X线荧光反射检测铁矿石的不同成分（ISO-9516-1-2003） .pdf

Reference number ISO 9516-1:2003(E) © ISO 2003 INTERNATIONAL STANDARD ISO 9516-1 First edition 2003-04-01 Iron ores Determination of various elements by X-ray fluorescence spectrometry Part 1: Comprehensive procedure Minerais de fer Dosage de divers éléments par spectrométrie de fluorescence de rayons X Partie 1: Procédure détaillée ISO 9516-1:2003(E) PDF disclaimer This PDF file may contain embedded typefaces. In accordance with Adobe's licensing policy, this file may be printed or viewed but shall not be edited unless the typefaces which are embedded are licensed to and installed on the computer performing the editing. In downloading this file, parties accept therein the responsibility of not infringing Adobe's licensing policy. The ISO Central Secretariat accepts no liability in this area. Adobe is a trademark of Adobe Systems Incorporated. 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ISO copyright office Case postale 56 CH-1211 Geneva 20 Tel. + 41 22 749 01 11 Fax + 41 22 749 09 47 E-mail copyrightiso.org Web www.iso.org Published in Switzerland ii © ISO 2003 All rights reserved ISO 9516-1:2003(E) © ISO 2003 All rights reserved iii Contents Page Forewordiv Introduction v 1 Scope1 2 Normative references .2 3 Principle.2 4 Reagents and materials2 5 Apparatus.6 6 Sampling and samples.7 7 Procedure.7 8 Calculation of results17 9 General treatment of results20 10 Test report24 Annex A (normative) Preparation of flux A25 Annex B (normative) Preparation of flux B or flux C27 Annex C (normative) Preparation of synthetic calibration standard 28 Annex D (normative) Standard deviation of specimen preparation30 Annex E (normative) Spectrometer precision tests35 Annex F (normative) Determination of the dead time and maximum count rate of the equipment39 Annex G (informative) Air cooling block for fused discs .46 Annex H (informative) Computer program for calculation of results47 Annex I (informative) Sample of data for use with calculation program 60 Annex J (normative) Flowchart for acceptance of results.65 ISO 9516-1:2003(E) iv © ISO 2003 All rights reserved 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. 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 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 % of the member bodies casting a vote. 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 9516-1 was prepared by Technical Committee ISO/TC 102, Iron ore and direct reduced iron, Subcommittee SC 2, Chemical analysis. This first edition, together with ISO 9516-2, cancels and replaces ISO 9516:1992 by the augmentation of the range of elements under analysis and the diversification into two procedures. ISO 9516 consists of the following parts, under the general title Iron ores Determination of various elements by X-ray fluorescence spectrometry: Part 1: Comprehensive procedure Part 2: Simplified procedure ISO 9516-1:2003(E) © ISO 2003 All rights reserved v Introduction In this part of ISO 9516, Table 1 indicates that some determinations may be used for referee purposes and others for routine analysis only. A simplified procedure for routine use with all determination will be published in ISO 9516-2. INTERNATIONAL STANDARD ISO 9516-1:2003(E) © ISO 2003 All rights reserved 1 Iron ores Determination of various elements by X-ray fluorescence spectrometry Part 1: Comprehensive procedure WARNING This part of ISO 9516 may involve hazardous materials, operations and equipment. This part of ISO 9516 does not purport to address all of the safety problems associated with its use. It is the responsibility of the user of this part of ISO 9516 to establish appropriate health and safety practices and determine the applicability of regulatory limitations prior to use. 1 Scope This part of ISO 9516 sets out a wavelength dispersive X-ray fluorescence procedure for the determination of iron, silicon, calcium, manganese, aluminium, titanium, magnesium, phosphorus, sulfur, potassium, tin, vanadium, chromium, cobalt, nickel, copper, zinc, arsenic, lead and barium in iron ores. The method has been designed to cope with iron ores having high ignition losses. The method is applicable to iron ores regardless of mineralogical type. The concentration range covered for each of the component elements is given in Table 1. The determination of total iron cannot be