1、BSI Standards Publication BS ISO 6101-4:2014 Rubber Determination of metal content by atomic absorption spectrometry Part 4: Determination of manganese contentBS ISO 6101-4:2014 BRITISH STANDARD National foreword This British Standard is the UK implementation of ISO 6101-4:2014. It supersedes BS 716
2、4-26.1:1997 which is withdrawn. The UK participation in its preparation was entrusted to Technical Committee PRI/23, Test methods for rubber and non-black compounding ingredients. A list of organizations represented on this committee can be obtained on request to its secretary. This publication does
3、 not purport to include all the necessary provisions of a contract. Users are responsible for its correct application. The British Standards Institution 2014. Published by BSI Standards Limited 2014 ISBN 978 0 580 82377 0 ICS 83.060 Compliance with a British Standard cannot confer immunity from lega
4、l obligations. This British Standard was published under the authority of the Standards Policy and Strategy Committee on 31 July 2014. Amendments issued since publication Date Text affectedBS ISO 6101-4:2014 ISO 2014 Rubber Determination of metal content by atomic absorption spectrometry Part 4: Det
5、ermination of manganese content Caoutchouc Dtermination de la teneur en mtal par spectromtrie dabsorption atomique Partie 4: Dosage du manganse INTERNATIONAL STANDARD ISO 6101-4 Third edition 2014-08-01 Reference number ISO 6101-4:2014(E)BS ISO 6101-4:2014ISO 6101-4:2014(E)ii ISO 2014 All rights res
6、erved COPYRIGHT PROTECTED DOCUMENT ISO 2014 All rights reserved. Unless otherwise specified, no part of this publication may be reproduced or utilized otherwise in any form or by any means, electronic or mechanical, including photocopying, or posting on the internet or an intranet, without prior wri
7、tten permission. Permission can be requested from either ISO at the address below or ISOs member body in the country of the requester. 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 SwitzerlandB
8、S ISO 6101-4:2014ISO 6101-4:2014(E) ISO 2014 All rights reserved iii Contents Page Foreword iv 1 Scope . 1 2 Normative references 1 3 Principle 1 4 Reagents 2 5 Apparatus . 2 6 Sampling 3 7 Procedure. 4 7.1 Test portion 4 7.2 Preparation of test solution . 4 7.3 Preparation of the calibration graph
9、4 7.4 Determination . 5 7.5 Blank determination 6 7.6 Number of determinations . 6 8 Expression of results 6 9 Test report . 7 Annex A (normative) Method of standard additions . 8 Annex B (informative) Precision 10 Bibliography .11BS ISO 6101-4:2014ISO 6101-4:2014(E) Foreword ISO (the International
10、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 esta
11、blished 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 standardiza
12、tion. The procedures used to develop this document and those intended for its further maintenance are described in the ISO/IEC Directives, Part 1. In particular the different approval criteria needed for the different types of ISO documents should be noted. This document was drafted in accordance wi
13、th the editorial rules of the ISO/IEC Directives, Part 2 (see www.iso.org/directives). 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. Details of any
14、 patent rights identified during the development of the document will be in the Introduction and/or on the ISO list of patent declarations received (see www.iso.org/patents). Any trade name used in this document is information given for the convenience of users and does not constitute an endorsement
15、. For an explanation on the meaning of ISO specific terms and expressions related to conformity assessment, as well as information about ISOs adherence to the WTO principles in the Technical Barriers to Trade (TBT) see the following URL: Foreword - Supplementary information The committee responsible
16、 for this document is ISO/TC 45, Rubber and rubber products, Subcommittee SC 2, Testing and analysis. This third edition cancels and replaces the second edition (ISO 6101-4:1997), which has been technically revised. ISO 6101 consists of the following parts, under the general title Rubber Determinati
17、on of metal content by atomic absorption spectrometry: Part 1: Determination of zinc content Part 2: Determination of lead content Part 3: Determination of copper content Part 4: Determination of manganese content Part 5: Determination of iron content Part 6: Determination of magnesium contentiv ISO
18、 2014 All rights reservedBS ISO 6101-4:2014INTERNATIONAL ST ANDARD ISO 6101-4:2014(E) Rubber Determination of metal content by atomic absorption spectrometry Part 4: Determination of manganese content WARNING Persons using this part of ISO 6101 should be familiar with normal laboratory practice. Thi
