1、BRITISH STANDARD BS EN 14242:2004 Aluminium and aluminium alloys Chemical analysis Inductively coupled plasma optical emission spectral analysis The European Standard EN 14242:2004 has the status of a British Standard ICS 77.040.30; 77.120.10 BS EN 14242:2004 This British Standard was published unde
2、r the authority of the Standards Policy and Strategy Committee on 22 September 2004 BSI 22 September 2004 ISBN 0 580 44498 8 National foreword This British Standard is the official English language version of EN 14242:2004. The UK participation in its preparation was entrusted to Technical Committee
3、 NFE/35, Light metals and their alloys, which has the responsibility to: 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 b
4、e found in the BSI Catalogue under the section entitled “International Standards Correspondence Index”, or by using the “Search” facility of the BSI Electronic Catalogue or of British Standards Online. This publication does not purport to include all the necessary provisions of a contract. Users are
5、 responsible for its correct application. Compliance with a British Standard does not of itself confer immunity from legal obligations. aid enquirers to understand the text; present to the responsible international/European committee any enquiries on the interpretation, or proposals for change, and
6、keep the UK interests informed; monitor related international and European developments and promulgate them in the UK. Summary of pages This document comprises a front cover, an inside front cover, the EN title page, pages 2 to 21 and a back cover. The BSI copyright notice displayed in this document
7、 indicates when the document was last issued. Amendments issued since publication Amd. No. Date CommentsEUROPEANSTANDARD NORMEEUROPENNE EUROPISCHENORM EN14242 September2004 ICS77.040.30;77.120.10 Englishversion AluminiumandaluminiumalloysChemicalanalysis Inductivelycoupledplasmaopticalemissionspectr
8、alanalysis AluminiumetalliagesdaluminiumAnalysechimique Analyseparspectromtriedmissionoptiqueenplasma induit AluminiumundAluminiumlegierungenChemische AnalyseOptischeEmissionspektralanalysemitinduktiv gekoppelterPlasmaanregung ThisEuropeanStandardwasapprovedbyCENon1July2004. CENmembersareboundtocomp
9、lywiththeCEN/CENELECInternalRegulationswhichstipulatetheconditionsforgivingthisEurope an Standardthestatusofanationalstandardwithoutanyalteration.Uptodatelistsandbibliographicalreferencesconcernings uchnational standardsmaybeobtainedonapplicationtotheCentralSecretariatortoanyCENmember. ThisEuropeanS
10、tandardexistsinthreeofficialversions(English,French,German).Aversioninanyotherlanguagemadebytra nslation undertheresponsibilityofaCENmemberintoitsownlanguageandnotifiedtotheCentralSecretariathasthesamestatusast heofficial versions. CENmembersarethenationalstandardsbodiesofAustria,Belgium,Cyprus,Czec
11、hRepublic,Denmark,Estonia,Finland,France, Germany,Greece,Hungary,Iceland,Ireland,Italy,Latvia,Lithuania,Luxembourg,Malta,Netherlands,Norway,Poland,Portugal, Slovakia, Slovenia,Spain,Sweden,SwitzerlandandUnitedKingdom. EUROPEANCOMMITTEEFORSTANDARDIZATION COMITEUROPENDENORMALISATION EUROPISCHESKOMITEE
12、FRNORMUNG ManagementCentre:ruedeStassart,36B1050Brussels 2004CEN Allrightsofexploitationinanyformandbyanymeansreserved worldwideforCENnationalMembers. Ref.No.EN14242:2004:EEN 14242:2004 (E) 2 Contents page Foreword3 Introduction .4 1 Scope 5 2 Normative references 5 3 Terms and definitions .5 4 Prin
13、ciple5 5 Reagents.6 6 Equipment 7 7 Sampling and samples8 8 Procedure .9 9 Correction of short-term fluctuations and drift 12 10 Investigation of interferences.12 11 Expression of the results13 12 Test report 13 Annex A (informative) Analytical lines .15 Annex B (informative) Preparation of stock so
14、lutions .17 Bibliography 21 EN 14242:2004 (E) 3 Foreword This document (EN 14242:2004) has been prepared by Technical Committee CEN/TC 132 “Aluminium and alumin- ium alloys“, the secretariat of which is held by AFNOR. This European Standard shall be given the status of a national standard, either by
15、 publication of an identical text or by endorsement, at the latest by March 2005, and conflicting national standards shall be withdrawn at the latest by March 2005. Within its programme of work, Technical Committee CEN/TC 132 requested CEN/TC 132/WG 17 “Chemical analysis“ to prepare the following st
16、andard: EN 14242, Aluminium and aluminium alloys Chemical analysis Inductively coupled plasma optical emission spectral analysis. This document includes a Bibliography. According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following coun- tries are bound to i
17、mplement this European Standard: Austria, Belgium, Cyprus, Czech Republic, Denmark, Esto- nia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Ki
