1、BSI Standards PublicationBS EN 15703-2:2014Copper and copper alloys Determination of manganesecontentPart 2: Flame atomic absorptionspectrometric method (FAAS)BS EN 15703-2:2014 BRITISH STANDARDNational forewordThis British Standard is the UK implementation of EN 15703-2:2014. The UK participation i
2、n its preparation was entrusted to TechnicalCommittee NFE/34/1, Wrought and unwrought copper and copper alloys.A list of organizations represented on this committee can be obtained on request to its secretary.This publication does not purport to include all the necessary provisions of a contract. Us
3、ers are responsible for its correct application. The British Standards Institution 2014.Published by BSI Standards Limited 2014ISBN 978 0 580 83959 7 ICS 77.040.30; 77.120.30 Compliance with a British Standard cannot confer immunity from legal obligations.This British Standard was published under th
4、e authority of the Standards Policy and Strategy Committee on 31 December 2014.Amendments/corrigenda issued since publicationDate T e x t a f f e c t e dEUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 15703-2 December 2014 ICS 77.040.30; 77.120.30 English Version Copper and copper alloys - Dete
5、rmination of manganese content - Part 2: Flame atomic absorption spectrometric method (FAAS)Cuivre et alliages de cuivre - Dtermination de manganse - Partie 2: Mthode par spectromtrie dabsorption atomique dans la flamme (SAAF) Kupfer und Kupferlegierungen - Bestimmung des Mangangehaltes - Teil 2: Fl
6、ammenatomabsorptionsspektrometrisches Verfahren (FAAS) This European Standard was approved by CEN on 8 November 2014. CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this European Standard the status of a national standard without a
7、ny alteration. Up-to-date lists and bibliographical references concerning such national standards may be obtained on application to the CEN-CENELEC Management Centre or to any CEN member. This European Standard exists in three official versions (English, French, German). A version in any other langu
8、age made by translation under the responsibility of a CEN member into its own language and notified to the CEN-CENELEC Management Centre has the same status as the official versions. CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark
9、, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and United Kingdom. EUROPEAN COMMITTEE FO
10、R STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels 2014 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 15703-2:2014 EBS EN 15703-2:2014E
11、N 15703-2:2014 (E) 2 Contents Page Foreword 3 1 Scope 4 2 Normative references 4 3 Principle 4 4 Reagents .4 4.1 Hydrochloric acid, HCl ( = 1,19 g/ml) .4 4.2 Nitric acid, HNO3( = 1,40 g/ml) 4 4.3 Hydrofluoric acid, HF ( = 1,13 g/ml) .4 4.4 Nitric acid solution, 1 + 1 4 4.5 Lanthanum(III) chloride so
12、lution, 100 g/l .4 4.6 Sulphuric acid, H2SO4( = 1,84 g/ml) .4 4.7 Sulphuric acid solution, 1 + 9 .5 4.8 Manganese stock solution, 1,0 g/l Mn .5 4.9 Manganese standard solution, 0,10 g/l 5 4.10 Manganese standard solution, 0,010 g/l 5 4.11 Copper matrix solution, 20 g/l Cu 5 4.12 Copper matrix soluti
13、on, 2 g/l Cu 5 5 Apparatus .5 5.1 Atomic absorption spectrometer, fitted with an air/acetylene burner .5 5.2 Manganese hollow-cathode lamp 6 6 Sampling .6 7 Procedure .6 7.1 Preparation of the test portion solution 6 7.2 Blank test 7 7.3 Check test .7 7.4 Establishment of the calibration curve .7 7.