19、s part of ISO 6101 does not purport to address all of the safety problems, if any, associated with its use. It is the responsibility of the user to establish appropriate safety and health practices and to ensure compliance with any national regulatory conditions. 1 Scope This part of ISO 6101 specif
20、ies an atomic absorption spectrometric method for the determination of the manganese content of rubbers. The method is applicable to raw rubber and rubber products having manganese content above 0,5 ppm. Manganese contents below this limit can be determined, provided that suitable adjustments are ma
21、de to the mass of the test portion and/or to the concentrations of the solutions used. The use of the standard additions method might lower the bottom limit of detection. 2 Normative references The following documents, in whole or in part, are normatively referenced in this document and are indispen
22、sable for its application. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies. ISO 123, Rubber latex Sampling ISO 247, Rubber Determination of ash ISO 648, Laboratory glassware Single-volume p
23、ipettes ISO 1042, Laboratory glassware One-mark volumetric flasks ISO 1772, Laboratory crucibles in porcelain and silica ISO 1795, Rubber, raw natural and raw synthetic Sampling and further preparative procedures ISO 4793, Laboratory sintered (fritted) filters Porosity grading, classification and de
24、signation 3 Principle A test portion is ashed at 550 C 25 C in accordance with ISO 247, method A. The ash is dissolved in hydrochloric acid or nitric acid. The solution is aspirated into an atomic absorption spectrometer and the absorption is measured at a wavelength of 279,5 nm, using a manganese h
25、ollow-cathode lamp as the manganese emission source. Any silicates are volatilized by sulfuric and hydrofluoric acid. NOTE ISO 6955:1982, Analytical spectroscopic methods Flame emission, atomic absorption, and atomic fluorescence Vocabulary, defines the spectrometric terms used in this part of ISO 6
26、101. ISO 2014 All rights reserved 1BS ISO 6101-4:2014ISO 6101-4:2014(E) 4 Reagents During the analysis, unless otherwise stated, use only reagents of recognized analytical grade and only distilled water or water of equivalent purity. 4.1 Hydrochloric acid, 20= 1,18 Mg/m 3 , 37 % (m/m). 4.2 Hydrochlo
27、ric acid diluted 1 + 2, dilute 1 volume of concentrated hydrochloric acid (4.1) with 2 volumes of water. 4.3 Sulfuric acid, 20= 1,84 Mg/m 3 , 95 % to 97 % (m/m). 4.4 Sulfuric acid diluted 1 + 3, add carefully 1 volume of concentrated sulfuric acid (4.3) to 3 volumes of water. 4.5 Hydrofluoric acid,
28、20= 1,13 Mg/m 3 , 38 % (m/m) to 40 % .(m/m). 4.6 Concentrated nitric acid, 20= 1,41 Mg/m 3 , 65 % (m/m). 4.7 Dilute nitric acid, 1,6 % (by mass), prepared by carefully pipetting 11,5 cm 3of concentrated nitric acid (4.6) into a 1 000 cm 3one-mark volumetric flask, making up to the mark with water an
29、d mixing thoroughly. 4.8 Standard manganese stock solution, containing 1 g of Mn per 1 000 cm 3 . Either use a commercially available standard manganese solution, or prepare as follows. Using electrolytic manganese of purity 99,9 %, free the surface of any manganese oxides by placing a few grams of
30、the metal in a beaker containing 60 cm 3to 80 cm 3of 1 + 3 sulfuric acid (4.4) with about 100 cm 3of water. Stir and, after a few minutes, decant the acid solution and pour water into the beaker. Repeat the decantation and washing with water several times. Then place the manganese metal in acetone a
31、nd stir. Decant the acetone, dry the metal in a hot-air oven (see 5.14), maintained at 100 C 5 C for about 2 min, and allow it to cool in a desiccator. In a 600 cm 3tall-form beaker, weigh, to the nearest 0,1 mg, 1 g of this purified manganese metal, and dissolve it with 40 cm 3of 1 + 3 sulfuric aci
32、d solution (4.4) and about 80 cm 3of water. Boil the solution for several minutes. Allow to cool and transfer quantitatively to a 1 000 cm 3one-mark volumetric flask (see 5.5). Dilute to the mark and mix thoroughly. 1 cm 3of this standard stock solution contains 1 000 g of Mn. 4.9 Standard manganese
33、 solution, containing 10 mg of Mn per 1 000 cm 3 . Carefully pipette 10 cm 3of the standard manganese stock solution (4.8) into a 1 000 cm 3one-mark volumetric flask (see 5.5), dilute to the mark with 1 + 2 hydrochloric acid (4.2) or dilute nitric acid (4.7) and mix thoroughly. Prepare this solution
34、 on the day of use. 1 cm 3of this standard solution contains 10 g of Mn. 5 Apparatus Ordinary laboratory apparatus, plus the following.2 ISO 2014 All rights reservedBS ISO 6101-4:2014ISO 6101-4:2014(E) 5.1 Atomic absorption spectrometer, fitted with a burner fed with acetylene and air, compressed to
