when the mid-point calibration absorbance exceeds 0,55 times the absorbance of the maximum calibration solution. If this situation is encountered, the calibration solutions (7.
49、4.1) should be diluted to the minimum standard volume needed to attain the curvature criterion stated. The test solutions (7.5.1) should be also diluted in the same proportion. 7.5 Determination 7.5.1 General The analyses shall be carried out independently, in duplicate. 7.5.2 Spectrophotometric measurements of the test solutions Measure the absorbances of the test portion solutions immediately, using the spectrophotometer (5.2) set at 530 nm, in 1 cm, 2 cm or 4 cm cells (see 7.4.2), in comparison with the background colour of each sample solution,
