1、August 2016 English price group 10No part of this translation may be reproduced without prior permission ofDIN Deutsches Institut fr Normung e. V., Berlin. Beuth Verlag GmbH, 10772 Berlin, Germany,has the exclusive right of sale for German Standards (DIN-Normen).ICS 77.080.01!%Y.R“2541147www.din.deD
2、IN EN ISO 4946Steel and cast iron Determination of copper 2,2-Biquinoline spectrophotometric method (ISO 4946:2016);English version EN ISO 4946:2016,English translation of DIN EN ISO 4946:2016-08Stahl und Gusseisen Bestimmung des Kupferanteils Spektrophotometrisches Verfahren mit 2,2-Dichinolin (ISO
3、 4946:2016);Englische Fassung EN ISO 4946:2016,Englische bersetzung von DIN EN ISO 4946:2016-08Aciers et fontes Dtermination du cuivre Mthode spectrophotomtrique au 2,2-biquinolyle (ISO 4946:2016);Version anglaise EN ISO 4946:2016,Traduction anglaise de DIN EN ISO 4946:2016-08SupersedesDIN EN 24946:
4、1992-11www.beuth.deDocument comprises 15 pagesDTranslation by DIN-Sprachendienst.In case of doubt, the German-language original shall be considered authoritative.07.16 DIN EN ISO 4946:2016-08 2 A comma is used as the decimal marker. National foreword This document (EN ISO 4946:2016) has been prepare
5、d by Technical Committee ISO/TC 17 “Steel” in collaboration with Technical Committee ECISS/TC 102 “Methods of chemical analysis for iron and steel” (Secretariat: SIS, Sweden). The responsible German body involved in its preparation was DIN-Normenausschuss Eisen und Stahl (DIN Standards Committee Iro
6、n and Steel), Working Committee NA 021-00-30 AA Analysenverfahren. The DIN Standards corresponding to the International Standards referred to in this document are as follows: ISO 648 DIN EN ISO 648 ISO 1042 DIN EN ISO 1042 ISO 3696 DIN ISO 3696 ISO 5725*)DIN ISO 5725*)ISO 14284 DIN EN ISO 14284 Amen
7、dments This standard differs from DIN EN ISO 24946:1992-11 as follows: a) the specification of plotting the calibration graphs in 7.4.3 has been corrected; b) some items in accordance with the updated ISO/IEC Directives, Part 2 have been editorially revised; c) the standard has been editorially revi
8、sed. Previous editions DIN EN ISO 24946: 1992-11 National Annex NA (informative) Bibliography DIN EN ISO 648, Laboratory glassware Single-volume pipettes DIN EN ISO 1042, Laboratory glassware One-mark volumetric flasks DIN ISO 3696, Water for analytical laboratory use Specification and test methods
9、DIN ISO 5725, Precision of test methods Determination of repeatability and reproducibility for a standard test method by interlaboratory tests*)DIN EN ISO 14284, Steel and iron Sampling and preparation of samples for the determination of chemical composition *)Has been replaced by the ISO 5725 stand
10、ards series. *)Has been replaced by the DIN ISO 5725 standards series. EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN ISO 4946 March 2016 ICS 77.080.01 Supersedes EN 24946:1990English Version Steel and cast iron - Determination of copper - 2,2-Biquinoline spectrophotometric method (ISO 4946:20
11、16)Aciers et fontes - Dtermination du cuivre - Mthode spectrophotomtrique au 2,2-biquinolyle(ISO 4946:2016) Stahl und Gusseisen - Bestimmung des Kupferanteils - Spektrophotometrisches Verfahren mit 2,2-Dichinolin (ISO 4946:2016) This European Standard was approved by CEN on 21 November 2015. CEN mem
12、bers are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this European Standard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such national standards may be obtained on applicat
13、ion to the CEN-CENELEC Management Centre or to any CEN member. This European Standard exists in three official versions (English, French, German). A version in any other language made by translation under the responsibility of a CEN member into its own language and notified to the CEN-CENELEC Manage
14、ment Centre has the same status as the official versions. CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia,
15、 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 KOMITEE FR NORMUNG CEN-CENELEC Management Centre: Avenue Marnix
16、17, B-1000 Brussels 2016 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN ISO 4946:2016 EEuropean foreword .31 Scope . 52 Normative references 53 Principle 54 Reagents 55 Apparatus . 66 Sampling 67 Procedure. 77.1 Test portion 77.2
17、Blank test . 77.3 Determination . 77.3.1 Preparation of the test solution 77.3.2 Colour development 77.3.3 Preparation of the compensating solution 87.3.4 Spectrophotometric measurement 87.4 Establishment of the calibration graph . 87.4.1 Preparation of the calibration solutions 87.4.2 Spectrophotom
