1、BSI Standards PublicationBS ISO 13933:2014Steel and iron Determination of calcium andmagnesium Inductivelycoupled plasma atomicemission spectrometric methodBS ISO 13933:2014 BRITISH STANDARDNational forewordThis British Standard is the UK implementation of ISO 13933:2014.The UK participation in its
2、preparation was entrusted to TechnicalCommittee ISE/102, Methods of Chemical Analysis for Iron and Steel.A list of organizations represented on this committee can beobtained on request to its secretary.This publication does not purport to include all the necessaryprovisions of a contract. Users are
3、responsible for its correctapplication. The British Standards Institution 2014. Published by BSI StandardsLimited 2014ISBN 978 0 580 68913 0ICS 77.080.01Compliance with a British Standard cannot confer immunity fromlegal obligations.This British Standard was published under the authority of theStand
4、ards Policy and Strategy Committee on 31 July 2014.Amendments issued since publicationDate Text affectedBS ISO 13933:2014 ISO 2014Steel and iron Determination of calcium and magnesium Inductively coupled plasma atomic emission spectrometric methodAciers et fontes - Dtermination du calcium et du magn
5、sium - Mthode par spectromtrie dmission atomique avec plasma induitINTERNATIONAL STANDARDISO13933First edition2014-07-15Reference numberISO 13933:2014(E)BS ISO 13933:2014ISO 13933:2014(E)ii ISO 2014 All rights reservedCOPYRIGHT PROTECTED DOCUMENT ISO 2014All rights reserved. Unless otherwise specifi
6、ed, no part of this publication may be reproduced or utilized otherwise in any form or by any means, electronic or mechanical, including photocopying, or posting on the internet or an intranet, without prior written permission. Permission can be requested from either ISO at the address below or ISOs
7、 member body in the country of the requester.ISO copyright officeCase postale 56 CH-1211 Geneva 20Tel. + 41 22 749 01 11Fax + 41 22 749 09 47E-mail copyrightiso.orgWeb www.iso.orgPublished in SwitzerlandBS ISO 13933:2014ISO 13933:2014(E) ISO 2014 All rights reserved iiiContents PageForeword iv1 Scop
8、e . 12 Normative references 13 Principle 14 Reagents 15 Apparatus . 35.1 Inductively coupled plasma atomic emission spectrometer . 35.2 Polytetrafluoroethylene (PTFE) beakers with PTFE cover . 46 Sampling 57 Procedure. 57.1 Test portion 57.2 Blank test . 57.3 Determination . 57.4 Adjustment of the a
9、pparatus 77.5 Measurement of the calibration solutions 77.6 Plotting a calibration curve 87.7 Measurements of the test solution 88 Expression of results 88.1 Method of calculation 88.2 Precision . 89 Test report . 9Annex A (normative) Procedure for the determination of instrumental criteria 10Annex
10、B (informative) Additional information on international cooperative test .12Annex C (informative) Graphical representation of precision data 14Bibliography .16BS ISO 13933:2014ISO 13933:2014(E)ForewordISO (the International Organization for Standardization) is a worldwide federation of national stan
11、dards 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 org
12、anizations, 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.The procedures used to develop this document and those intended for its
13、 further maintenance 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/dir
14、ectives). 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. Details of any patent rights identified during the development of the document will be in t
15、he Introduction 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 rela
16、ted to conformity 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 informationThe committee responsible for this document is ISO/TC 17, Steel, Subcommittee SC 1, Methods of determina
17、tion of chemical composition.iv ISO 2014 All rights reservedBS ISO 13933:2014INTERNATIONAL STANDARD ISO 13933:2014(E)Steel and iron Determination of calcium and magnesium Inductively coupled plasma atomic emission spectrometric method1 ScopeThis International Standard specifies a method for determin
18、ation of calcium and magnesium contents in iron, cast iron, steel, and alloyed steel by inductively coupled plasma (ICP) atomic emission spectrometry.The method is applicable to the determination of calcium and magnesium contents (mass fraction) in the range of 0,000 5 % to 0,006 % and 0,000 5 % to
19、0,20 %, respectively.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
