1、 ISO 2013 Rubber Trapping and identification of volatile components of rubber fumes with active sampling on a poly(2,6-diphenylphenylene oxide) type sorbent, using thermodesorption and gas chromatographic method with mass spectrometric detection Caoutchouc Pigeage et identification des composs volat
2、ils des fumes de procds du caoutchouc, par chantillonnage actif sur un sorbant de type poly(oxyde de 2,6-diphnylphnylne), en utilisant une mthode par thermodsorption et chromatographie en phase gazeuse avec dtection par spectromtrie de masse TECHNICAL SPECIFICATION ISO/TS 17796 First edition 2013-06
3、-15 Reference number ISO/TS 17796:2013(E) ISO/TS 17796:2013(E)ii ISO 2013 All rights reserved COPYRIGHT PROTECTED DOCUMENT ISO 2013 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 mechanic
4、al, including photocopying, or posting on the internet or an intranet, without prior written 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
5、 Fax + 41 22 749 09 47 E-mail copyrightiso.org Web www.iso.org Published in Switzerland ISO/TS 17796:2013(E) ISO 2013 All rights reserved iii Contents Page Foreword iv 1 Scope . 1 2 Terms and definitions . 1 3 Principle 2 4 Sampling 2 4.1 Equipment . 2 4.2 Operating conditions . 2 4.3 Procedure 3 5
6、Thermal desorption, gas chromatography mass spectrometry . 3 5.1 General . 3 5.2 Reagents 3 5.3 Apparatus 4 5.4 Procedure 4 6 Test report . 6 Annex A (informative) Example of application to a laboratory EPDM/peroxide mix .7 Annex B (informative) Example of application to a laboratory NR mix 10 Bibli
7、ography .13 ISO/TS 17796:2013(E) Foreword ISO (the International 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 inte
8、rested in a subject for which a technical committee has been established 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 Electrotechnica
9、l Commission (IEC) on all matters of electrotechnical standardization. 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 docu
10、ments should be noted. This document was drafted in accordance with the editorial rules of the ISO/IEC Directives, Part 2. 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 fo
11、r identifying any or all such patent rights. Details of any patent rights identified during the development of the document will be in the Introduction and/or on the ISO list of patent declarations received. www.iso.org/patents Any trade name used in this document is information given for the conven
12、ience of users and does not constitute an endorsement. The committee responsible for this document is ISO/TC 45, Rubber and rubber products, Subcommittee SC 2, Testing and analysis.iv ISO 2013 All rights reserved TECHNICAL SPECIFICATION ISO/TS 17796:2013(E) Rubber Trapping and identification of vola
13、tile components of rubber fumes with active sampling on a poly(2,6-diphenylphenylene oxide) type sorbent, using thermodesorption and gas chromatographic method with mass spectrometric detection 1 Scope This Technical Specification specifies a qualitative method of thermodesorption gas chromatography
14、 mass spec t romet r y ( TD-GC-MS ) for t he ident if icat ion of volat ile component s in r ubber f umes, af ter t rapping on a solid sorbent based on 2,6-diphenylphenylene-oxide polymer resin. It is applicable to a screening of emissions from the processing of rubber compounds in the ambient workp
15、lace and storage environment. CAUTION Persons using this Technical Specification should be familiar with the procedures for gas chromatography mass spectrometry measurement and analysis. All the operative details for the application and set-up of the GC-MS are assumed to be in agreement with the ope
16、rative instructions provided by the manufacturer. Therefore, the detailed procedure for the operation is not included in this Technical Specification. This Technical Specification specifies a qualitative method which is not aimed at quantitative analyses. 2 Terms and definitions For the purposes of
17、this document, the following terms and definitions apply. 2.1 semi-volatile organic compound SVOC organic compound whose boiling point is in the range from (240 to 260) C to (380 to 400) C Note 1 to entry: This classification has been defined by the World Health Organization. 4 Note 2 to entry: Boil
18、ing points of some compounds are difficult or impossible to determine because they decompose before they boil at atmospheric pressure. Vapour pressure is another criterion for the classification of compound volatility that may be used for the classification of organic chemicals. SVOCs have vapour pr