35、 at least 60 kPa and 300 kPa, respectively, and also fitted with a manganese hollow-cathode lamp as the manganese emission source. The instrument shall be operated in accordance with the manufacturers instructions for optimum performance. Alternatively, an electrothermal atomization device (graphite
36、 furnace) may be used. It shall be operated by a competent person in accordance with the manufacturers instructions for optimum performance. 5.2 Balance, accurate to 0,1 mg. 5.3 Muffle furnace, capable of being maintained at a temperature of 550 C 25 C. 5.4 Glass filter crucible, filter pore size 16
37、 m to 40 m (porosity grade P40 according to ISO 4793). 5.5 One-mark volumetric flasks, glass-stoppered, of capacities 50 cm 3 , 100 cm 3 , 200 cm 3 , 500 cm 3 , and 1 000 cm 3 , complying with the requirements of ISO 1042, class A. 5.6 Volumetric pipettes, of capacities 5 cm 3 , 10 cm 3 , 20 cm 3 ,
38、and 50 cm 3 , complying with the requirements of ISO 648, class A. 5.7 Graduated pipette, of capacity 1cm 3 , complying with the requirements of ISO 835, class A. 5.8 Electric hotplate or heated sand bath. 5.9 Steam bath. 5.10 Platinum or borosilicate-glass rod, for use as a stirrer. 5.11 Crucible (
39、platinum), and of capacity 50 cm 3to 150 cm 3depending on the test portion size. 5.12 Crucible (silica, porcelain, or borosilicate glass), of capacity 50 cm 3to 150 cm 3depending on the test portion size, complying with the requirements of ISO 1772. 5.13 Ashless filter paper. 5.14 Hot-air oven, capa
40、ble of being maintained at a temperature of 100 C 5 C. 6 Sampling Carry out sampling as follows: raw rubber: in accordance with ISO 1795; latex: in accordance with ISO 123; products: to be representative of the whole batch. ISO 2014 All rights reserved 3BS ISO 6101-4:2014ISO 6101-4:2014(E) 7 Procedu
41、re 7.1 Test portion Weigh, to the nearest 0,1 mg, approximately 1 g to 5 g of rubber product and 5 g to 10 g of raw rubber, milled or finely cut into an appropriate crucible. Wrap the sample in an ashless filter paper and place into an appropriate crucible (5.11 or 5.12). The size of the test portio
42、n shall be judged by prior knowledge of the approximate amount of manganese present. 7.2 Preparation of test solution 7.2.1 Destruction of organic matter Ash the test portion in accordance with method A of ISO 247, in the muffle furnace (5.3), maintained at 550 C 25 C. If the ash is black, caused by
43、 small amounts of carbon black, stir carefully with the platinum or borosilicate-glass rod (5.10) and continue heating. 7.2.2 Dissolution of inorganic residue using hydrochloric acid After ashing, allow the crucible and its contents to cool to ambient temperature. Add 20 cm 3of concentrated hydrochl
44、oric acid (4.1). Heat the mixture on the steam bath (5.9) for at least 10 min. Do not let the reaction mixture boil. Allow to cool to ambient temperature and transfer the solution quantitatively, with the aid of water, to a 50 cm 3one-mark volumetric flask (5.5). If the ash is not totally dissolved,
45、 proceed as follows. Transfer the solution and the undissolved ash quantitatively, with the aid of water, to a platinum crucible (5.10). Add a few drops of concentrated sulfuric acid (4.3) and 5 cm 3of hydrofluoric acid (4.5). Heat on the electric hotplate or heated sand bath (5.8) in a fume cupboar
46、d and evaporate until dry while stirring with a platinum rod (5.10). Repeat this digestion with the same quantities of sulfuric and hydrofluoric acids two more times. Allow to cool to ambient temperature, add 20 cm 3of concentrated hydrochloric acid (4.1), heat for 10 min and transfer quantitatively
47、, with the aid of water, to a 50 cm 3one-mark volumetric flask (5.5). Dilute to the mark with water and mix thoroughly. Insoluble matter might settle and, if so, shall be filtered off using a filter crucible (5.4) just before making spectrometric measurements in accordance with 7.3. Test solutions s
48、hould contain approximately 12 % hydrochloric acid. If evaporation, etc., has reduced or increased this concentration, adjust accordingly with concentrated hydrochloric acid (4.1) or water. 7.2.3 Dissolution of inorganic residue using nitric acid Alternative method Add 10 cm 3of dilute nitric acid (
49、4.7) to the cooled residue. Cover with a watch glass and heat on a steam bath (5.9) for at least 30 min. Allow to cool to ambient temperature. Filter the contents of the crucible into a 50 cm 3one-mark volumetric flask, rinsing the crucible and making up to the mark with dilute nitric acid (4.7). 7.3 Preparation of the calibration graph 7.3.1 Preparation of calibration solutions 7.3.1.1 Into a series of five 100 cm 3one-mark volumetric flasks (5.5), introduce using pi
