BS-6200-3.40.4-1997 ISO-13898-4-1997.pdf

BRITISH STANDARD BS 6200-3.40.4: 1997 ISO 13898-4: 1997 Sampling and analysis of iron, steel and other ferrous metals Part 3: Methods of analysis Section 3.40 Multi-element methods Subsection 3.40.4 Determination of nickel, copper and cobalt contents by inductively coupled plasma atomic emission spectrometric method Determination of cobalt content ICS 77.080.01 Licensed Copy: sheffieldun sheffieldun, na, Wed Dec 06 15:09:44 GMT+00:00 2006, Uncontrolled Copy, (c) BSI BS 6200-3.40.4:1997 This British Standard, having been prepared under the direction of the Engineering Sector Board, was published under the authority of the Standards Board and comes into effect on 15 September 1997 © BSI 09-1999 ISBN 0 580 28418 2 National foreword This British Standard reproduces verbatim ISO 13898-4:1997 and implements it as the UK national standard. The UK participation in its preparation was entrusted to Technical Committee ISE/18, Sampling and analysis of iron and steel, which has the responsiblity to: aid enquirers to understand the text; present to the responsible international/European committee any enquiries on the interpretation, or proposals for change, and keep the UK interests informed; monitor related international and European developments and promulgate them in the UK. A list of organizations represented on this committee can be obtained on request to its secretary. Cross-references The British Standards which implement international or European publications referred to in this document may be found in the BSI Standards Catalogue under the section entitled “International Standards Correspondence Index”, or by using the “Find” facility of the BSI Standards Electronic Catalogue. A British Standard does not purport to include all the necessary provisions of a contract. Users of British Standards are responsible for their correct 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, the ISO title page, pages ii to iv, pages 1 to 4 and a back cover. This standard has been updated (see copyright date) and may have had amendments incorporated. This will be indicated in the amendment table on the inside front cover. Amendments issued since publication Amd. No.DateComments Licensed Copy: sheffieldun sheffieldun, na, Wed Dec 06 15:09:44 GMT+00:00 2006, Uncontrolled Copy, (c) BSI BS 6200-3.40.4:1997 © BSI 09-1999i Contents Page National forewordInside front cover Forewordiii Text of ISO 13898-41 Licensed Copy: sheffieldun sheffieldun, na, Wed Dec 06 15:09:44 GMT+00:00 2006, Uncontrolled Copy, (c) BSI ii blank Licensed Copy: sheffieldun sheffieldun, na, Wed Dec 06 15:09:44 GMT+00:00 2006, Uncontrolled Copy, (c) BSI Licensed Copy: sheffieldun sheffieldun, na, Wed Dec 06 15:09:44 GMT+00:00 2006, Uncontrolled Copy, (c) BSI BS 6200-3.40.4:1997 ii © BSI 09-1999 Contents Page Forewordiii 1Scope1 2Normative references1 3Principle1 4Reagents1 5Apparatus1 6Sampling1 7Procedure1 8Expression of results2 9Test report2 Annex A (informative) Additional information on the international cooperative tests3 Annex B (informative) Graphical representation of precision data4 Figure B.1 Logarithmic relationship between cobalt content () and repeatability limit (r) or reproducibility limits (R and RW)4 Table 1 Cobalt contents between 0,001 % (m/m) and 0,10 % (m/m)2 Table 2 Example for cobalt contents up to 0,010 % (m/m)2 Table 32 Table A.13 wCo Licensed Copy: sheffieldun sheffieldun, na, Wed Dec 06 15:09:44 GMT+00:00 2006, Uncontrolled Copy, (c) BSI BS 6200-3.40.4:1997 © BSI 09-1999iii Foreword 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 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 collaborates closely with the International Electrotechnical Commission (IEC) on all matters of electrotechnical standardization. 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. International Standard ISO 13898-3 was prepared by Technical Committee ISO/TC 17, Steel, Subcommittee SC 1, Methods of determination of chemical composition. ISO 13898 consists of the following parts, under the general title Steel and iron Determination of nickel, copper and cobalt contents Inductively coupled plasma atomic emission spectrometric method. Part 1: General requirements and sample dissolution; Part 2: Determination of nickel content; Part 3: Determination of copper content; Part 4: Determination of cobalt content. Annex A and Annex B of this part of ISO 13898 are for information only. Descriptors: Iron and steel products, unalloyed steels, unalloyed cast iron, chemical analysis, determination of content, cobalt, spectrometric method, atomic emission spectrometric method. Licensed Copy: sheffieldun sheffieldun, na, Wed Dec 06 15:09:44 GMT+00:00 2006, Uncontrolled Copy, (c) BSI iv blank Licensed Copy: sheffieldun sheffieldun, na, Wed Dec 06 15:09:44 GMT+00:00 2006, Uncontrolled Copy, (c) BSI BS 6200-3.40.4:1997 © BSI 09-19991 1 Scope This part of ISO 13898 specifies an inductively coupled plasma atomic emission spectrometric method for the determination of cobalt content in unalloyed steel and unalloyed iron. The method is applicable to cobalt contents between 0,001 % (m/m) and 0,10 % (m/m). 