18、ngdom. EN 14242:2004 (E) 4 Introduction This document describes detailed steps for dissolution and preparation of calibration solutions. The preferred use is for certification and referee analysis. All instrumentation, including software used in the testing laboratories, are different and subject to
19、 change. Therefore, general criteria for calibration and measurement are specified. This method has to be used with primary reference materials whose mass of substance have a significant smaller uncertainty as required of the repeatability of the testing procedure. EN 14242:2004 (E) 5 1 Scope This d
20、ocument specifies the inductively coupled plasma optical emission spectral analysis (ICP-OES) of aluminium and aluminium alloys. This method is applicable to the determination of silicon, iron, copper, manganese, magnesium, chromium, nickel, zinc, titanium, gallium, vanadium, beryllium, bismuth, cal
21、cium, cadmium, cobalt, lithium, sodium, lead, antimony, tin, strontium, and zirconium in aluminium and aluminium alloys. NOTE The national safety instructions should be taken into consideration. 2 Normative references The following referenced documents are indispensable for the application of this d
22、ocument. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies. prEN 12258-2:2001, Aluminium and aluminium alloys Terms and definitions Part 2: Chemical analysis. prEN 14361, Aluminium and alumin
23、ium alloys Chemical analysis Sampling from metal melts. EN ISO 3696, Water for analytical laboratory use Specification and test methods (ISO 3696:1987). EN ISO/IEC 17025, General requirements for the competence of testing and calibration laboratories (ISO/IEC 17025:1999). ISO 3534-1, Statistics Voca
24、bulary and symbols Part 1: Probability and general statistical terms. 3 Terms and definitions For the purposes of this document, the terms and definitions given in prEN 12258-2:2001 apply. 4 Principle A test portion is dissolved with: sodium hydroxide solution and acidification with a mixture of nit
25、ric acid and hydrochloric acid; or nitric acid and hydrofluoric acid; or a mixture of hydrochloric acid and nitric acid; or hydrochloric acid and hydrogen peroxide according to the alloy type and the element contents to be determined. This solution is nebulized and excited in an inductively coupled
26、plasma connected with an optical emission spectrometer. The emission signals on selected analytical lines (see Annex A) are compared with those of calibration solutions. The ranges of application and the accuracy of the method or any alternative steps shall be validated by the labora- tory. Approxim
27、ate ranges of application are given in Annex A. EN 14242:2004 (E) 6 5 Reagents 5.1 General All volumetric measurements shall be made at the temperature specified on the pipettes and volumetric flasks. Each mixture shall be thoroughly mixed. For the analysis, reagents of recognized analytical grade a
28、nd deionized water, shall be used in accordance with EN ISO 3696. 5.2 Sodium hydroxide solution (10 M) Dissolve 400,0 g sodium hydroxide NaOH in a plastic beaker with a lid. Transfer the solution to a 1 000 ml volumet- ric plastic flask and make up to volume with water. 5.3 Hydrogen peroxide, 30 % (
29、mass fraction) solution 5.4 Nitric acid ( = 1,4 g/ml, 65 % mass fraction) 5.5 Nitric acid (1 + 1) Carefully add 500 ml nitric acid (5.4) to 400 ml water, allow to cool, and make up the volume to 1 000 ml with water. 5.6 Nitric acid (4 M) Carefully add 27,7 ml nitric acid (5.4) to 50 ml water, allow
30、to cool, and make up the volume to 100 ml with water. 5.7 Hydrochloric acid ( = 1,18 g/ml, 37 % mass fraction) 5.8 Hydrochloric acid (1 + 1) Carefully add 500 ml hydrochloric acid (5.7) to 400 ml water, allow to cool, and make up the volume to 1 000 ml with water. 5.9 Sodium nitrite 5.10 High-purity
31、 aluminium Aluminium, purity equal or better than 99,999 % mass fraction; the content of the elements to be determined shall not be higher than 10 % of the detection limits of this method or of the element content to be determined. 5.11 Hydrofluoric acid, ( = 1,14 g/ml, 40 % mass fraction) 5.12 Stoc
32、k solutions The concentrations of the stock solutions shall be traceable to international standard units mass and amount of substances i.e. kilogram (kg) and mol (mol) according to EN ISO/IEC 17025. Examples of preparation of stock so- lutions are described in B.3. Stock solutions containing sulphat
33、e ions shall not be used if the determination of an element is required which forms insoluble compounds with sulphate. Stock solutions shall not to be used when the time of stability is expired. EN 14242:2004 (E) 7 5.13 Standard solutions Prepare standard solutions from the stock solutions by diluti