14、5 Determination 10 8 Expression of results . 10 8.1 Use of the calibration curve . 10 8.2 Use of the bracketing method . 11 9 Precision 12 10 Test report . 13 Bibliography . 14 BS EN 15703-2:2014EN 15703-2:2014 (E) 3 Foreword This document (EN 15703-2:2014) has been prepared by Technical Committee C
15、EN/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 endorsement, at the latest by June 2015 and conflicting national standards shall be withdrawn at th
16、e latest by June 2015. Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. CEN and/or CENELEC shall not be held responsible for identifying any or all such patent rights. Within its programme of work, Technical Committee CEN/TC 133 re
17、quested CEN/TC 133/WG 10 “Methods of analysis” to prepare the following standard: EN 15703-2, Copper and copper alloys Determination of manganese content Part 2: Flame atomic absorption spectrometric method (FAAS) This is one of two Parts of the standard/Technical Specification for the determination
18、 of manganese content in copper and copper alloys. The other Part is: CEN/TS 15703-1, Copper and copper alloys Determination of manganese content Part 1: Spectrophotometric method According to the CEN-CENELEC Internal Regulations, the national standards organizations of the following countries are b
19、ound to implement this European Standard: Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portu
20、gal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom. BS EN 15703-2:2014EN 15703-2:2014 (E) 4 1 Scope This European Standard specifies a flame atomic absorption spectrometric method (FAAS) for the determination of the manganese content of copper and copper allo
21、ys in the form of unwrought, wrought and cast products. The method is applicable to products having manganese mass fractions between 0,001 0 % and 6,0 %. 2 Normative references The following documents, in whole or in part, are normatively referenced in this document and are indispensable for its app
22、lication. 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
23、 products 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 nitric acid followed, after suitable dilution and the addition of lanthanum c
24、hloride to mask the effect of interfering ions, by aspiration into an air/acetylene flame of an atomic absorption spectrometer. Measurement of the absorption of the 279,5 nm or 403,1 nm line emitted by a manganese hollow-cathode lamp. 4 Reagents During the analysis, use only reagents of recognized a
25、nalytical grade and only distilled water or water of equivalent purity. 4.1 Hydrochloric acid, HCl ( = 1,19 g/ml) 4.2 Nitric acid, HNO3( = 1,40 g/ml) 4.3 Hydrofluoric acid, HF ( = 1,13 g/ml) WARNING Hydrofluoric acid is extremely irritating and corrosive to skin and mucous membranes producing severe
26、 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. 4.4 Nitric acid solution, 1 + 1 Add 500 ml of nitric acid (4.2) to 500 ml of water. 4.5 Lanthanum(
27、III) chloride solution, 100 g/l Dissolve 100 g of lanthanum(III) chloride (LaCl3 7H2O) in a 600 ml beaker with water and transfer the solution into a 1 000 ml one-mark volumetric flask. Dilute to the mark with water and mix well. 4.6 Sulphuric acid, H2SO4( = 1,84 g/ml) BS EN 15703-2:2014EN 15703-2:2
28、014 (E) 5 4.7 Sulphuric acid solution, 1 + 9 Add 20 ml of sulphuric acid (4.6) in 180 ml water. 4.8 Manganese stock solution, 1,0 g/l Mn 4.8.1 Cleaning of manganese metal Transfer several grams of electrolytic manganese (purity 99,9 %) into a 250 ml beaker containing about 150 ml of sulphuric acid s
29、olution (4.7). Stir, then allow the manganese to settle for several minutes. Decant and discard the sulphuric acid solution. Rinse several times with water and finally with acetone. Dry the metal for about 2 min at 100C and cool in a desiccator. 4.8.2 Preparation of stock solution Weigh, (1 0,001) g
30、, of manganese cleaned as in 4.8.1 and transfer it into a 250 ml beaker. Add 20 ml of hydrochloric acid (4.1) and 20 ml of the nitric acid solution (4.4). Cover with a watch glass and, if necessary, heat gently to assist dissolution. When dissolution is complete, allow to cool and transfer the solut
31、ion 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 1,0 mg of Mn. 4.9 Manganese standard solution, 0,10 g/l Transfer 20,0 ml of manganese stock solution (4.8) into a 200 ml one-mark volumetric flask. Dilute to the m
32、ark with water and mix well. Prepare this solution immediately prior to use. 1 ml of this solution contains 0,10 mg of Mn. 4.10 Manganese standard solution, 0,010 g/l Transfer 5,0 ml of manganese stock solution (4.8) to a 500 ml one-mark volumetric flask. Dilute to the mark with water and mix well.
