BS DD ISO TS 13899-3-2006 Steel - Determination of Mo Nb and W contents in alloyed steel - Inductively coupled plasma atomic emission spectrometric method - Determination of W cont.pdf

1、 g49g50g3g38g50g51g60g44g49g42g3g58g44g55g43g50g56g55g3g37g54g44g3g51g40g53g48g44g54g54g44g50g49g3g40g59g38g40g51g55g3g36g54g3g51g40g53g48g44g55g55g40g39g3g37g60g3g38g50g51g60g53g44g42g43g55g3g47g36g58steel Inductively coupled plasma atomic emission spectrometric method Part 3: Determination of W co

2、ntentICS 77.080.20Steel Determination of Mo, Nb and W contents in alloyed DRAFT FOR DEVELOPMENTDD ISO/TS 13899-3:2005DD ISO/TS 13899-3:2005This Draft for Development was published under the authority of the Standards Policy and Strategy Committee on 29 December 2006 BSI 2006ISBN 0 580 49855 7an inte

3、rnational Standard, to extend the life of the Technical Specification or to withdraw it. Comments should be sent to the Secretary of the responsible BSI Technical Committee at British Standards House, 389 Chiswick High Road, London W4 4AL.The UK participation in its preparation was entrusted to Tech

4、nical Committee ISE/18, Sampling and analysis of iron and steel.A list of organizations represented on ISE/18 can be obtained on request to its secretary.This publication does not purport to include all the necessary provisions of a contract. Users are responsible for its correct application.Amendme

5、nts issued since publicationAmd. No. Date Commentsthat UK experience can be reported to the international organization responsible for its conversion to an international standard. A review of this publication will be initiated not later than 3 years after its publication by the international organiz

6、ation so that a decision can be taken on its status. Notification of the start of the review period will be made 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 sup

7、port the conversion into National forewordThis Draft for Development was published by BSI. It is the UK implementation of ISO/TS 13899-3:2005.This publication is not to be regarded as a British Standard.It is being issued in the Draft for Development series of publications and is of a provisional na

8、ture. It should be applied on this provisional basis, so that information and experience of its practical application can be obtained.Comments arising from the use of this Draft for Development are requested so Reference numberISO/TS 13899-3:2005(E)TECHNICAL SPECIFICATION ISO/TS13899-3First edition2

9、005-02-15Steel Determination of Mo, Nb and W contents in alloyed steel Inductively coupled plasma atomic emission spectrometric method Part 3: Determination of W content Aciers Dosage du Mo, du Nb et du W dans les aciers allis Mthode par spectromtrie dmission atomique avec plasma induit par haute fr

10、quence Partie 3: Dosage du W DD ISO/TS 13899-3:2005ii iiiContents Page Foreword iv 1 Scope 1 2 Normative references . 1 3 Principle . 1 4 Reagents 2 5 Apparatus 3 6 Sampling and samples . 4 7 Procedure 4 7.1 Preparation of test solution, Tn. 4 7.2 Preparation for spectrometric measurements. 5 7.3 Pr

11、e-analysis of the test solution 5 7.4 Preparation of calibration solutions for bracketing, KLnand KHn6 7.5 Analysis of test solutions 6 8 Expression of results 6 8.1 Method of calculation . 6 8.2 Precision 6 9 Test report . 7 Annex A (normative) Procedure for the determination of instrumental criter

12、ia 8 Annex B (informative) Additional information on the international collaborative trial . 10 Annex C (informative) Graphical representation of precision data. 12 DD ISO/TS 13899-3:2005iv Foreword ISO (the International Organization for Standardization) is a worldwide federation of national standa

13、rds bodies (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 organ

14、izations, governmental 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. International Standards are drafted in accordance with the rules given i

15、n the ISO/IEC Directives, Part 2. The main task of technical committees is to prepare International Standards. Draft International Standards adopted by the technical committees are circulated to the member bodies for voting. Publication as an International Standard requires approval by at least 75 %

16、 of the member bodies casting a vote. In other circumstances, particularly when there is an urgent market requirement for such documents, a technical committee may decide to publish other types of normative document: an ISO Publicly Available Specification (ISO/PAS) represents an agreement between t

17、echnical experts in an ISO working group and is accepted for publication if it is approved by more than 50 % of the members of the parent committee casting a vote; an ISO Technical Specification (ISO/TS) represents an agreement between the members of a technical committee and is accepted for publica