34、on steps not more than 1 : 5 using calibrated pipettes not smaller than 10 ml and calibrated volumetric flasks not smaller than 100 ml. Standard solutions and calibration solutions with element contents equal or less than 50 mg/l can be unstable and shall be prepared just before use. NOTE Calibratio
35、n solutions can be made directly from stock solutions by means of weight measurement (see 8.4). 5.14 Reference element solutions 5.14.1 Reference element solution lanthanum, 1 g/l Transfer 1,173 g lanthanum oxide La 2 O 3 , purity equal or better than 99,99 % mass fraction, previously dried at 150 C
36、 to constant mass, to a 400 ml beaker with a lid. Add 40 ml hydrochloric acid solution (5.8), transfer the solu- tion into a 1 000 ml volumetric flask and make up to volume with water. 5.14.2 Reference element solution, lanthanum, 200 mg/l Transfer 20,00 ml of reference element solution, lanthanum (
37、5.14.1) into a 100 ml volumetric flask, add 1 ml hydro- chloric acid solution (5.8) and make up to volume with water. 5.14.3 Reference element solution, scandium, 0,1 g/l Transfer 100,0 mg scandium purity equal or better than 99,99 % mass fraction into a 400 ml beaker with a lid. Add 20 ml hydrochlo
38、ric acid solution (5.8). Heat gently, if necessary, until the dissolution is complete, allow to cool, and transfer the solution into a 1 000 ml volumetric flask and make up to volume with water. NOTE Scandium solutions can be unstable. 5.14.4 Reference element solution, scandium, 20 mg/l Transfer 20
39、,00 ml of reference element solution scandium (5.14.3) into a 100 ml volumetric flask, add 1 ml hydrochloric acid solution (5.8) and make up to volume with water. 5.14.5 Reference element solution, molybdenum, 1 g/l Transfer 1,84 g ammonium molybdate (NH 4 ) 6 Mo 7 O 24 4 H 2 O into a 1 000 ml volum
40、etric flask and make up to volume with water. 5.14.6 Reference element solution, molybdenum, 200 mg/l Transfer 20,00 ml of reference element solution molybdenum (5.14.5) into a 100 ml volumetric flask, add 1 ml hydrochloric acid solution (5.8) and make up to volume with water. 6 Equipment 6.1 Optica
41、l emission spectrometer with inductively coupled argon plasma excitation and polychromator or monochromator (for analytical lines, see Annex A), for solutions containing hydrofluoric acid. The spectrometer shall be equipped with a fluoride-resistant nebulizer. NOTE The nebulizer should be selected c
42、arefully. Many of the available fluoride-resistant nebulizers are not as stable as standard nebulizers. EN 14242:2004 (E) 8 6.2 PTFE-beakers with lid, 400 ml 6.3 Platinum crucibles with a lid, 100 ml to 120 ml 6.4 Plastic measuring pipettes, 2,0 ml, 6,0 ml and 10,0 ml NOTE The plastic equipment shou
43、ld be selected carefully to avoid losses and contaminations. 6.5 Plastic bottle with small neck and cap, approximately 100 ml NOTE The plastic equipment should be selected carefully to avoid losses and contaminations. 6.6 Glass beakers with lid, 250 ml 6.7 Volumetric flasks, 100 ml and 500 ml 7 Samp
44、ling and samples 7.1 General Sampling from aluminium melts shall be carried out in accordance with prEN 14361. The analytical result shall indicate the average chemical composition of a test sample, a laboratory sample or an inspection lot. For an inspection lot or a laboratory sample the minimum qu
45、antity of laboratory samples or test samples, respectively shall be investigated by preliminary tests, for the determination of the average chemical composition of the inspection lot with the required accuracy. NOTE The aim is to determine the uncertainty contribution from the inconsistency of the c
46、hemical composition of the sam- ple and to determine the number of samples necessary to meet the required accuracy for the result with test portions of 0,5 g. 7.2 Laboratory sample A sufficient number of samples shall be taken to indicate the chemical composition of the inspection lot within the req
47、uired uncertainty range. Usually, the analytical result refers to the average content of one or more laboratory samples supplied. If required, uncertainties that result from differences between the test samples and the average composition of one or more laboratory samples or an inspection lot outsid
48、e the laboratory shall also be taken into account. 7.3 Test sample Make chips by milling or drilling of each laboratory sample. If the chemical composition of the laboratory sample is thought to be not uniform, e.g. in case of unwrought products, the preparation of the test sample shall follow a documented procedure to ensure the required representativity. If necessary, e.g. for the determination of low contents of alkaline or alkaline earth elements, clean with a suitable procedure (solution, temperature and time). The cleaning proced
