1、raising standards worldwideNO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAWBSI Standards PublicationPD CEN/TR 10353:2011Chemical analysis of ferrousmaterials Analysis of ferro-silicon Determination of Al,Ti and P by inductively coupledplasma optical emissionspectrometryPD CEN/T
2、R 10353:2011 PUBLISHED DOCUMENTNational forewordThis Published Document is the UK implementation of CEN/TR10353:2011.The UK participation in its preparation was entrusted to TechnicalCommittee ISE/102, Methods of Chemical Analysis for Iron and Steel.A list of organizations represented on this commit
3、tee can beobtained on request to its secretary.This publication does not purport to include all the necessaryprovisions of a contract. Users are responsible for its correctapplication. BSI 2011ISBN 978 0 580 73228 7ICS 77.080.10Compliance with a British Standard cannot confer immunity fromlegal obli
4、gations.This Published Document was published under the authority of theStandards Policy and Strategy Committee on 30 November 2011.Amendments issued since publicationDate Text affectedPD CEN/TR 10353:2011TECHNICAL REPORT RAPPORT TECHNIQUE TECHNISCHER BERICHT CEN/TR 10353 November 2011 ICS 77.080.10
5、 English Version Chemical analysis of ferrous materials - Analysis of ferro-silicon - Determination of Al, Ti and P by inductively coupled plasma optical emission spectrometry Analyse chimique des matriaux ferreux - Analyse du ferro-silicium - Dtermination de Al, Ti et P par spectromtrie dmission op
6、tique avec source plasma induit Chemische Analyse von Ferrolegierungen - Analyse von Ferrosilizium - Bestimmung von Al, Ti und P durch induktiv gekoppeltes Plasma und optische EmissionsspektrometrieThis Technical Report was approved by CEN on 24 April 2011. It has been drawn up by the Technical Comm
7、ittee ECISS/TC 102. CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania
8、, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG Management Centre: Avenue Marnix 17, B-1000 Brussels 2011 CEN All rights of exploitation in any form and by any means reserved wor
9、ldwide for CEN national Members. Ref. No. CEN/TR 10353:2011: EPD CEN/TR 10353:2011CEN/TR 10353:2011 (E) 2 Contents Page Foreword 3 1 Scope 4 2 Normative references 4 3 Principle 4 4 Reagents .5 5 Apparatus .6 6 Sampling .6 7 Procedure .7 8 Expression of results . 12 9 Precision 12 10 Test report . 1
10、2 Annex A (informative) Plasma optical emission spectrometer - Suggested performance criteria to be checked 13 Annex B (informative) Test samples used for the precision test 16 Annex C (informative) Detailed results obtained from the precision test 17 Bibliography . 29 PD CEN/TR 10353:2011CEN/TR 103
11、53:2011 (E) 3 Foreword This document (CEN/TR 10353:2011) has been prepared by Technical Committee ECISS/TC 102 “Methods of chemical analysis for iron and steel”, the secretariat of which is held by SIS. Attention is drawn to the possibility that some of the elements of this document may be the subje
12、ct of patent rights. CEN and/or CENELEC shall not be held responsible for identifying any or all such patent rights. PD CEN/TR 10353:2011CEN/TR 10353:2011 (E) 4 1 Scope This Technical Report describes an inductively coupled plasma optical emission spectrometric method for the determination of Al, Ti
13、 and P contents in ferro-silicon materials. The method is applicable to: Al contents between 0,2 and 2 %; Ti contents between 0,02 and 0,25 %; P contents between 0,005 and 0,05 %. The procedure is valid for the analytical lines given in Table 1. This table also gives, for each line, the spectral int
14、erferences, which shall be corrected. NOTE The interferences extent as well as other possible interferences depend on the temperature in the plasma and on the optical resolution of the spectrometer used. Table 1 Spectral lines recommended together with the interferences which shall be corrected Elem
15、ent Wavelength (nm) Interferences Al 308,22 V Ti 337,28 V, NiP 178,29 Mo 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 reference
16、d document (including any amendments) applies. EN ISO 648, Laboratory glassware Single-volume pipettes (ISO 648:2008) EN ISO 1042, Laboratory glassware One-mark volumetric flasks (ISO 1042:1998) 3 Principle Dissolution of a test portion with nitric, hydrofluoric and perchloric acids. Addition of hyd
17、rochloric acid. Filtration and ignition of the acid insoluble residue. Fusion of the residue with sodium hydrogen sulphate, dissolution of the melt and addition of this solution to the reserved filtrate. After suitable dilution and, if necessary, addition of an internal reference element, the soluti
18、on is filtered and nebulised into an inductively coupled plasma optical emission spectrometer. The intensity of the emitted light from each element is then measured (simultaneously with that emitted from the internal reference element, where relevant). PD CEN/TR 10353:2011CEN/TR 10353:2011 (E) 5 4 R
