BS EN 24503-1993 Hardmetals - Determination of contents of metallic elements by X-ray fluorescence - Fusion method《硬质合金 用X射线荧光分析法对金属元素含量的测定 熔化法》.pdf

1、BRITISH STANDARD BS EN 24503:1993 ISO 4503:1978 Hardmetals Determination of contentsof metallic elements by X-ray fluorescence Fusion method The European Standard EN 24503:1993 has the status of a British Standard UDC 669.018.25:620.1:543.422.8:546.3BSEN24503:1993 This British Standard, having been

2、prepared under the directionof the Iron and Steel Standards Policy Committee, waspublished under the authorityof the Standards Boardand comes into effect on 15June1993 BSI 01-2000 The following BSI references relate to the work on this standard: Committee reference ISM/65 Special annoucement in BSIN

3、ews January1993 ISBN 0 580 21739 6 Cooperating organizations The European Committee for Standardization (CEN), under whose supervision this European Standard was prepared, comprises the national standards organizations of the following countries: Austria Oesterreichisches Normungsinstitut Belgium In

4、stitut belge de normalisation Denmark Dansk Standardiseringsraad Finland Suomen Standardisoimisliito, r.y. France Association franaise de normalisation Germany Deutsches Institut fr Normung e.V. Greece Hellenic Organization for Standardization Iceland Technological Institute of Iceland Ireland Natio

5、nal Standards Authority of Ireland Italy Ente Nazionale Italiano di Unificazione Luxembourg Inspection du Travail et des Mines Netherlands Nederlands Normalisatie-instituut Norway Norges Standardiseringsforbund Portugal Instituto Portugus da Qualidade Spain Asociacin Espaola de Normalizacin y Certif

6、icacin Sweden Standardiseringskommissionen i Sverige Switzerland Association suisse de normalisation United Kingdom British Standards Institution Amendments issued since publication Amd. No. Date CommentsBSEN24503:1993 BSI 01-2000 i Contents Page Cooperating organizations Inside front cover National

7、 foreword ii Foreword 2 1 Scope 3 2 Field of application 3 3 Principle 3 4 Interfering elements 3 5 Reagents 3 6 Apparatus 3 7 Sampling 3 8 Procedure 3 9 X-ray fluorescence analysis 4 10 Preparation of calibration curves 4 11 Expression of results 4 12 Test report 4 National annex NA (informative) C

8、ommittees responsible Inside back cover Table 1 3 Table 2 4 Table 3 4 Table 4 4BSEN24503:1993 ii BSI 01-2000 National foreword This British Standard has been prepared under the direction of the Iron and Steel Standards Policy Committee and is the English language version of EN24503:1993 Hardmetals D

9、etermination of contents of metallic elements by X-ray fluorescence, published by the European Committee for Standardization (CEN). It is identical with ISO4503:1978, prepared by Technical Committee119, Powder metallurgy, of the International Organization for Standardization (ISO) with the active pa

10、rticipation of the UK. This British Standard supersedes BS5600-4.15:1980 which is withdrawn. This edition makes no technical changes to the standard. A British Standard does not purport to include all the necessary provisions of a contract. Users of British Standards are responsible for their correc

11、t application. Compliance with a British Standard does not of itself confer immunity from legal obligations. Summary of pages This document comprises a front cover, an inside front cover, pages i and ii, theEN title page, pages 2 to 4, an inside back cover and a back cover. This standard has been up

12、dated (see copyright date) and may have had amendments incorporated. This will be indicated in the amendment table on the inside front cover.EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 24503 April 1993 UDC 669.018.25:620.1:543.422.8:546.3 Descriptors: Powder metallurgy, hard metals, chemica

13、l analysis, metals, spectrophotometric analysis, X ray fluorescence spectrometry English version Hardmetals Determination of contents of metallic elements by X-ray fluorescence Fusion method (ISO 4503:1978) Mtaux-durs Dosage des lments mtalliques par fluorescence de rayons X Mthode par fusion (ISO 4

14、503:1978) Hartmetalle Bestimmung des Gehaltes metallischer Elemente durch Rntgenfluoreszenz in fester Lsung (ISO4503:1978) This European Standard was approved by CEN on1993-04-02. CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this

15、 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 application to the Central Secretariat or to any CEN member. This European Standard exists in three official versions (En

16、glish, 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 Central Secretariat has the same status as the official versions. CEN members are the national standards bodies of Austria, Belgium, Denmark,

17、 Finland, France, Germany, Greece, Iceland, Ireland, Italy, Luxembourg, Netherlands, Norway, Portugal, Spain, Sweden, Switzerland and UnitedKingdom. CEN European Committee for Standardization Comit Europen de Normalisation Europisches Komitee fr Normung Central Secretariat: rue de Stassart 36, B-105