18、tion if it is approved by 2/3 of the members of the committee casting a vote. An ISO/PAS or ISO/TS is reviewed after three years in order to decide whether it will be confirmed for a further three years, revised to become an International Standard, or withdrawn. If the ISO/PAS or ISO/TS is confirmed

19、, it is reviewed again after a further three years, at which time it must either be transformed into an International Standard or be withdrawn. Attention 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

20、identifying any or all such patent rights. ISO/TS 13899-3 was prepared by Technical Committee ISO/TC 17, Steel, Subcommittee SC 1, Methods of determination of chemical composition. ISO/TS 13899 consists of the following parts, under the general title Steel Determination of Mo, Nb and W contents in a

21、lloyed steel Inductively coupled plasma atomic emission spectrometric method: Part 1: Detemination of Mo content Part 2: Detemination of Nb content Part 3: Detemination of W content DD ISO/TS 13899-3:20051Steel Determination of Mo, Nb and W contents in alloyed steel Inductively coupled plasma atomic

22、 emission spectrometric method Part 3: Determination of W content 1 Scope This Technical Specification specifies a method for the determination of tungsten content in steel by means of inductively coupled plasma atomic emission spectrometry. This method is applicable to tungsten contents between 0,1

23、 % and 20 % (mass fraction). 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) applie

24、s. ISO 648:1977, Laboratory glassware One-mark pipettes ISO 1042:1998, Laboratory glassware One-mark volumetric flasks ISO 3696:1987, Water for analytical laboratory use Specification and test methods ISO 5725-1:1994, Accuracy (trueness and precision) of measurement methods and results Part 1: Gener

25、al principles and definitions ISO 5725-2:1994, Accuracy (trueness and precision) of measurement methods and results Part 2: Basic method for the determination of repeatability and reproducibility of a standard measurement method ISO 5725-3:1994, Accuracy (trueness and precision) of measurement metho

26、ds and results Part 3: Intermediate measures of the precision of a standard measurement method ISO 14284:1996, Steel and iron Sampling and preparation of samples for the determination of chemical composition 3 Principle The sample is dissolved in a hydrochloric, nitric and hydrofluoric acid mixture

27、and fumed with a phosphoric and perchloric acid mixture. Hydrofluoric acid and an internal standard element (if used) are added and the solution is diluted to known volume. The solution is filtered and nebulized into an inductively coupled plasma (ICP) spectrometer and the intensity of the emitted l

28、ight from the element is measured simultaneously with the light emitted from the internal standard element. DD ISO/TS 13899-3:20052 The method uses a calibration based on close matrix matching of the calibration solutions to the sample and close bracketing of the tungsten content around the approxim

29、ate concentration of tungsten in the sample to be analysed. This compensates for matrix interferences and provides high accuracy, even in highly alloyed steels where spectral interferences can be severe. Nonetheless, all interferences shall be kept to a minimum and it is therefore essential that the

30、 spectrometer used meets the performance criteria specified in the method for the selected analytical lines. In order to accurately matrix match, it is necessary to know the content of all elements in the sample (to the nearest %). To this end, it may be necessary to carry out a preliminary analysis

31、 of the sample by a semi-quantitative method. 4 Reagents During the analysis, unless otherwise stated, use only reagents of recognised analytical grade and only grade 2 water as specified in ISO 3696. 4.1 Hydrofluoric acid, HF, 40 % (mass fraction), approximately 1,14 g/ml 4.2 Hydrochloric acid, HCl

32、, approximately 1,19 g/ml 4.3 Nitric acid, HNO3, approximately 1,40 g/ml 4.4 Phosphoric acid, H3PO4, approximately 1,70 g/ml, diluted 1 + 1 4.5 Perchloric acid, HClO4, approximately 1,54 g/ml, diluted 1 + 1 4.6 Fuming acid mixture: mix 100 ml of the phosphoric acid (4.4) and 300 ml of the perchloric

33、 acid (4.5) 4.7 Internal standard solution, 1 000 mg/l Choose a suitable element to be added as internal standard and prepare a 1 000 mg/l solution. The internal standard chosen shall be pure, shall not be present in the sample, and shall not interfere with analytical wavelengths, nor should the int

34、ernal standard element wavelength be interfered with by elements in the test solution. The internal standard shall be soluble in the acids used and it shall not cause precipitation. Moreover, the excitation conditions of the analytical line and the internal standard element line should match. 4.8 Tu