19、eagents During the analysis, use only reagents of recognised analytical grade and only distilled water or water of equivalent purity. The same reagents should be used for the preparation of calibration solutions and of sample solutions. 4.1 Hydrofluoric acid, HF (20= 1,13 g/ml) WARNING Hydrofluoric
20、acid is extremely irritating and corrosive to skin and mucous membranes producing severe skin burns which are slow to heal. In the case of contact with skin, wash well with water, apply a topical gel containing 2,5 % (mass fraction) calcium gluconate, and seek immediate medical treatment. 4.2 Hydroc
21、hloric acid, HCl (20 = 1,19 g/ml) 4.3 Hydrochloric acid, solution 1 + 1 Add 500 ml of hydrochloric acid (4.2) to 500 ml of water. 4.4 Hydrochloric acid, solution 1 + 9 Add 50 ml of hydrochloric acid (4.2) to 450 ml of water. 4.5 Nitric acid, HNO3(20= 1,40 g/ml) 4.6 Perchloric acid, HClO4(20 = 1,68 g
22、/ml) 4.7 Sodium hydrogen sulphate 4.8 Pure iron The purity of the iron selected shall be at least ten times better than the low limit of the scope of each element included in the present method. 4.9 Aluminium, 0,5 g/l standard solution Weigh (0,5 0,001) g of aluminium (99,98 % purity) and transfer i
23、nto a 400 ml beaker. Add 50 ml of hydrochloric acid solution (4.3) and heat gently until aluminium is completely dissolved. After cooling, transfer the solution quantitatively into a 1 000 ml one-mark volumetric flask, dilute to the mark with water and mix well. 1 ml of this solution contains 0,5 mg
24、 of Al. 4.10 Titanium, 0,5 g/l standard solution Weigh (0,5 0,001) g of titanium (99,98 % purity) and transfer into a 400 ml beaker. Add 25 ml hydrochloric acid solution (4.3) and 5 to 10 drops of hydrofluoric acid (4.1). Heat gently until titanium is completely dissolved. After cooling, transfer th
25、e solution quantitatively into a 1 000 ml one-mark volumetric flask, dilute to the mark with water and mix well. 1 ml of this solution contains 0,5 mg of Ti. PD CEN/TR 10353:2011CEN/TR 10353:2011 (E) 6 4.11 Titanium, 0,05 g/l standard solution freshly prepared Transfer 20 ml of titanium standard sol
26、ution (4.10) into a 200 ml one-mark volumetric flask. Dilute to the mark with water and mix well. 1 ml of this solution contains 0,05 mg of Ti. 4.12 Phosphorus, 0,1 g/l standard solution freshly prepared Weigh (0,4393 0,001) g of dried potassium dihydrogen phosphate and transfer into a 250 ml beaker
27、. Dissolve it with water. Transfer the solution quantitatively into a 1 000 ml one-mark volumetric flask, dilute to the mark with water and mix well. 1 ml of this solution contains 0,1 mg of P. 4.13 Phosphorus, 0,01 g/l standard solution freshly prepared Transfer 20,0 ml of phosphorus standard solut
28、ion (4.12) into a 200 ml one-mark volumetric flask. Dilute to the mark with water and mix well. 1 ml of this solution contains 0,01 mg of P. 4.14 Scandium, 1 g/l solution Weight (1,534 0,001) g of scandium oxide, Sc2O3, (99,98 % purity) and transfer into a 600 ml beaker. Dissolve in 40 ml nitric aci
29、d (4.5). Transfer into a 1 000 ml one-mark volumetric flask. Dilute to the mark with water and mix well. 5 Apparatus All volumetric glassware shall be class A and calibrated, in accordance with EN ISO 648 or EN ISO 1042 as appropriate. 5.1 Platinum crucibles and covers 5.2 Polytetrafluoroethylene (P
30、TFE) beakers 5.3 Optical emission spectrometer, equipped with inductively coupled plasma This shall be equipped with a nebulisation system. The instrument used will be satisfactory if, after optimising in accordance with the manufacturers instructions, it meets the performance criteria given in Anne
31、x A. The spectrometer can be either of simultaneous or of sequential type. A sequential spectrometer can be equipped with an extra arrangement for simultaneous measurement of the internal reference element emitted light. In this case the sequential spectrometer can be used for the measurement method
32、 using the internal reference element. If the sequential spectrometer is not equipped with this arrangement, the internal reference element shall not be used. 6 Sampling Sampling shall be carried out in accordance with appropriate international or national standards for ferro alloys. PD CEN/TR 10353
33、:2011CEN/TR 10353:2011 (E) 7 7 Procedure 7.1 Preparation of the test solution 7.1.1 Test portion Weigh, to the nearest 0,001 g, 0,5 g of the test sample. 7.1.2 Dissolution of the test portion Transfer the test portion (7.1.1) into a platinum crucible (5.1) having a suitable capacity or into a polyte
34、trafluoroethylene (PTFE) beaker (5.2). Add 10 ml of nitric acid (4.5) and, in small portions, 10 ml of hydrofluoric acid (4.1). After each addition swirl the crucible or the beaker and allow the reaction to subside. Then heat to complete the dissolution. NOTE If the internal reference element is not