18、etric measurement 87.4.3 Calibration graph . 88 Expression of results 99 Precision . 99.1 General 99.2 Repeatability . 109.3 Reproducibility . 1010 Test report 10Annex A (informative) Additional information on the international interlaboratory test . 11Annex B (informative) Graphical representation
19、of precision data . 12Bibliography . 13Contents PageDIN EN ISO 4946:2016-08 EN ISO 4946:2016 (E) 2Foreword .4European foreword This document (EN ISO 4946:2016) has been prepared by Technical Committee ISO/TC 17 “Steel” in collaboration with Technical Committee ECISS/TC 102 “Methods of chemical analy
20、sis for iron and steel” the secretariat of which is held by SIS. This European Standard shall be given the status of a national standard, either by publication of an identical text or by endorsement, at the latest by September 2016, and conflicting national standards shall be withdrawn at the latest
21、 by September 2016. Attention is drawn to the possibility 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 EN 24946:1990. This document has been pre
22、pared under a mandate given to CEN by the European Commission and the European Free Trade Association. According to the CEN-CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Croatia
23、, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic 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 the
24、United Kingdom. Endorsement notice The text of ISO 4946:2016 has been approved by CEN as EN ISO 4946:2016 without any modification. DIN EN ISO 4946:2016-08 EN ISO 4946:2016 (E) 3 ForewordISO (the International Organization for Standardization) is a worldwide federation of national standards bodies (
25、ISO member bodies). The work of preparing International Standards is normally carried out through ISO technical committees. Each member body interested in a subject for which a technical committee has been established has the right to be represented on that committee. International organizations, go
26、vernmental and non-governmental, in liaison with ISO, also take part in the work. ISO collaborates closely with the International Electrotechnical Commission (IEC) on all matters of electrotechnical standardization.The procedures used to develop this document and those intended for its further maint
27、enance are described in the ISO/IEC Directives, Part 1. In particular the different approval criteria needed for the different types of ISO documents should be noted. This document was drafted in accordance with the editorial rules of the ISO/IEC Directives, Part 2 (see www.iso.org/directives).Atten
28、tion is drawn to the possibility that some of the elements of this document may be the subject of patent rights. ISO shall not be held responsible for identifying any or all such patent rights. Details of any patent rights identified during the development of the document will be in the Introduction
29、 and/or on the ISO list of patent declarations received (see www.iso.org/patents).Any trade name used in this document is information given for the convenience of users and does not constitute an endorsement.For an explanation on the meaning of ISO specific terms and expressions related to conformit
30、y assessment, as well as information about ISOs adherence to the WTO principles in the Technical Barriers to Trade (TBT) see the following URL: Foreword - Supplementary information.The committee responsible for this document is ISO/TC 17, Steel, Subcommittee SC 1, Methods of determination of chemica
31、l composition.This second edition cancels and replaces the first edition (ISO 4946:1984), which has been technically revised to include the following changes: correction of the specification of plotting the calibration graphs in 7.4.3; editorial revision of some items in accordance with the updated
32、ISO/IEC Directives, Part 2.DIN EN ISO 4946:2016-08 EN ISO 4946:2016 (E) 4 1 ScopeThis International Standard specifies a spectrophotometric method for the determination of copper in steel and cast iron by 2,2-biquinoline.The method is applicable to the determination of copper mass fraction in the ra
33、nge of 0,02 % and 5 %.2 Normative referencesThe following documents, in whole 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
34、 (including any amendments) applies.ISO 648, Laboratory glassware Single-volume pipettesISO 1042, Laboratory glassware One-mark volumetric flasksISO 3696, Water for analytical laboratory use Specification and test methodsISO 14284, Steel and iron Sampling and preparation of samples for the determina