20、(including any amendments) applies.ISO 385, Laboratory glassware BurettesISO 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 pre
21、paration of samples for the determination of chemical composition3 PrincipleA test portion is dissolved in a hydrochloric, nitric and hydrofluoric acid mixture and fumed with perchloric acid. Hydrochloric acid, nitric acid, and an internal standard element (if used) are added and the solution is dil
22、uted to a known volume. The solution is filtered if necessary, nebulized into an ICP spectrometer and the intensity of the emitted light from each element measured simultaneously with the intensity of the light emitted by the internal standard element.4 ReagentsDuring the analysis, unless otherwise
23、stated, use only reagents of recognized analytical grade with very low calcium and magnesium contents and only grade 2 water as specified in ISO 3696.4.1 Pure iron, containing less than 0,5 g/g of calcium and magnesium.4.2 Hydrochloric acid, about 1,19 g/ml.4.3 Hydrochloric acid, about 1,19 g/ml, di
24、luted 1 + 1.4.4 Hydrochloric acid, about 1,19 g/ml, diluted 1 + 4.4.5 Hydrochloric acid, about 1,19 g/ml, diluted 1 + 100. ISO 2014 All rights reserved 1BS ISO 13933:2014ISO 13933:2014(E)4.6 Nitric acid, about 1,42 g/ml.4.7 Hydrofluoric acid, about 1,14 g/ml.4.8 Perchloric acid, about 1,67 g/ml.4.9
25、Acid mixture.Mix two volumes of hydrochloric acid (4.2), one volume of nitric acid (4.6), and three volumes of water.4.10 Calcium standard solutions.4.10.1 Calcium stock solution, corresponding to 1 000 mg of calcium per litre.Dry several grams of calcium carbonate purity 99,9 % (mass fraction) in a
26、n oven at 100 C 5 C for at least 1 h and cool to room temperature in a desiccator. Weigh, to the nearest 0,000 1 g, 2,497 g of the dried product into a 400 ml beaker, add 20 ml of hydrochloric acid (4.3), cover with a watch-glass and heat gently until the product is completely dissolved. Cool to roo
27、m temperature and transfer the solution into a 1 000 ml one-mark volumetric flask. Dilute to the mark with water and mix.1 ml of this stock solution contains 1,000 mg of calcium.4.10.2 Calcium standard solution A, corresponding to 100 mg of calcium per litre.Transfer 10,00 ml of calcium stock soluti
28、on (4.10.1) into a 100 ml one-mark volumetric flask. Add 10 ml of hydrochloric acid (4.4). Dilute to the mark with water and mix.1 ml of this standard solution contains 0,100 mg of calcium.4.10.3 Calcium standard solution B, corresponding to 10 mg of calcium per litre.Transfer 10,00 ml of calcium st
29、andard solution A (4.10.2) into a 100 ml one-mark volumetric flask. Add 10 ml of hydrochloric acid (4.4). Dilute to the mark with water and mix.1 ml of this standard solution contains 0,010 mg of calcium.4.10.4 Calcium standard solution C, corresponding to 1,0 mg of calcium per litre.Transfer 10,00
30、ml of calcium standard solution B (4.10.3) into a 100 ml one-mark volumetric flask. Add 10 ml of hydrochloric acid (4.4). Dilute to the mark with water and mix.1 ml of this standard solution contains 0,001 mg of calcium.4.11 Magnesium standard solutions4.11.1 Magnesium stock solution, corresponding
31、to 1 000 mg of magnesium per litre.Weigh, to the nearest 0,000 1 g, 1,000 g of pure magnesium purity 99,9 % (mass fraction) and transfer into a 250 ml beaker. Add 20 ml of water, then add hydrochloric acid (4.3) drop by drop while swirling until the acid action ceases and continue adding hydrochlori
32、c acid (4.3) to a total volume of 20 ml. Cover with a watch-glass and heat to boil for 10 min. After cooling, transfer the solution quantitatively into a 1 000 ml one-mark volumetric flask. Dilute to the mark with water and mix.1 ml of this stock solution contains 1,000 mg of magnesium.2 ISO 2014 Al
33、l rights reservedBS ISO 13933:2014ISO 13933:2014(E)4.11.2 Magnesium standard solution A, corresponding to 100 mg of magnesium per litre.Transfer 10,00 ml of magnesium stock solution (4.11.1) into a 100 ml one-mark volumetric flask. Add 10 ml of hydrochloric acid (4.4). Dilute to the mark with water
34、and mix.1 ml of this standard solution contains 0,100 mg of magnesium.4.11.3 Magnesium standard solution B, corresponding to 10 mg of magnesium per litre.Transfer 10,00 ml of magnesium standard solution A (4.11.2) into a 100 ml one-mark volumetric flask. Add 10 ml of hydrochloric acid (4.4). Dilute
35、to the mark with water and mix.1 ml of this standard solution contains 0,010 mg of magnesium.4.11.4 Magnesium standard solution C, corresponding to 1,0 mg of magnesium per litre.Transfer 10,00 ml of magnesium standard solution B (4.11.3) into a 100 ml one-mark volumetric flask. Add 10 ml of hydrochl