35、ngsten stock standard solution, 1 000 mg/l Weigh, to the nearest 0,001 g, 0,5 g of high purity tungsten minimum 99,95 % (mass fraction) and dissolve in a mixture of 10 ml hydrofluoric acid (4.1) and 20 ml nitric acid (4.3). Cool and transfer the solution quantitatively to a calibrated 500 ml one-mar

36、k plastic volumetric flask. Dilute to the mark with water and mix. 1 ml of this solution contains 1 mg of W. It is not permitted to use pre-prepared tungsten standard solutions supplied by second parties. 4.9 Tungsten standard solution, 100 mg/l Transfer, with a calibrated micropipette, 25 ml of the

37、 tungsten stock standard solution (4.8) into a calibrated 250 ml one-mark plastic volumetric flask. Add 5 ml of hydrofluoric acid (4.1) and 10 ml of nitric acid (4.3). Dilute to the mark with water and mix. 1 ml of this solution contains 0,1 mg of W. DD ISO/TS 13899-3:20053NOTE If calibrated micropi

38、pettes of suitable volume are not available it would be more advantageous to use more concentrated standard solutions. These solutions must, however, be prepared for each series of analysis, in order to avoid possible precipitation. 4.10 Standard solutions of interfering and matrix elements Prepare

39、standard solutions for each element of which more than 1 % (mass fraction) is contained in the test sample. Use pure elements or oxides with tungsten contents less than 10 g/g. Commercial certified standard solutions can also be used if the tungsten content is less than the value specified above. NO

40、TE If a large amount of an element is to be added (e.g. iron), it might be more advantageous to use the pure metal and weigh the correct amount (see 7.3 and 7.4). In this case, use the dissolution procedure described in 7.1.2. 5 Apparatus The plastic pipettes and flasks to be used shall be calibrate

41、d in accordance with ISO 648 or ISO 1042, as appropriate. Ordinary laboratory apparatus and 5.1 Atomic emission spectrometer, equipped with an inductively coupled plasma (ICP) and a nebulization system resistant to hydrofluoric acid. When a polytetrafluoroethylene (PTFE) nebulizer is used, it is rec

42、ommended that a surface active agent should be added to improve wetting in the nebulizer and spray chamber. Modern nebulizers are, however, often manufactured of plastic materials with better wetting-characteristics than PTFE and can therefore (as is the case with sapphire nebulizers) be used withou

43、t a surface active agent. The ICP-ES spectrometer used will be satisfactory if, after optimising according to 7.2.1 to 7.2.4, it meets the performance criteria given in 5.1.2 to 5.1.4. The spectrometer can be either the simultaneous or the sequential type. A sequential type can be used either with o

44、r without an internal standard. However, if a sequential spectrometer is to be used with an internal standard, it shall be fitted with an arrangement which allows for the simultaneous measurement of the internal standard line. 5.1.1 Analytical lines This standard does not specify any particular emis

45、sion line. It is mandatory that each laboratory carefully investigates the line/lines available on its own equipment to find the most suitable one regarding sensitivity and freedom from interferences. In Table 1, however, a suggestion is given together with possible interferences. The line for the i

46、nternal standard element should be selected according to 4.7. Table 1 Example of analytical line and lines for internal standard element Wavelength Element nm Possible interferences W 207,91 Cr, V, Mo Sr (as internal standard) 407,77 Sc (as internal standard) 363,07 Cd (as internal standard) 214,44

47、DD ISO/TS 13899-3:20054 5.1.2 Minimum practical resolution of the spectrometer Calculate the bandwidth, according to Clause A.1, for the wavelength used including the line for internal standard. The bandwidth shall be less than 0,030 nm. 5.1.3 Minimum short-term precision Calculate the short-term pr

48、ecision according to Clause A.2. The relative standard deviation shall not exceed 0,5 % of the mean absolute or ratioed intensities for concentrations 100 to 1 000 times the LOD (5.1.4) mg/l. For concentrations 10 to 100 times the LOD the RSD shall not exceed 5 %. 5.1.4 Limit of Detection (LOD) and

49、Limit of Quantification (LOQ) Calculate the LOD and LOQ, according to Clause A.3, for the analytical line used. The values shall be below the values in Table 2. Table 2 Limit of Detection (LOD) and Limit of Quantification (LOQ) LOD LOQ Element mg/l mg/l W 1 5 5.2 Polytetrafluoroethylene (PTFE) beakers 5.3 100 ml polypropylene volumetric flasks 6 Sampling and samples Sampling and preparation of the laboratory sample shall be carried out in accordance with ISO 14284 or appropri