18、0 Brussels 1993 Copyright reserved to CEN members Ref. No. EN 24503:1993 EEN24503:1993 BSI 01-2000 2 Foreword In 1992, ISO 4503:1978Hardmetals Determination of contents of metallic elements by X- ray fluorescence Fusion method was submitted to the CEN Primary Questionnaire procedure. Following the p

19、ositive result of the CEN/CS Proposal ISO4503:1978 was submitted to the CEN Formal Vote. The result of the Formal Vote was positive. This European Standard shall be given the status of national standard, either by publication of an identical text or by endorsement, at the latest by October1993, and

20、conflicting national standards shall be withdrawn at the latest by October1993. According to the Internal Regulations of CEN/CENELEC, the following countries are bound to implement this European Standard: Austria, Belgium, Denmark, Finland, France, Germany, Greece, Iceland, Ireland, Italy, Luxembour

21、g, Netherlands, Norway, Portugal, Spain, Sweden, Switzerland, UnitedKingdom.EN24503:1993 BSI 01-2000 3 1 Scope This International Standard specifies an X-ray fluorescence fusion method for the determination of cobalt, chromium, iron, manganese, molybdenum, nickel, niobium, tantalum, titanium, tungst

22、en, vanadium and zirconium contents of carbides and hardmetals. 2 Field of application The method is applicable to carbides of niobium, tantalum, titanium, vanadium, tungsten and zirconium, mixtures of these carbides and binder metals, all grades of presintered or sintered hardmetals, produced from

23、these carbides, with the element contents shown inTable 1. Table 1 3 Principle Measurement of the intensity of the characteristic X-ray spectrum of the elements being determined. To eliminate the effects of particle size and inter-element effects, the test portion is dissolved ina suitable mixture o

24、f acids and converted to sulphates, or is directly oxidized. Either the sulphates or the oxides are then fused with a mixture of sodium tetraborate and a barium compound. 4 Interfering elements The effect of interfering elements, such as line interference of titanium and tungsten on vanadium, shall

25、be taken into account. 5 Reagents During the analysis, use only reagents of recognized analytical grade, and only distilled water or water of equivalent purity. 5.1 Barium peroxide, anhydrous, or barium carbonate, anhydrous. 5.2 Sodium tetraborate, anhydrous. To ensure freedom from water, heat the s

26、odium tetraborate to approximately400 C. 5.3 Hydrofluoric acid, 1,12g/ml. 5.4 Nitric acid, 1,24g/ml (nitric acid, 1,42g/ml, diluted1+1). 5.5 Sulphuric acid, 1,54g/ml (sulphuric acid, 1,84g/ml, diluted1+1). 6 Apparatus Ordinary laboratory apparatus and 6.1 X-ray spectrometer 6.2 Furnaces for oxidatio

27、n of the test portion at700to900 C and for preparation of the borate melt at approximately1100 C. 6.3 Platinum dishes, 50 to100ml. NOTEDishes of95%Pt+5%Au are to be preferred. 6.4 Plate, with polished surface, of platinum alloy, for example85%Pt +10%Rh +5%Au or95%Pt+5%Au. The plate shall be maintain

28、ed at a surface temperature between300 and400 C so that the borate disk (see8.4) loosens easily and does not crack. 6.5 Brass rings or heat-resisting steel cylinders or graphite cylinders NOTEInstead of the plate(6.4) and brass rings(6.5), moulds of graphite or heat-resisting steel may be used. 6.6

29、Wet or dry grinding device 7 Sampling 7.1 The sample shall be crushed in a mortar made of material which does not alter the sample composition. The crushed material shall pass a2mm sieve when using the acid solution method or a0,18mm sieve when using the oxidation method. 7.2 The analysis shall be c

30、arried out on two or three test portions. 8 Procedure 8.1 Weigh, to the nearest0,001g, approximately0,5g of the test sample. NOTEIf the sample includes lubricant, a correction for the lubricant content must be applied. 8.2 Transform the test portion in a platinum dish by the preferred procedure of d

31、issolution(8.2.1) or by oxidation(8.2.2). The oxidation procedure shall not be used if molybdenum may be present in quantities above0,1% (m/m). Element Content, %(m/m) min. max. Co Cr Fe Mn Mo Nb Ni Ta Ti V W Zr 0,05 0,05 0,05 0,05 0,05 0,05 0,05 0,10 0,3 0,15 45 0,05 50 2,0 2,0 2,5 5,0 15 5,0 30 30

32、 4,0 95 2,0EN24503:1993 4 BSI 01-2000 8.2.1 Add15ml of the nitric acid(5.4) to the unoxidized or partially oxidized test portion, heat the dish moderately, add2ml of the hydrofluoric acid(5.3), drop by drop, and maintain the dish at moderate temperature. Following complete dissolution of the test po