33、Prepare this solution immediately prior to use. 1 ml of this solution contains 0,010 mg of Mn. 4.11 Copper matrix solution, 20 g/l Cu Transfer (10 0,01) g of manganese-free copper (Cu 99,95 %) into a 600 ml beaker. Add 100 ml of hydrochloric acid (4.1) and, cautiously, 100 ml of the nitric acid solu
34、tion (4.4). Cover with a watch glass and heat gently until the copper has been completely dissolved, then heat up to the boiling point until the nitrous fumes have been expelled. Allow to cool and transfer the solution quantitatively into a 500 ml one-mark volumetric flask, dilute to the mark with w
35、ater and mix well. 4.12 Copper matrix solution, 2 g/l Cu Transfer 50,0 ml of the copper matrix solution (4.11) into a 500 ml one-mark volumetric flask. Add 90 ml of hydrochloric acid (4.1) and 90 ml of the nitric acid solution (4.4). Dilute to the mark with water and mix well. 5 Apparatus 5.1 Atomic
36、 absorption spectrometer, fitted with an air/acetylene burner BS EN 15703-2:2014EN 15703-2:2014 (E) 6 5.2 Manganese hollow-cathode lamp 6 Sampling Sampling shall be carried out in accordance with ISO 1811-1 or ISO 1811-2, as appropriate. Test samples shall be in the form of fine drillings, chips or
37、millings with a maximum thickness of 0,5 mm. 7 Procedure 7.1 Preparation of the test portion solution 7.1.1 Test portion Weigh (1 0,001) g of the test sample. 7.1.2 Test portion solution Transfer the test portion (7.1.1) into a 250 ml beaker. Add 10 ml of hydrochloric acid (4.1) and 10 ml of the nit
38、ric acid solution (4.4). Cover with a watch glass and heat gently until the test portion is completely dissolved. Allow to cool. If undissolved matter remains, indicating the presence of silicon, filter the solution. Place the filter and retained residues in a platinum crucible and ash, taking care
39、that the filter does not flame. Calcine at about 550 C. Allow to cool and add 5 ml of hydrofluoric acid (4.3) and five drops of nitric acid (4.2). Evaporate to dryness and calcine again for several minutes at about 700 C to completely volatilize the silicon. Cool, and then dissolve the residue with
40、the least possible volume of nitric acid solution (4.4). Filter, if necessary, and add this filtrate quantitatively to the original filtrate. 7.1.3 Manganese mass fractions between 0,001 % and 0,020 % Transfer the dissolved test portion or the combined filtrates quantitatively into a 100 ml one-mark
41、 volumetric flask. Add 10 ml of the lanthanum(III) chloride solution (4.5), dilute to the mark with water and mix well. NOTE The validation exercise of this method showed that for manganese mass fractions between 0,015 % and 0,020 % results are better when the determination is carried out following
42、7.1.3. 7.1.4 Manganese mass fractions between 0,020 % and 0,50 % Transfer the dissolved test portion or the combined filtrates quantitatively into a 100 ml one-mark volumetric flask. Dilute to the mark with water and mix well. Transfer 5,0 ml of this solution into a 100 ml one-mark volumetric flask.
43、 Add 4,5 ml of hydrochloric acid (4.1), 4,5 ml of the nitric acid solution (4.4) and 10 ml of the lanthanum(III) chloride solution (4.5). Dilute to the mark with water and mix well. 7.1.5 Manganese mass fractions between 0,50 % and 2,0 % Transfer the dissolved test portion or the combined filtrates
44、quantitatively into a 100 ml one-mark volumetric flask. Dilute to the mark with water and mix well. Transfer 10,0 ml of this solution into a 100 ml one-mark volumetric flask. Add 9 ml of hydrochloric acid (4.1), 9 ml of the nitric acid solution (4.4) and 10 ml of the lanthanum(III) chloride solution
45、 (4.5). Dilute to the mark with water and mix well. NOTE The validation exercise of this method showed that for manganese mass fractions near 0,5 % results are better when the determination is carried out following 7.1.5. 7.1.6 Manganese mass fractions between 2,0 % and 6,0 % Transfer the dissolved
46、test portion or the combined filtrates quantitatively into a 100 ml one-mark volumetric flask. Dilute to the mark with water and mix well. Transfer 2,5 ml of this solution into a 100 ml one-mark BS EN 15703-2:2014EN 15703-2:2014 (E) 7 volumetric flask. Add 2,3 ml of hydrochloric acid (4.1), 2,3 ml o
47、f the nitric acid solution (4.4) and 10 ml of the lanthanum(III) chloride solution (4.5). Dilute to the mark with water and mix well. NOTE The validation exercise of this method showed that for manganese mass fractions near 2,0 % results are better when the determination is carried out following 7.1
48、.6. 7.2 Blank test Carry out a blank test simultaneously with the determination, following the same procedure and using the same quantities of all reagents as used for the determination, but substituting pure copper for the test portion. 7.3 Check test Make a preliminary check of the apparatus by pr
49、eparing a solution of a reference material or a synthetic sample containing a known amount of manganese 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 In all cases, copper, chloride and nitrate concentrations, and acidity in the calibration solutions shall be similar to those of the test portion solutions. The presence of copper in the calibration solutions compensates for chemical
