1、 g49g50g3g38g50g51g60g44g49g42g3g58g44g55g43g50g56g55g3g37g54g44g3g51g40g53g48g44g54g54g44g50g49g3g40g59g38g40g51g55g3g36g54g3g51g40g53g48g44g55g55g40g39g3g37g60g3g38g50g51g60g53g44g42g43g55g3g47g36g58Part 3: Low tin content Flame atomic absorption spectrometry method (FAAS)The European Standard EN
2、15022-3:2006 has the status of a British StandardICS 77.120.30Copper and copper alloys Determination of tin content BRITISH STANDARDBS EN 15022-3:2006BS EN 15022-3:2006This British Standard was published under the authority of the Standards Policy and Strategy Committee on 31 October 2006 BSI 2006IS
3、BN 0 580 49476 4Amendments issued since publicationAmd. No. Date Commentscontract. Users are responsible for its correct application.Compliance with a British Standard cannot confer immunity from legal obligations.National forewordThis British Standard was published by BSI. It is the UK implementati
4、on of EN 15022-3:2006.The UK participation in its preparation was entrusted to Technical Committee NFE/34, Copper and copper alloys.A list of organizations represented on NFE/34 can be obtained on request to its secretary.This publication does not purport to include all the necessary provisions of a
5、 EUROPEAN STANDARDNORME EUROPENNEEUROPISCHE NORMEN 15022-3October 2006ICS 77.120.30English VersionCopper and copper alloys - Determination of tin content - Part 3:Low tin content - Flame atomic absorption spectrometry method(FAAS)Cuivre et alliages de cuivre - Dosage de ltain - Partie 3 :Etain en fa
6、ible teneur - Mthode par spectromtriedabsorption atomique dans la flamme (SAAF)Kupfer und Kupferlegierungen - Bestimmung desZinngehaltes - Teil 3: Niedriger Zinngehalt -Flammenatomabsorptionsspektrometrisches Verfahren(FAAS)This European Standard was approved by CEN on 14 August 2006.CEN members are
7、 bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this EuropeanStandard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such nationalstandards may be obtained on application to the
8、 Central Secretariat or to any CEN member.This European Standard exists in three official versions (English, French, German). A version in any other language made by translationunder the responsibility of a CEN member into its own language and notified to the Central Secretariat has the same status
9、as the officialversions.CEN members are the national standards bodies of Austria, Belgium, Cyprus, Czech Republic, Denmark, Estonia, Finland, France,Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania,Slovakia, Slove
10、nia, Spain, Sweden, Switzerland and United Kingdom.EUROPEAN COMMITTEE FOR STANDARDIZATIONCOMIT EUROPEN DE NORMALISATIONEUROPISCHES KOMITEE FR NORMUNGManagement Centre: rue de Stassart, 36 B-1050 Brussels 2006 CEN All rights of exploitation in any form and by any means reservedworldwide for CEN natio
11、nal Members.Ref. No. EN 15022-3:2006: EEN 15022-3:2006 (E) 2 Contents Page Foreword3 1 Scope 4 2 Normative references 4 3 Principle4 4 Reagents and materials 4 5 Apparatus .5 6 Sampling.5 7 Procedure .6 8 Expression of results 8 9 Precision.9 10 Test report 10 Bibliography 11 EN 15022-3:2006 (E) 3 F
12、oreword This European Standard (EN 15022-3:2006) has been prepared by Technical Committee CEN/TC 133 “Copper and copper alloys”, the secretariat of which is held by DIN. This European Standard shall be given the status of a national standard, either by publication of an identical text or by endorsem
13、ent, at the latest by April 2007, and conflicting national standards shall be withdrawn at the latest by April 2007. Within its programme of work, Technical Committee CEN/TC 133 requested CEN/TC 133/WG 10 “Methods of analysis“ to prepare the following standard: EN 15022-3, Copper and copper alloys D
14、etermination of tin content Part 3: Low tin content Flame atomic absorption spectrometry method (FAAS) This is one of four parts of the standard/Technical Specification for the determination of tin content in copper and copper alloys. The other parts are: prEN 15022-1, Copper and copper alloys Deter
15、mination of tin content Part 1: Titrimetric method prEN 15022-2, Copper and copper alloys Determination of tin content Part 2: Spectrometric method prEN 15022-4, Copper and copper alloys - Determination of tin content - Part 4: Medium tin content Flame atomic absorption spectrometry method (FAAS) Ac
16、cording to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lith
17、uania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom. EN 15022-3:2006 (E) 4 1 Scope This part of this European Standard specifies a flame atomic absorption spectrometric method (FAAS) for the determination of tin
18、content of copper and copper alloys in the form of unwrought, wrought and cast products. The method is applicable to products having low tin mass fractions between 0,001 % and 0,6 %. 2 Normative references The following referenced documents are indispensable for the application of this European Stan