19、essures of between 10 2kPa and 10 8kPa. 2.2 volatile organic compound VOC organic compound whose boiling point is in the range from (50 to 100) C to (240 to 260) C Note 1 to entry: This classification has been defined by the World Health Organization. 4 Note 2 to entry: Boiling points of some compou
20、nds are difficult or impossible to determine because they decompose before they boil at atmospheric pressure. Vapour pressure is another criterion for the classification of compound volatility that may be used for the classification of organic chemicals. VOCs generally have saturation vapour pressur
21、es at 25 C greater than 10 2kPa. 2.3 very volatile organic compound VVOC organic compound whose boiling point is in the range from 0 C to (50 to 100) C Note 1 to entry: This classification has been defined by the World Health Organization. 4 ISO 2013 All rights reserved 1 ISO/TS 17796:2013(E) Note 2
22、 to entry: Boiling points of some compounds are difficult or impossible to determine because they decompose before they boil at atmospheric pressure. Vapour pressure is another criterion for the classification of compound volatility that may be used for the classification of organic chemicals. VVOCs
23、 typically have vapour pressures of greater than 15 kPa. 3 Principle Rubber fumes are sampled on an adsorbent support using a pump. They are recovered from the trap by thermal desorption and the substances composing the desorbed fume are identified by the mass spectrometer. The method identifies the
24、 components adsorbed on the trap support used, except benzene. The actual composition of the emissions depends on the selection of ingredients used for compounding and on the thermal and mechanical conditions applied to the rubber. Moreover, environmental humidity might interfere with the sorption c
25、apability of the sorbent material. The sorbent tube is used for the trapping of volatile (VOC) (boiling point 50 C to 100 C) and semi- volatile (SVOC) (boiling point 240 C) organic compounds in the C6 to C26 range, which are chemically stable against a desorption temperature of 200 C. Very volatile
26、compounds (VVOC) (boiling point approximately 50 C to 100 C) are only partially retained by the sorbent. Other sorbents based on carbon molecular sieve or by multi-sorbent bed tube may be more appropriate in this case. The upper limit of the useful range is set by the sorptive capacity of the sorben
27、t used and by the linear dynamic range of the gas chromatograph column and detector or by the sample-splitting capability of the analytical instrumentation used. The sorptive capacity is measured as a breakthrough volume of air, which determines the maximum air volume that shall not be exceeded when
28、 sampling. NOTE Small amounts of benzene could be created by the thermal decomposition of the sorbent. 4 Sampling 4.1 Equipment 4.1.1 Trap support, poly(2,6-diphenylphenylene oxide) 1) , of quantity 180 mg to 200 mg, of particle size 0,18 mm to 0,25 mm (60/80 mesh), and of specific surface 20 m 2 /g
29、 to 35 m 2 /g. Another quantity, particle size or specific surface may be chosen if the test result is proven to be equivalent. 4.1.2 Adsorbent tubes, stainless steel tube. 4.1.3 Calibrated pump Calibrate the pump with the sorbent tube assembly inline, using a calibrated external flowmeter. One end
30、of the calibrated flowmeter shall be kept at atmospheric pressure to ensure proper operation. 4.2 Operating conditions 4.2.1 Trap support Recondition the trap sorbent material before sampling, heating it at 300 C under inert gas for 1 h (minimum) to 8 h (maximum). Check the cleaning of the trap supp
31、ort by GC-MS analysis. Recondition tubes stored for more than four weeks before sampling. 1) One example of poly(2,6-diphenylphenylene oxide) is Tenax TA , which is an example of a suitable product available commercially. This information is given for the convenience of users of this Technical Speci
32、fication and does not constitute an endorsement by ISO of this product.2 ISO 2013 All rights reserved ISO/TS 17796:2013(E) 4.2.2 Sampling flowrate The sampling flowrate shall be 100 ml/min maximum at room temperature. 4.2.3 Sampling volume The sampling volume shall be 6 l maximum. Two sampling tubes
33、 should be placed in parallel, in the same location, and operated simultaneously in case of trap or analysis dysfunction. Only one tube shall be analysed. 4.3 Procedure When used for fixed-location sampling, a suitable sampling site is to be chosen. The location of sampling shall be close to the sou
34、rce. Sampling the surrounding atmosphere is also admissible. Assemble the sampling line. The sampling train includes, in the following order, a sample source, a sampling tube(s), a flow controller and a pump. Prepare a tube assembly by joining the tubes in series with a union if more than one tube i