36、oric acid (4.4). Dilute to the mark with water and mix.1 ml of this standard solution contains 0,001 mg of magnesium.4.12 Yttrium internal standard solution, corresponding to 100 mg of yttrium per litre.Calcine several grams of yttrium oxide purity 99,9 % (mass fraction) in a muffle furnace at 850 C
37、 10 C for at least 40 min and then cool to room temperature in a desiccator. Weigh 0,127 0 g of the calcined product into a 400 ml beaker, add 10 ml of hydrochloric acid (4.3), cover with a watch-glass, and heat gently until the product is completely dissolved. Cool to room temperature and transfer
38、the solution to a 1 000 ml one-mark volumetric flask. Dilute to the mark with water and mix.1 ml of this standard solution contains 0,100 mg of yttrium.5 ApparatusAll volumetric glassware shall be class A and calibrated in accordance with ISO 385, ISO 648, or ISO 1042, as appropriate.Ordinary labora
39、tory apparatus and the following shall be used.5.1 Inductively coupled plasma atomic emission spectrometerThe inductively coupled plasma atomic emission spectrometer used will be satisfactory if, after optimizing according to 7.4, it meets the performance criteria given in 5.1.2 to 5.1.4.The spectro
40、meter can be either a simultaneous or a sequential one. 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 standard technique. If the sequential spectrometer is not equipped with this arr
41、angement, the internal standard cannot be used and an alternative technique without an internal standard shall be applied.5.1.1 Analytical wavelengthsThis method does not specify any particular emission line. It is mandatory that each laboratory carefully investigates the wavelengths available on it
42、s own equipment to find the most suitable one regarding sensitivity and absence of interferences.In Table 1, however, several suggestions are given together with possible interferences. These wavelengths have been carefully investigated ISO 2014 All rights reserved 3BS ISO 13933:2014ISO 13933:2014(E
43、)The wavelength of the internal standard element chosen shall not interfere with the analytical wavelengths, nor should the internal element wavelength be interfered by elements present in the test solution. It is, however, recommended to use Y 371,03 nm or Y 360,07 nm. This wavelength is free of in
44、terferences from the elements.Table 1 Analytical wavelengths together with interfering elementsElementWavelength nmPossible interferencesCa 393,66 noneMg 279,55 noneY371,03 none360,07 noneOther elements can be used as internal standards, but they shall not be present in the sample, and shall not int
45、erfere with the elements to be determined at the appropriate wavelengths. Likewise, the elements present in the test solution shall not interfere with the internal standard at the wavelength chosen. The excitation requirements of the internal standard should be similar to those of the elements to be
46、 determined.5.1.2 Minimum practical resolution of the spectrometerCalculate the bandwidth, according to A.1, for the wavelength used. The bandwidth shall be less than 0,030 nm.5.1.3 Minimum short-term precisionCalculate the short-term precision according to A.2. The relative standard deviation (RSD)
47、 shall not exceed 1 % of the mean absolute or ratioed intensities for concentrations 100 to 1 000 times the limit of detection (LOD) (5.1.4). For concentrations that are 10 to 100 times the LOD (5.1.4), the RSD shall not exceed 5 %.5.1.4 Limit of Detection (LOD) and Limit of Quantification (LOQ)Calc
48、ulate the LOD and LOQ, according to A.3, for the analytical wavelengths used. The calculated values shall be below the values given in Table 2.Table 2 Limit of Detection (LOD) and Limit of Quantification (LOQ)ElementWavelength nmLOD mg/lLOQ mg/lCa 393,66 0,003 4 0,010Mg 279,55 0,004 6 0,0145.1.5 Lin
49、earity of the calibration curveThe linearity of the calibration curve is checked by calculating the correlation coefficient. This coefficient shall be higher than 0,999.5.2 Polytetrafluoroethylene (PTFE) beakers with PTFE coverNOTE For the determination of magnesium, glass beakers and watch-glass covers can be used.5.3 Volumetric flask, of capacity 100 ml, made of polypropylene or polyethylene terephthalate (PET).4 ISO 2014 All rights reservedBS ISO 13933:2014ISO 13933:2014(E)5.4 Filter, 0,22 m por