35、tion of chemical composition3 PrincipleDissolution of a test portion in appropriate acids.Fuming with perchloric acid to remove hydrochloric and nitric acids and dehydrate silicic acid.Reduction of copper(II) to copper(I) in hydrochloric acid solution by means of ascorbic acid. Formation of a colour
36、ed compound of copper(I) with 2,2-biquinoline.Spectrophotometric measurement at a wavelength of about 545 nm.4 ReagentsDuring the analysis, unless otherwise stated, use only reagents of recognized analytical grade and only grade 2 water as specified in ISO 3696.4.1 High-purity iron, containing coppe
37、r 0,001 % (mass fraction) or less.4.2 Hydrochloric acid, approximately 1,19 g/ml.4.3 Nitric acid, approximately 1,40 g/ml.4.4 Perchloric acid, approximately 1,54 g/ml.WARNING Perchloric acid vapour might cause explosions in the presence of ammonia, nitrous fumes or organic material in general.DIN EN
38、 ISO 4946:2016-08 EN ISO 4946:2016 (E) 5 Perchloric acid, approximately 1,67 g/ml, may also be used. 100 ml of perchloric acid, approximately 1,54 g/ml is equivalent to 79 ml of perchloric acid, approximately 1,67 g/ml.4.5 Perchloric acid, approximately 1,54 g/ml, diluted 1 + 7.4.6 Dimethylformamide
39、 (N,N-dimethylformamide), approximately 0,944 g/ml.WARNING Dimethylformamide is a hazardous substance and can cause birth defects. It should be handled with safety gloves in a fume hood.4.7 Ascorbic acid, 200 g/l solution.Dissolve 20 g of ascorbic acid in water, dilute to 100 ml with water and mix.P
40、repare this solution immediately before use.4.8 2,2-Biquinoline solution.Dissolve 0,60 g of 2,2-biquinoline (cuproine, 2,2-diquinolyl) in dimethylformamide (4.6), dilute to 1 l with the same dimethylformamide and mix.Keep this solution in a dark-coloured glass flask and protect it from the light.4.9
41、 Copper standard solution, 1 g/l.Weigh, to the nearest 0,001 g, 1,000 g of high purity copper and dissolve in the minimum of nitric acid (4.3).Heat to boiling to remove nitrous fumes. Cool and transfer the solution quantitatively to a 1 000 ml one-mark volumetric flask, dilute to the mark with water
42、 and mix.1 ml of this standard solution contains 1 mg of copper.4.10 Copper standard solution, 0,05 g/l.Transfer 25,0 ml of the copper standard solution (4.9) to a 500 ml one-mark volumetric flask, dilute to the mark with water and mix.1 ml of this standard solution contains 0,05 mg of copper.5 Appa
43、ratusAll volumetric glassware shall be Class A, in accordance with ISO 648 and ISO 1042.Ordinary laboratory apparatus and the following shall be used.Spectrophotometer, suitable for measuring the absorbance of the solution at a wavelength of 545 nm with cells of 2 cm or 4 cm optical path length.6 Sa
44、mplingCarry out sampling in accordance with ISO 14284 or appropriate national standards for steel and cast iron.DIN EN ISO 4946:2016-08 EN ISO 4946:2016 (E) 6 7 Procedure7.1 Test portionWeigh, to the nearest 0,001 g, approximately 0,5 g of the test sample.7.2 Blank testIn parallel with the determina
45、tion and following the same procedure, carry out two blank tests using the same quantities of all the reagents but using, to the nearest 0,001 g, approximately 0,5 g of pure iron (4.1) instead of test portion.7.3 Determination7.3.1 Preparation of the test solutionIntroduce the test portion (7.1) int
46、o a 250 ml beaker. Add 10 ml of hydrochloric acid (4.2) and 5 ml of nitric acid (4.3). Cover the beaker with a watch-glass and heat until acids action ceases.NOTE For samples of high chromium content, first dissolve in hydrochloric acid (4.2) and then, when all effervescence has ceased, oxidize by a
47、dding nitric acid (4.3), drop by drop.Add 10 ml of perchloric acid (4.4) and evaporate to fuming. Continue fuming for 3 min.Cool, dissolve the salts with 20 ml of water, transfer the solution quantitatively to a one-mark volumetric flask of suitable capacity (see Table 1), dilute to the mark with wa
48、ter and mix.Filter by decantation through a dry filter to remove any residue or precipitate, e.g. graphite, silica, tungstic acid. Collect the filtrate in a dry beaker, discarding the first fractions of the filtrate.7.3.2 Colour developmentTake an aliquot portion, according to the expected copper content, as indicated in Table 1.Table 1 Volume of test solution and aliquot portionCopper content Volume of test solutionV