19、dard. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies. ISO 1811-1, Copper and copper alloys Selection and preparation of samples for chemical analysis Part 1: Sampling of cast unwrought pro
20、ducts ISO 1811-2, Copper and copper alloys Selection and preparation of samples for chemical analysis Part 2: Sampling of wrought products and castings 3 Principle Dissolution of a test portion in hydrochloric acid and hydrogen peroxide. Extraction of tin into the organic phase with a solution of tr
21、ioctylphosphine oxide in methylisobutylketone followed by aspiration of the organic solution into a nitrous oxide/acetylene flame of an atomic absorption spectrometer. Measurement of the absorption of the 286,3 nm line emitted by a tin hollow-cathode lamp. 4 Reagents and materials 4.1 General During
22、 the analysis, use only reagents of recognised analytical grade and only distilled water or water of equivalent purity. 4.2 Ethanol, C2H5OH 4.3 4-methylpentan-2-one (methylisobutylketone) (M.I.B.K.), CH3COCH2CH(CH3)2WARNING 4-methylpentan-2-one is a volatile, flammable organic material. Normal safet
23、y precautions should be taken. 4.4 M.I.B.K. alcoholic solution Mix 92 parts of M.I.B.K. solution (4.3) with 8 parts of ethanol (4.2). 4.5 Hydrochloric acid, HCl ( = 1,19 g/ml) 4.6 Hydrochloric acid solution, 1 + 1 Dilute 500 ml of hydrochloric acid (4.5) in 500 ml of water. EN 15022-3:2006 (E) 5 4.7
24、 Hydrogen peroxide, H2O230 % (mass fraction) solution, free from tin base stabilizers 4.8 Trioctylphosphine oxide (T.O.P.O.), CH3(CH2)73PO 25 g/l solution in 4-methylpentan-2-one In a 200 ml one-mark volumetric flask, dissolve 5 g of trioctylphosphine oxide CH3(CH2)73PO in 4-methylpentan-2-one (4.3)
25、. Dilute to the mark with 4-methylpentan-2-one and mix well. 4.9 T.O.P.O. alcoholic solution Mix 92 parts of T.O.P.O. solution (4.8) with 8 parts of ethanol (4.2). 4.10 Tin stock solution, 0,5 g/l Sn Weigh (0,5 0,001) g of tin (Sn 99 %) and transfer it into a 500 ml narrow-necked conical flask. Add
26、100 ml of hydrochloric acid (4.5) and cover with a watch glass. When dissolution is complete, add 100 ml of water and several drops of hydrogen peroxide solution (4.7). Cool and transfer this solution quantitatively into a 1 000 ml one-mark volumetric flask. Dilute to the mark with water and mix wel
27、l. 1 ml of this solution contains 0,5 mg of Sn. 4.11 Tin standard solution, 0,05 g/l Sn Using a calibrated pipette, transfer 10 ml of the tin stock solution (4.10) into a 100 ml one-mark volumetric flask. Add 9 ml of hydrochloric acid (4.5) and dilute to about 90 ml with water. Cool, dilute to the m
28、ark with water and mix well. 1 ml of this solution contains 0,05 mg of Sn. 5 Apparatus 5.1 Ordinary laboratory apparatus 5.2 Atomic absorption spectrometer, fitted with a nitrous oxide/acetylene burner. 5.3 Tin hollow-cathode lamp 6 Sampling Sampling shall be carried out in accordance with ISO 1811-
29、1 or ISO 1811-2, as appropriate. Test samples shall be in the form of fine drillings, chips or millings, with a maximum thickness of 0,5 mm. EN 15022-3:2006 (E) 6 7 Procedure 7.1 Preparation of the test portion solution 7.1.1 Test portion Weigh (5 0,001) g of the test sample. 7.1.2 Test portion solu
30、tion Transfer the test portion (7.1.1) into a 250 ml beaker and cover. Add 30 ml of hydrochloric acid (4.5) and in small portions, 40 ml of the hydrogen peroxide solution (4.7), cooling if necessary. When the test portion is completely dissolved, heat gently to decompose the hydrogen peroxide. Cool
31、and transfer into a 250 ml separatory funnel, rinsing the beaker with about 10 ml of water. 7.1.3 Extraction of tin Add 20 ml of the T.O.P.O. solution (4.8) to the separatory funnel containing the test portion solution (7.1.2), close with a stopper and shake for 1 min. Allow to stand for about 5 min
32、 until the phases have separated, then discard the aqueous phase. Wash the organic phase twice with 20 ml of the hydrochloric acid solution (4.6), shaking gently for several seconds to eliminate most of the copper. The remaining trace of copper will not interfere. Transfer the washed organic phase i
33、nto a 25 ml one-mark volumetric flask containing 2 ml ethanol (4.2). Rinse the separatory funnel with several ml of T.O.P.O. solution (4.8) and add to the volumetric flask. Dilute to the mark with T.O.P.O. solution (4.8) and mix well. 7.2 Blank test Carry out a blank test simultaneously with the det
34、ermination, following the same procedure and using the same quantities of all reagents as used for the determination, but omitting the test portion. 7.3 Check test Make a preliminary check of the apparatus by preparing a solution of a standard material or a synthetic sample containing a known amount