2 Normative references The following standards contain provisions which, through reference in this text, constitute provisions of this part of ISO 13898. At the time of publication, the editions indicated were valid. All standards are subject to revision, and parties to agreements based on this part of ISO 13898 are encouraged to investigate the possibility of applying the most recent editions of the standards indicated below. Members of IEC and ISO maintain registers of currently valid International Standards. ISO 3696:1987, Water for analytical laboratory use Specification and test methods. ISO 5725-2:1994, Accuracy (trueness and precision) of measurement methods and results Part 2: 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: Intermediate measures of the precision of a standard measurement method. ISO 13898-1:1997, Steel and iron Determination of nickel, cobalt and copper contents Inductively coupled plasma atomic emission spectrometric method Part 1: General requirements and sample dissolution. ISO 14284:1996, Steel and iron Sampling and preparation of samples for the determination of chemical composition. 3 Principle The principle is described in clause 3 of ISO 13898-1:1997. 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. In addition to the reagents given in clause 4 of ISO 13898-1:1997, the following are required. 4.1 Cobalt, standard solution. 4.1.1 Stock solution, corresponding to 1,0 g of cobalt per litre. Weigh, to the nearest 0,1 mg, 1,000 g of cobalt metal purity 99,99 % (m/m) and transfer to a 200 ml beaker. Add 50 ml of nitric acid (4.3 of ISO ISO 13898-1:1), cover with a watch-glass and heat to dissolve gently. Cool to ambient temperature, transfer into a 1 000 ml one-mark volumetric flask quantitatively and dilute to the mark with water and mix. 1 ml of this stock solution contains 1,0 mg Co. 4.1.2 Standard solution, corresponding to 0,020 g of cobalt per litre. Transfer 10,0 ml of the cobalt stock solution (4.1.1) to a 500 ml one-mark volumetric flask, dilute to the mark with water and mix. If the calibration graph is found to be non-linear, an additional calibration series may be used. Prepare this standard solution immediately before use. 1 ml of this standard solution contains 0,020 mg Co. 5 Apparatus The apparatus required is given in clause 5 of ISO 13898-1:1). 6 Sampling Carry out sampling in accordance with ISO 14284. 7 Procedure 7.1 Test portion Weigh, to the nearest 1 mg, about 1,00 g of the test sample. 7.2 Blank test (corresponding to the zero member) Proceed as directed in 7.2 of ISO 13898-1:1997. 7.3 Determination 7.3.1 Preparation of the test solution Proceed as directed in 7.3.1 of ISO 13898-1:1997. 7.3.2 Preparation of the calibration solutions Introduce into a series of six 200 ml beakers 1,00 g ± 0,001 g of the pure iron (4.1 of ISO 13898-1:1997). Add to each beaker 10 ml of nitric acid (4.3 of ISO 13898-1:1997), cover the beaker with a watch-glass and heat gently until the end of effervescence. Add 10 ml of hydrochloric acid (4.2 of ISO 13898-1:1997) and continue the heating until complete dissolution occurs. Cool to ambient temperature and transfer the solution to six 200 ml one-mark volumetric flasks, rinsing the beakers with the minimum quantity of water. Licensed Copy: sheffieldun sheffieldun, na, Wed Dec 06 15:09:44 GMT+00:00 2006, Uncontrolled Copy, (c) BSI BS 6200-3.40.4:1997 2 © BSI 09-1999 Using a pipette or burette, add to the volumetric flasks the volume of cobalt standard solution (4.1.2) indicated in Table 1. If the calibration graph is found to be non-linear, an additional calibration series may be used (e.g. Table 2). If the internal standard technique is used, using a pipette, add 2 ml of the scandium internal standard solution (4.4 of ISO ISO 13898-1:1997) or 10 ml of the yttrium internal standard solution (4.5 of ISO 13898-1:1997). Dilute to the mark with water and mix. Table 1 Cobalt contents between 0,001 % (m/m) and 0,10 % (m/m) Table 2 Example for cobalt contents up to 0,010 % (m/m) 7.4 Spectrometric measurements 7.4.1 Optimization of the instrument Proceed as directed in 7.4.1 of ISO 13898-1:1997. 