1、 Reference number ISO/TS 13899-1:2004(E) ISO 2004TECHNICAL SPECIFICATION ISO/TS 13899-1 First edition 2004-04-01 Steel Determination of Mo, Nb and W contents in alloyed steel Inductively coupled plasma atomic emission spectrometric method Part 1: Determination of Mo content Aciers Dosage du Mo, du N
2、b et du W dans les aciers allis Mthode par spectromtrie dmission atomique avec plasma induit par haute frquence Partie 1: Dosage du Mo ISO/TS 13899-1:2004(E) PDF disclaimer This PDF file may contain embedded typefaces. In accordance with Adobes licensing policy, this file may be printed or viewed bu
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7、.org Web www.iso.org Published in Switzerland ii ISO 2004 All rights reservedISO/TS 13899-1:2004(E) ISO 2004 All rights reserved 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 Determination procedure . 4 7.1
8、Test portion . 4 7.2 Preparation of test solution, T n4 7.3 Optimization of spectrometer 4 7.4 Pre-determination of the test solution 4 7.5 Preparation of calibration solutions for bracketing, K Lnand K Hn5 7.6 Determination of test solutions . 5 8 Expression of results 6 8.1 Method of calculation .
9、 6 8.2 Precision 6 9 Test report 7 Annex A (informative) Suggested analytical lines together with possible spectral interferences in determination of molybdenum in steel by ICP-AES 8 Annex B (informative) Additional information on international cooperative tests 9 Annex C (informative) Graphical rep
10、resentation of precision data. 11 ISO/TS 13899-1:2004(E) iv ISO 2004 All rights reservedForeword ISO (the International Organization for Standardization) is a worldwide federation of national standards bodies (ISO member bodies). The work of preparing International Standards is normally carried out
11、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, governmental and non-governmental, in liaison with ISO, also take part in the work. ISO coll
12、aborates closely with the International Electrotechnical Commission (IEC) on all matters of electrotechnical standardization. International Standards are drafted in accordance with the rules given in the ISO/IEC Directives, Part 2. The main task of technical committees is to prepare International St
13、andards. 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 % of the member bodies casting a vote. In other circumstances, particularly when there is an urgent mar
14、ket 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 technical experts in an ISO working group and is accepted for publication if it is approved by more tha
15、n 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 publication if it is approved by 2/3 of the members of the committee casting a vote. An ISO/PAS or ISO/TS is
16、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, it is reviewed again after a further three years, at which time it must either be transformed into a
17、n 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 identifying any or all such patent rights. ISO/TS 13899-1 was prepared by Technical Committee ISO/TC 1
18、7, 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 alloyed steel Inductively coupled plasma atomic emission spectrometric method: Part 1: Determination of
19、 Mo content Part 2: Determination of Nb content Part 3: Determination of W content TECHNICAL SPECIFICATION ISO/TS 13899-1:2004(E) ISO 2004 All rights reserved 1Steel Determination of Mo, Nb and W contents in alloyed steel Inductively coupled plasma atomic emission spectrometric method Part 1: Determ
20、ination of Mo content 1 Scope This Technical Specification specifies an inductively coupled plasma atomic emission spectrometric method for the determination of molybdenum content in steel. The method is applicable to molybdenum contents between 0,03 % (mass fraction) and 8,5 % (mass fraction). 2 No
21、rmative 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 648:1977, Laboratory glass
22、ware 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: General principles and definitions ISO
23、 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 methods and results Part 3: Intermedia
24、te 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 Dissolution of a test portion in a mixture of hydrochloric, nitric and phosphoric acid and fuming with a mixture
25、of phosphoric and perchloric acids. Addition of hydrofluoric acid and, if necessary, an internal reference element and dilution of the solution to known volume. Nebulization of the solution into an inductively coupled plasma atomic emission spectrometer and measurement of the intensity of the emitte
26、d light from molybdenum, or with emitted light from the internal reference element, simultaneously. ISO/TS 13899-1:2004(E) 2 ISO 2004 All rights reservedNOTE 1 The method uses a calibration graph based on a very close matrix matching of the calibration solutions to the sample and close bracketing of
27、 the contents around the approximate concentration of molybdenum in the sample to be analysed. The concentrations of all elements in the sample must, therefore, be approximately known. If the concentrations are not known, the sample must be analysed by some semi-quantitative method. NOTE 2 The advan
28、tage with this procedure is that all possible interferences from the matrix are automatically compensated, which results in high accuracy. This is most important for spectral interferences, which can be severe in very highly alloyed steels. However, all possible interferences must be kept on a minim
29、um level. Therefore it is essential that the spectrometer used meets the performance criteria specified in the method for the selected analytical lines. Examples of the analytical lines are given in Table 1. Table 1 Examples of analytical lines together with interfering elements Element Analytical l
30、ine nm Interferences 202,03 Ta Molybdenum 281,61 Al, Hf NOTE 3 These lines have been carefully investigated (see Annex A). The strongest possible interferences are given in Table 1. If other lines are used, they have to be carefully checked so that interferences are not higher than the values given