35、 used, care must be taken in order to avoid uncontrolled evaporation of the acids, since differences in acid concentrations in the different solutions will give interference. A way to homogenise the residual acid concentration is the evaporation of the sample solution to dryness, followed by the dis
36、solution of the salts. Add 2,5 ml of perchloric acid (4.6) and heat until copious white fumes appear. Cool, rinse the sides of the crucible or that of the beaker with water and swirl to dissolve the salts. Repeat the heating to copious fumes. Cool and add 15 ml of hydrochloric acid (4.4). Heat gentl
37、y, in order to dissolve all salts. Filter the solution through a close texture filter paper, collect the filtrate into a 250 ml beaker and rinse the crucible or the PTFE beaker and the filter with hot water. Reserve the filtrate. Transfer the filter into a platinum crucible (5.1), dry at about 105 C
38、 and then heat at about 600 C to remove organic matter. Ignite at 1 000 C, to remove volatile oxides, for 15 min. Cool, add 0,5 g of sodium hydrogen sulphate (4.7) and melt. Cool and dissolve the fusion products with the minimum quantity of water. Add this solution quantitatively to the filtrate in
39、the 250 ml beaker. Transfer the solution quantitatively into a 100 ml volumetric flask. If the internal reference element is used add, with a calibrated pipette, 0,5 ml of the scandium solution (4.14). Make up to the mark with water and mix well. 7.2 Preparation of the calibration solutions 7.2.1 Al
40、uminium: calibration solutions Transfer 0,15 g of pure iron (4.8) in each of a series of six 400 ml beakers and dissolve with 10 ml of nitric acid (4.5). NOTE The iron amount (0,15 g) corresponds to a test portion of a ferro-silicon having a 30-70 % average composition. After dissolution add 2,5 ml
41、of perchloric acid (4.6) and evaporate to copious fumes. After cooling at room temperature, add 15 ml of hydrochloric acid (4.4) and heat gently, in order to dissolve the salts. Add 0,5 g of sodium hydrogen sulphate (4.7) and swirl to dissolve this reagent. With calibrated pipettes, add the volumes
42、of the aluminium standard solution (4.9) shown in Table 2. Transfer each solution quantitatively into a series of 100 ml volumetric flasks. If the internal reference element is used add, with a calibrated pipette, 0,5 ml of the scandium solution (4.14). PD CEN/TR 10353:2011CEN/TR 10353:2011 (E) 8 Di
43、lute to the mark with water and mix well. Table 2 Composition of the calibration solutions for aluminium Calibration solution label Aluminium standard solution volumes (4.9) (ml) Corresponding aluminium mass (mg) Corresponding aluminium content in the sample (%) 0 0 0 0 1 2 1,0 0,2 2 4 2,0 0,43 7 3,
44、5 0,7 4 10 5,0 1,05 20 10,0 2,0 7.2.2 Titanium: calibration solutions Proceed as specified in 7.2.1 from “Transfer 0,15 g of pure iron“ until “and swirl to dissolve the salts.“ With calibrated pipettes, add the volumes of the titanium standard solutions (4.10 or 4.11) shown in Table 3. Transfer each
45、 solution quantitatively into a series of 100 ml volumetric flasks. If the internal reference element is used add, with a calibrated pipette, 0,5 ml of the scandium solution (4.14). Dilute to the mark with water and mix well. PD CEN/TR 10353:2011CEN/TR 10353:2011 (E) 9 Table 3 Composition of the cal
46、ibration solutions for titanium Calibration solution label Titanium standard solutions volumes (4.10 or 4.11) (ml) Corresponding titanium mass (mg) Corresponding titanium content in the sample (%) 0 0 0 0 1 2,0 (4.11) 0,10 0,02 2 5,0 (4.11) 0,25 0,05 3 10,0 (4.11) 0,50 0,10 4 2,0 (4.10) 1,00 0,20 5
47、2,5 (4.10) 1,25 0,25 7.2.3 Phosphorus: calibration solutions Proceed as specified in 7.2.1 from “Transfer 0,15 g of pure iron“ until “and swirl to dissolve the salts.“ With calibrated pipettes, add the volumes of the phosphorus standard solutions (4.12 or 4.13) shown in Table 4. Transfer each soluti
48、on quantitatively into a series of 100 ml volumetric flasks. If the internal reference element is used add, with a calibrated pipette, 0,5 ml of the scandium solution (4.14). Dilute to the mark with water and mix well. Table 4 Composition of the calibration solutions for phosphorus Calibration solut
49、ion label Phosphorus standard solutions volumes (4.12 or 4.13) (ml) Corresponding phosphorus mass (mg) Corresponding phosphorus content in the sample (%) 0 0 0 0 1 2,5 (4.13) 0,025 0,005 2 5,0 (4.13) 0,050 0,010 3 10,0 (4.13) 0,100 0,020 4 15,0 (4.13) 0,150 0,030 5 2,5 (4.12) 0,250 0,050 7.2.4 Multi-elemental calibration solutions (Al, Ti and P) Proceed as specified in 7.2.1 from “Transfer 0,15 g of pure iron“ until “and swirl to dissolve the salts.“ With calibrated pipettes, add the volumes of the aluminium, titanium and p