7.4.2 Measurements of the emitted intensities Proceed as directed in 7.4.2 of ISO 13898-1:1997. 7.4.3 Preparation of the calibration graph Proceed as directed in 7.4.3 of ISO 13898-1:1997. 8 Expression of results 8.1 Method of calculation Proceed as directed in 8.1 of ISO 13898-1:1997. 8.2 Precision A planned trial of this method was carried out by 26 laboratories in 12 countries at eight levels of cobalt, each laboratory making three determinations of cobalt content at each level (see notes). The test samples used are listed in Table A.1. The results obtained were treated statistically in accordance with ISO 5725-1, ISO 5725-2 and ISO 5725-3, using the data obtained from the samples containing eight levels of cobalt within the application range. The data obtained showed a logarithmic relationship between cobalt content and repeatability limit (r) and reproducibility limits (R and Rw) of the test results (see notes), as summarized in Table 3. (see notes). The graphical representation of the data is given in Annex B. Table 3 NOTE 1Two of the three determinations were carried out under repeatability conditions as defined in ISO 5725-1, i.e. one operator, same apparatus, identical operating conditions, same calibration, and a minimum period of time. NOTE 2The third determination was carried out at a different time (on a different day) by the same operator as in note 1 using the same apparatus with a new calibration. NOTE 3From the results obtained on day 1 the repeatability limit (r) and reproducibility limit (R) were calculated using the procedure specified in ISO 5725-2. From the first result obtained on day 1 and the result obtained on day 2, the within-laboratory reproducibility limit (Rw) was calculated using the procedure given in ISO 5725-3. 9 Test report Proceed as directed in clause 9 of ISO 13898-1:1997. Volume of cobalt standard solution (4.1.2) Cobalt concentration Corresponding cobalt content in the test portion ml 4g/ml% (m/m) 0a 5,0 10,0 20,0 30,0 50,0 0 0,50 1,00 2,00 3,00 5,00 0 0,010 0,020 0,040 0,060 0,100 a Zero member. Volume of cobalt standard solution (4.1.2) Cobalt concentration Corresponding cobalt content in the test portion ml4g/ml% (m/m) 0a 0,5 1,0 2,0 3,0 5,0 0 0,050 0,100 0,200 0,300 0,500 0 0,001 0 0,002 0 0,004 0 0,006 0 0,010 0 a Zero member. Cobalt content Repeatability limitReproducibility limits % (m/m)rRRw 0,001 0,002 0,005 0,010 0,020 0,050 0,100 0,000 18 0,000 25 0,000 37 0,000 50 0,000 68 0,001 02 0,001 4 0,000 51 0,000 70 0,001 05 0,001 4 0,001 9 0,002 9 0,004 0 0,000 30 0,000 40 0,000 57 0,000 75 0,000 98 0,001 4 0,001 8 Licensed Copy: sheffieldun sheffieldun, na, Wed Dec 06 15:09:44 GMT+00:00 2006, Uncontrolled Copy, (c) BSI BS 6200-3.40.4:1997 © BSI 09-19993 Annex A (informative) Additional information on the international cooperative tests The repeatability and reproducibility data in Table 3 were derived from the results of international analytical trials carried out in 1993 on seven steel samples and one iron sample in 12 countries involving 26 laboratories. The results of the trials were reported in document ISO/TC 17/SC 1 N 1024, March 1994. The graphical presentation of the precision data is given in Annex B. The test samples used are listed in Table A.1. Table A.1 SampleCobalt content % (m/m) Precision data CertifiedFoundRepeatability limit Reproducibility limits rRRW JSS 003-3 (unalloyed steel) 0,001 00,000 970,000 980,000 240,000 480,000 39 NR 1C (unalloyed steel) 0,004 60,004 70,004 70,000 260,000 840,000 38 NR 21 (unalloyed steel) 0,0080,008 00,008 00,000 430,001 70,000 60 NBS 16f (unalloyed steel) 0,0030,003 60,003 60,000 340,000 870,000 49 BAS 087-1 (unalloyed steel) 0,0150,014 90,014 80,000 420,001 30,000 93 BCS 456-1 (unalloyed steel) 0,0520,0540,0540,001 50,003 60,002 3 IRSID 081-1 (unalloyed steel) 0,0170,017 50,017 40,000 640,001 70,001 01 EURO 487-1 (pig iron) 0,008 80,008 50,008 50,000 660,009 40,000 60 : general mean within a day : general mean between days wCo,1wCo,2 wCo,1 wCo,2 Licensed Copy: sheffieldun sheffieldun, na, Wed Dec 06 15:09:44 GMT+00:00 2006, Uncontrolled Copy, (c) BSI BS 6200-3.40.4:1997 4 © BSI 09-1999 Annex B (informative) Graphical representation of precision data lg r = 0,439 5 lg 2,421 1 lg R = 0,445 9 lg 1,953 8 lg RW = 0,392 8 lg 2,340 9 where is the average cobalt content, expressed as a percentage by mass, obtained within a day; is the average cobalt content, expressed as a percentage by mass, obtained between days. Figure B.1 Logarithmic relationship between cobalt content () and repeatability limit (r) or reproducibility limits (R and Rw) wCo,1 wCo,1 wCo,2 wCo,1 wCo,2 wCo Licensed Copy: sheffieldun sheffieldun, na, Wed Dec 06 15:09:44 GMT