35、s used to ensure that the breakthrough volume for the analyte of interest is not exceeded. Attach the pump to the sorbent tube or tube assembly with plastic (PE or PTFE) or rubber tubing. Turn on the pump and adjust the flowrate so that the recommended sample volume is taken within the available tim
36、e. The recommended air sample volume for the VOCs covered by this Technical Specification amounts to a total of 6 l maximum. An appropriate sampling flowrate is in the range of 50 ml/min to 100 ml/min. Note the starting time, temperature and, if necessary for calculation, also the barometric pressur
37、e. At the end of the sampling period, note the flowrate or register the readings. Turn off the pump, and note the time, temperature and, if necessary, barometric pressure. Disconnect the sampling tube from the sampling line and seal both ends using screw-cap fittings with PTFE ferrules. If the sampl
38、ing flowrate is determined by using an integrated flow-measuring device, e.g. a mass flowmeter, connect the sampling tube to the sampling line, start the pump, note the time and flowrate or register readings. Note temperature and, if necessary, barometric pressure. An appropriate sampling flowrate i
39、s in the range of 50 ml/min to 100 ml/min. At the end of the sampling period, note the flowrate or register readings. Turn off the pump, note and register the time the pump was turned off. Disconnect the sampling tube from the sampling line and seal both ends using screw-cap fittings with PTFE ferru
40、les. For storage between sampling and analyses, store the closed tubes at room temperature in a container free of any emission. The storage time shall not exceed four weeks. 5 Thermal desorption, gas chromatography mass spectrometry 5.1 General For analysis, volatile compounds are thermally desorbed
41、 from the sampling tubes. The individual substances are separated using a capillary column in a gas chromatograph and detected with a mass spectrometric detector. 5.2 Reagents 5.2.1 Trap coolant, used for freezing the cool trap in the thermal desorption apparatus (30 C or colder). Liquid nitrogen or
42、 other alternatives (e.g. a Peltier device) are required. A secondary sorbent cold trap may be used to focus the analytes. 5.2.2 Gas chromatograph carrier gas, helium. ISO 2013 All rights reserved 3 ISO/TS 17796:2013(E) 5.3 Apparatus 5.3.1 Thermal desorption apparatus or equivalent, connectable with
43、 a gas chromatograph and capable of heating up to 300 C. 5.3.2 Gas chromatograph, equipped with the following accessories: capillary column; stationary phase: 5 % diphenyl, 95 % polydimethylsiloxane; Experience shows that a column of 60 m, diameter 0,25 m and 0,20 m thickness film, with a flowrate o
44、f 1,2 ml/min is usually appropriate. injector system: depending on the desorption system; split value: properly adapted in accordance with the sampled amount; oven temperature program: established to separate compounds. 5.3.3 Mass spectrometer, quadrupole mass spectrometer in electronic impact mode,
45、 specified as follows: transfer line temperature: 300 C; ion source temperature: 230 C to 300 C; ionizing voltage: 70 eV; scan range: 25 m/z to 600 m/z; analysis mode: full scan. 5.4 Procedure 5.4.1 Principle Heat the support at 200 C and trap the volatile compounds generated during the heating peri
46、od at a temperature of 30 C or colder. After desorption and cold trapping to preconcentrate the analytes, start the GC-MS measurement in order to obtain the gas chromatogram and mass spectra. 5.4.2 Thermal desorption Typical desorption conditions for volatile compounds analysis using a secondary col
47、d trap and sampling tube containing 180 mg to 200 mg of sorbent are: desorption temperature: 200 C; desorption time: 30 min; desorption gas flowrate: 50 ml/min; cold-trap high temperature: 300 C; cold-trap low temperature: 30 C or colder; transfer-line temperature: 250 C minimum; split ratios: split
48、 ratios between the sample tube and secondary trap and between the secondary trap and analytical column (if applicable) should be selected depending on the expected atmospheric concent rat ion . (See t he ha ndbook of t he respec t ive ma nu f ac t u rer s of t he t her ma l desor pt ion appa rat u
49、s .).4 ISO 2013 All rights reserved ISO/TS 17796:2013(E) 5.4.3 Analysis For the identification of single, non-target substances, analyse the samples in the scan mode. Identify substances detected in the sample using the mass spectrometers total ion chromatogram and the retention time of the compounds. The identification of substances is achieved by matching the unknown mass spectrum with the reference mass spectrum stored in a library of pure substances. This