33、rtion, add1 to2ml of the sulphuric acid(5.5). Take to dryness and heat at approximately600 C until no more SO 3vapour is evolved. Cool. There is a possibility of transfer of molybdenum from one crucible to another, so care should be taken to avoid such transfer during the heating procedure. Therefor

34、e, do not heat samples with high and low molybdenum contents in the same furnace batch. 8.2.2 Oxidize the test portion in air in a furnace at700 to900 C for about1h. If complete oxidation is achieved, continue as in8.3. If complete oxidation is not achieved (as in the case of hardmetals with a high

35、content of titanium), continue as in8.2.1. 8.3 Mix the test portion well with the fused buffer mixture consisting of15 0,01g of the sodium tetraborate(5.2) and4 0,01g of the barium peroxide(5.1) or4,5 0,01g of the barium carbonate(5.1), and heat the dish moderately until the contents are completely

36、fused and the reaction has subsided. Cover the dish with a lid. Dissolve the oxides by melting at approximately1100 C for10 to15min. Swirl the melt to obtain a homogeneous mass. 8.4 Pour the melt into the preheated ring(6.5) placed on the support plate(6.4) lying on a heating device at about300 to40

37、0 C. Allow to cool until the disk loosens from the plate. Place the disk with the ring on an asbestos plate and allow it to cool to room temperature. 8.5 Grind the disk on the wet or dry grinding device(6.6) until an even and smooth surface is obtained. Immediately rinse and dry the surface. NOTEFin

38、al wet or dry grinding should be done on an abrasive paperN220. Care must be taken to avoid contamination of one specimen by another from the abrasive paper, when dry grinding is used. 8.6 Analyse with the X-ray spectrometer. 9 X-ray fluorescence analysis 9.1 All measuring parameters, including the

39、target material of the X-ray tube, shall be chosen to obtain the optimal number of impulses. 9.2 The analytical lines shown inTable 2 shall be used. Table 2 NOTEIt is recommended that all elements be measured in the first order of reflexion by a LiF(200) crystal. For titanium, a pentaerythritol crys

40、tal can be used, with measurements in the second order. 9.3 Background corrections shall be made when necessary. 10 Preparation of calibration curves The calibration curves shall be plotted on the basis of synthetically prepared samples with compositions as given in clause2 and roughly corresponding

41、 to the grades of hardmetals to be analysed. These samples shall be prepared by mixing accurately known amounts of metals or their suitable compounds. The mixture shall be analysed as described in8.2 to8.6. 11 Expression of results 11.1 Tolerances The deviations between two or three independent dete

42、rminations shall not exceed the values shown inTable 3. Table 3 11.2 Final result Report the arithmetical mean of acceptable determinations rounded to the nearest value as shown inTable 4. Table 4 12 Test report The test report shall include the following information: a) reference to this Internatio

43、nal Standard; b) all details necessary for identification of the test sample; c) the result obtained; d) all operations not specified by this International Standard, or regarded as optional; e) details of any occurrence which may have affected the result. Element Co, Cr, Fe, Mn, Mo, Nb, Ni, Ti, V, Z

44、r Ta, W Analytical line K !1,2 L !1 Content Range for two determinations Range for three determinations % % % from0,05 over0,4 over2 over 10 over 30 to0,4 to2 to 10 to 30 to 95 0,04 0,20 0,30 0,4 1,0 0,05 0,25 0,35 0,5 1,2 Content Round to the nearest % % from0,05 over0,4 over 30 to0,4 to 30 to 95 0

45、,01 0,1 1BSEN24503:1993 BSI 01-2000 National annex NA (informative) Committees responsible The United Kingdom participation in the preparation of this European Standard was entrusted by the Iron and Steel Standards Policy Committee (ISM/-) to Technical Committee ISM/65 upon which the following bodie

46、s were represented: British Hardmetal Association Federation of British Engineers (Test Manufacturers) Society of Motor Manufacturers and Traders Limited Coopted memberBS EN 24503:1993 ISO4503:1978 BSI 389 Chiswick High Road London W4 4AL BSIBritishStandardsInstitution BSI is the independent nationa

47、l body responsible for preparing BritishStandards. It presents the UK view on standards in Europe and at the international level. It is incorporated by Royal Charter. Revisions BritishStandards are updated by amendment or revision. Users of BritishStandards should make sure that they possess the lat

48、est amendments or editions. It is the constant aim of BSI to improve the quality of our products and services. We would be grateful if anyone finding an inaccuracy or ambiguity while using this BritishStandard would inform the Secretary of the technical committee responsible, the identity of which c

49、an be found on the inside front cover. Tel:02089969000. Fax:02089967400. BSI offers members an individual updating service called PLUS which ensures that subscribers automatically receive the latest editions of standards. Buying standards Orders for all BSI, international and foreign standards publications should be addressed to Customer Services. Tel:02089969001. Fax:02089967001. In response to orders for international standards, it is BSI policy to supply the BSI implementation of those that have been published