used for referee purposes. Table 1 Range of application of the method Component element Concentration range for referee purposes % Concentration range for analysis % Fe 38 to 72 Si 0,2 to 6,5 0,2 to 6,5 Ca 0,019 to 12,7 0,019 to 12,7 Mn 0,02 to 0,82 0,02 to 0,82 Al 0,1 to 3,5 0,1 to 3,5 Ti 0,016 to 4,7 0,016 to 4,7 Mg 0,2 to 2,0 0,2 to 2,0 P 0,006 to 0,6 0,006 to 0,6 S 0,04 to 0,6 0,007 to 0,6 K 0,008 to 0,45 0,012 to 0,45 Sn 0,006 to 0,015 V 0,001 7 to 0,3 0,001 7 to 0,3 Cr 0,006 to 0,024 Co 0,006 to 0,018 Ni 0,011 to 0,013 Cu 0,012 to 0,061 Zn 0,006 9 to 0,166 0,005 to 0,166 As 0,008 to 0,06 Pb 0,018 to 0,32 0,018 to 0,32 Ba 0,036 to 0,4 ISO 9516-1:2003(E) 2 © ISO 2003 All rights reserved 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) applies. ISO 3082:1998, Iron ores Sampling and sample preparation procedures ISO 7764:1985, Iron ores Preparation of predried test samples for chemical analysis 3 Principle The glass discs for X-ray fluorescence measurement are prepared by incorporating the test portion of the iron ore sample, via fusion, into a borate glass disc using a casting procedure. By using a fused glass disc, particle size effects are eliminated. Sodium nitrate is added to the flux to ensure complete oxidation of all components, particularly iron and sulfur. Any of three methods for glass disc preparation may be used: two use lithium borate as flux; the other uses sodium borate. X-ray fluorescence measurements are based on the “line only” principle. It is not necessary to measure backgrounds on each glass disc, as background equivalent concentrations (BEC) are determined on several blank glass discs at the line position using concentration-based line-overlap corrections. If desired, backgrounds can be measured to obtain net line intensities. The method is applicable to data from simultaneous and sequential X-ray fluorescence spectrometers. The method relies on measuring all components of the sample, other than volatiles. If some components are not measured, then errors will result in the measured components (see 7.2.2). Calibration is carried out using pure chemicals. Results are obtained after matrix corrections for inter-element effects. 4 Reagents and materials During analysis, only reagents of recognized high purity shall be used. NOTE 1 Where reagents have been ignited, they should be covered during cooling in the desiccator and weighed as soon as possible. NOTE 2 Reagents 4.2, 4.5, 4.7, 4.8, 4.9, 4.11, 4.13, 4.15, 4.16, 4.18 and 4.20 are used only for the preparation of the synthetic calibration standard, and are not required if the synthetic calibration standard is available commercially. 4.1 Silicon dioxide, (SiO2), nominally 99,999 % SiO2 The silicon dioxide shall contain less than 3 µg/g of each of the other elements listed in Table 1. It shall be heated to 1 000 °C in a platinum crucible for a minimum of 2 h and cooled in a desiccator. 4.2 Aluminium oxide, (Al2O3), analytical reagent grade, form If the form is used, it shall be heated to 1 000 °C in a platinum crucible for a minimum of 2 h. If the aluminium oxide is not the form, it shall be converted to the form by heating to 1 250 °C in a platinum crucible for a minimum of 2 h. It shall be cooled in a desiccator and weighed as soon as it is cool. ISO 9516-1:2003(E) © ISO 2003 All rights reserved 3 4.3 Iron(III) oxide, (Fe2O3), nominally 99,999 % Fe2O3 The iron(III) oxide shall contain less than 3 µg/g of each of the other elements listed in Table 1. It shall be heated at 1 000 °C in a platinum crucible for a minimum of 1 h and cooled in a desiccator. 4.4 Titanium dioxide, (TiO2) Analytical grade titanium dioxide shall be heated at 1 000 °C in a platinum crucible for a minimum of 1 h and cooled in a desiccator. Phosphorus is a common impurity in TiO2 and a reagent low in phosphorus shall be selected. The selected reagent shall be checked, as even nominally high-purity reagents can be significantly contaminated, e.g. a supposed 99,99 % TiO2 grade reagent has been found to contain about 0,5 % P2O5. 4.5 Potassium dihydrogen orthophosphate, (KH2PO4) Analytical grade potassium dihydrogen orthophosphate shall be dried at 105 °C for 1 h and cooled in a desiccator. 4.6 Calcium carbonate, (CaCO3) Analytical grade calcium carbonate shall be dried at 105 °C for 1 h and cooled in a desiccator. 