35、 of tin and of composition similar to the material to be analysed. Carry out the procedure specified in 7.5. 7.4 Establishment of the calibration curve 7.4.1 Preparation of the calibration solutions 7.4.1.1 General The range of calibration solutions is appropriate for most current models of equipmen
36、t of average performance. The range and operating conditions should be selected for optimum measurements by the particular equipment available, so that the curve of absorbance as a function of concentration is a straight line. 7.4.1.2 Calibration solutions Into each of a series of eight 250 ml separ
37、atory funnels, transfer 30 ml of hydrochloric acid (4.5), 50 ml of water and the volumes of tin stock solution (4.10) and tin standard solution (4.11) shown in Table 1. EN 15022-3:2006 (E) 7 Table 1 Calibration for tin mass fractions between 0,001 % and 0,60 % Tin stock or standard solution volume C
38、orrespondingtin mass Corresponding tin mass fraction (see 7.5.2) (4.11) (4.10) Correspondingtin concentration after final dilution Direct test portion Diluted 1:10 test portion ml ml mg mg/ml % %0a 0 0 0 0 1 0,050 0,002 0,001 3 0,15 0,006 0,003 0,03 6 0,30 0,012 0,006 0,06 10 0,50 0,020 0,010 0,10 2
39、 1,0 0,040 0,02 0,20 4 2,0 0,080 0,04 0,40 6 3,0 0,120 0,60 aBlank test on reagents for calibration curve. Add 20 ml of the T.O.P.O. solution (4.8) to each separatory funnel, close with a stopper and shake for 1 min. Allow to stand for about 5 min until the phases have separated, then discard the aq
40、ueous phase. Transfer each organic phase into eight 25 ml one-mark volumetric flasks each containing 2 ml of ethanol (4.2). Rinse the separatory funnel with several ml of T.O.P.O. solution (4.8) and add to the volumetric flasks. Dilute to the mark with T.O.P.O. solution (4.8) and mix well. 7.4.2 Adj
41、ustment of the atomic absorption spectrometer Fit the tin hollow-cathode lamp (5.3) into the atomic absorption spectrometer (5.2), switch on the current and allow it to stabilize. Adjust the wavelength in the region of 286,3 nm to maximum energy. Following the manufacturers instructions, fit the cor
42、rect burner, light the flame and allow the burner temperature to stabilize. Taking careful note of the manufacturers instructions regarding the minimum flow rate of acetylene, aspirate the calibration solution of highest concentration of analyte and adjust the burner configuration and gas flows to o
43、btain maximum absorbance. Also take into account that the flame should be slightly reducing with a red zone height of approximately 7 mm to 12 mm when aspirating the solution 4.9. NOTE The wavelength noted, 286,3 nm, was chosen because of its stability, linearity of calibration curve, sensitivity an
44、d lack of interference. Similar sensitivity can be obtained by using 235,5 nm wavelength. Use of other lines is not advised. 7.4.3 Spectrometric measurement of the calibration solutions Aspirate the series of calibration solutions (7.4.1) in succession into the flame and measure the absorbance for e
45、ach. Take care to keep the aspiration rate constant throughout the preparation of the calibration curve. Spray M.I.B.K. alcoholic solution (4.4) through the burner after each measurement. 7.4.4 Calibration curve Establish the calibration curve using measured absorbances and corresponding analyte amo
46、unts. Use appropriate spectrometer software or an off-line computer for regression calculations or prepare a graphical representation. EN 15022-3:2006 (E) 8 7.5 Determination 7.5.1 General The analyses shall be carried out independently, in duplicate. 7.5.2 Preliminary spectrometric measurement Carr
47、y out a preliminary measurement on the test solution (7.1.3) following the same procedure specified in 7.4.3 at the same time as the spectrometric measurements are carried out on the calibration solutions (see 7.4.1). Estimate the preliminary analyte amount by using the calibration curve (7.4.4). Sh
48、ould the absorbance values of the test portion solutions be more than 0,6, 10,0 ml of the 25 ml test solution (7.1.3) shall be transferred into a 100 ml one-mark volumetric flask, adjusted to the mark with T.O.P.O. solution (4.8) and mixed well. 7.5.3 Spectrometric measurements 7.5.3.1 Use of the ca
49、libration curve Repeat the measurements and determine the concentration directly using the calibration curve. 7.5.3.2 Use of bracketing method Carry out a second measurement on the test portion solution (7.1.2) following the procedure specified in 7.4.3, by bracketing between two new calibration solutions with a composition similar to that of the calibration solution (see 7.4.1), but having tin contents slightly higher and slightly lower ( 10 %) than the estimated tin concentr