31、in Annex A. It is recommended to use scandium 363.07 nm. This line is interference-free for the elements and concentrations given in Annex A. 4 Reagents During the analysis, unless otherwise stated, use only reagents of recognized analytical grade and only grade 2 water as specified in ISO 3696. 4.1
32、 Hydrofluoric acid, HF, 40 % (mass fraction), approximately 1,14 g/ml, or 50 % (mass fraction), approximately 1,17 g/ml. 4.2 Hydrochloric acid, HCl, approximately 1,19 g/ml 4.3 Nitric acid, HNO 3 , approximately 1,40 g/ml 4.4 Phosphoric acid, H 3 PO 4 , approximately 1,70 g/ml, diluted 1 + 1 4.5 Per
33、chloric acid, HClO 4 , approximately 1,54 g/ml, diluted 1 + 1 4.6 Internal standard solution, 1 000 mg/l Choose a suitable element to be added as internal reference and prepare a 1 000 mg/l solution. 4.7 Molybdenum stock standard solution, 1 000 mg/l Weigh, to the nearest 0,000 5 g, 0,5 g of high pu
34、rity molybdenum minimum 99,95 % (mass fraction) and dissolve in a mixture of 25 ml hydrochloric acid (4.2) and 25 ml nitric acid (4.3). Keep the temperature of a one-mark volumetric flask the same as that at which the volumetric flask was calibrated. Cool and transfer the solution quantitatively to
35、a calibrated 500 ml one-mark volumetric flask. Dilute to the mark with water and mix. 4.8 Molybdenum standard solution, 100 mg/l Keep the temperature of a one-mark volumetric flask the same as that at which the volumetric flask was calibrated. Using a calibrated pipette, transfer 100 ml of the molyb
36、denum stock standard solution (4.7) into a ISO/TS 13899-1:2004(E) ISO 2004 All rights reserved 3calibrated 1 000 ml one-mark volumetric flask. Add 10 ml of hydrochloric acid (4.2). Dilute to the mark with water and mix. 4.9 Molybdenum standard solution, 10 mg/l Keep the temperature of a one-mark vol
37、umetric flask the same as that at which the volumetric flask was calibrated. Using a calibrated pipette, transfer 100 ml of the molybdenum standard solution (4.8) into a calibrated 1 000 ml one-mark volumetric flask. Add 10 ml of hydrochloric acid (4.2). Dilute to the mark with water and mix. 4.10 S
38、tandard solutions of interfering elements Prepare standard solutions for each element of which more than 1 % by mass is contained in the test sample. Use pure metal or chemical substances with molybdenum contents less than 0,001 % (mass fraction). 5 Apparatus All volumetric glassware shall be class
39、A and calibrated, 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-AES) and a nebulization system resistant to hydrofluoric acid. NOTE When a Teflon nebulizer and/or spray chamb
40、er are used, surface active agent is recommended to be added in order to avoid liquefaction of spray due to poor wetting of fluid in nebulizer. The ICP-AES used will be satisfactory if, after optimizing in accordance with 7.4 a) to e), it meets the performance criteria given in 5.1.1 to 5.1.4. The s
41、pectrometer can be either the simultaneous or the sequential type. If a sequential spectrometer can be equipped with an extra arrangement for simultaneous measurement of the internal standard line, it can be used with the internal reference technique. If the sequential spectrometer is not equipped w
42、ith this arrangement, an internal reference cannot be used and an alternative technique without internal standard can be applied. 5.1.1 Practical resolution of the spectrometer Calculate the bandwidth (full width at half maximum) for the analytical line used including the line for internal reference
43、. The bandwidth shall be less than 0,030 nm. 5.1.2 Short-term stability Calculate the standard deviation of ten measurements of the absolute intensity or intensity ratio of the emitted light of the most concentrated calibration solution for a calibration solution for molybdenum. The relative standar
44、d deviation shall not exceed 0,4 %. 5.1.3 Background equivalent concentration and detection limit Calculate the background equivalent concentration (BEC) and detection limit (DL) for the analytical line in a solution containing only the analyte element. The values of BEC and DL shall be below 0,5 mg
45、/l and 0,015 mg/l respectively. 5.1.4 Graph linearity The graph is checked by calculating the correlation coefficient. This coefficient shall be more than 0,999. ISO/TS 13899-1:2004(E) 4 ISO 2004 All rights reserved5.2 Polytetrafluoroethylene (PTFE) beakers 5.3 100 ml polypropylene measuring flask,
46、calibrated in accordance with ISO 1042. 6 Sampling and samples Carry out sampling in accordance with ISO 14284. 7 Determination procedure 7.1 Test portion Weigh, to the nearest 0,000 5 mg, 0,25 g of the test sample. 7.2 Preparation of test solution, T n7.2.1 Place the test portion in a 200 ml Pyrex
47、Erlenmeyer flask. NOTE A PTFE or PFA beaker with a graphite base can also be used. In this case the solution has not been transferred to an other PTFE beaker after fuming (see 7.2.3). 7.2.2 Add 10 ml HCl (4.2), 2 ml HNO 3(4.3) and 5 ml H 3 PO 4(4.4). Heat to complete dissolution. Add 15 ml of HClO 4
48、(4.5) and heat until the perchloric acid starts to fume. Continue to fume for 2 min to 3 min (the white smoke shall form on the top of the Erlenmeyer flask). 7.2.3 Cool the solution and add 10 ml of water to dissolve the salts. Some residues can remain undissolved. Transfer the solution and possible
49、 undissolved residues quantitatively to a 100 ml PTFE beaker (5.2). Add 2 ml of HF (4.1). Heat slowly till the residues dissolve completely. 7.2.4 Cool the solution to room temperature and transfer the solution quantitatively to a 100 ml volumetric polypropylene flask (5.3). If internal standard is used, add, by pipette, 1 ml of the internal standard solution (4.6). 7.2.5 Dilute to the mark with water and mix. 7.3 Optimization of spectrometer 7.3.1 Start the ICP and allow it to warm up in a