4.7 Calcium sulfate, (CaSO4.2H2O) Analytical grade calcium sulfate dihydrate shall be dehydrated at 700 °C for 1 h and cooled in a desiccator. 4.8 Manganese oxide, (Mn3O4) Manganese oxide shall be prepared by heating analytical grade manganese oxide (MnO2, MnO or Mn3O4) for 15 h at 1 000 °C in a platinum crucible and then cooling. The lumpy material shall be crushed to a fine powder, heated for 1 h at 200 °C and cooled in a desiccator. 4.9 Magnesium oxide, (MgO) Analytical grade magnesium oxide shall be dried in a platinum crucible by slowly heating from room temperature to 1 000 °C. After 1 h at 1 000 °C, the crucible containing the magnesium oxide shall be placed in a desiccator and weighed as soon as it is cool, as magnesium oxide readily absorbs carbon dioxide from the atmosphere. 4.10 Sodium nitrate, (NaNO3) Analytical grade sodium nitrate shall be dried at 105 °C for 1 h and cooled in a desiccator. 4.11 Tin oxide, (SnO2) Analytical grade tin oxide shall be heated at 400 °C for a minimum of 1 h and cooled in a desiccator. 4.12 Vanadium(V) oxide, (V2O5) Analytical grade vanadium(V) oxide shall be heated at 400 °C for a minimum of 1 h and cooled in a desiccator. 4.13 Chromium(III) oxide, (Cr2O3) Analytical grade chromium(III) oxide shall be heated at 400 °C for a minimum of 1 h and cooled in a desiccator. ISO 9516-1:2003(E) 4 © ISO 2003 All rights reserved 4.14 Cobalt oxide, (Co3O4) Analytical grade cobalt oxide shall be heated at 400 °C for a minimum of 1 h and cooled in a desiccator. 4.15 Nickel oxide, (NiO) Analytical grade nickel oxide shall be heated at 400 °C for a minimum of 1 h and cooled in a desiccator. 4.16 Copper oxide, (CuO) Analytical grade copper oxide shall be heated at 400 °C for a minimum of 1 h and cooled in a desiccator. 4.17 Zinc oxide, (ZnO) Analytical grade zinc oxide shall be heated at 400 °C for a minimum of 1 h and cooled in a desiccator. 4.18 Di-sodium hydrogen arsenate, (Na2HAsO4.7H2O) The analytical grade reagent shall be weighed as received. 4.19 Lead oxide, (PbO) Analytical grade lead oxide shall be heated at 400 °C for a minimum of 1 h and cooled in a desiccator. 4.20 Barium carbonate, (BaCO3) Analytical grade barium carbonate shall be heated at 105 °C for a minimum of 1 h and cooled in a desiccator. 4.21 Ammonium iodide, (NH4I) Laboratory reagent grade ammonium iodide need not be dried, but shall be stored in a desiccator. 4.22 Desiccant The desiccant shall be freshly regenerated self-indicating silica gel. 4.23 Flux 4.23.1 General Flux A, flux B or flux C, as described in 4.23.2, 4.23.3 and 4.23.4, may be used. The levels of contamination in the flux shall be checked (see 9.1). Because levels of contamination may vary from batch to batch, the same batch of flux shall be used for all discs (iron ore, blank and calibration) involved in the batch of determinations. 4.23.2 Flux A Flux A shall be prepared by fusion of a mixture of anhydrous lithium tetraborate (Li2B4O7) and anhydrous lithium metaborate (LiBO2) using the procedure specified in Annex A. Flux shall be dried at 500 °C for a minimum of 4 h and stored in a desiccator. 4.23.3 Flux B Flux B shall be prepared using sodium tetraborate using the procedure specified in Annex B. Flux shall be dried at 500 °C for a minimum of 4 h and stored in a desiccator. ISO 9516-1:2003(E) © ISO 2003 All rights reserved 5 4.23.4 Flux C Flux C shall be prepared using lithium tetraborate using the procedure specified in Annex B. Flux shall be dried at 500 °C for a minimum of 4 h and stored in a desiccator. NOTE If this flux is used, sulfur will not be reported. 4.24 Calibration standard Two independent (i.e. prepared on different days) batches (labelled Day 1 and Day 2) of calibration standard shall be prepared by the procedure specified in Annex C. The composition of the calibration standard, given in Table 2, approximates that of an iron ore. The contents of some elements are higher than would be expected in an iron ore, but this is advantageous for obtaining a reliable calibration. Prior to weighing, a sufficient aliquot of the calibration standard shall be heated at 900 °C for 20 min and cooled in a desiccator. Table 2 Composition of the calibration standard Component element Content % Oxide content % Fe 44,764 64,000 Fe2O3 Si 4,44 9,500 SiO2 Ca 3,067 4,2913 CaO Mn 1,441 2,000 Mn3O4 Al 2,65 5,000 Al2O3 Ti 0,899 1,500 TiO2 Mg 3,016 5,000 Mg