1、BSI Standards PublicationPD CEN ISO/TS 16189:2013Footwear Critical substancespotentially present in footwearand footwear components Test method to quantitativelydetermine dimethylformamidein footwear materials (ISO/TS16189:2013)Copyright European Committee for Standardization Provided by IHS under l
2、icense with CENNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-PD CEN ISO/TS 16189:2013 PUBLISHED DOCUMENTNational forewordThis Published Document is the UK implementation of CEN ISO/TS 16189:2013.The UK participation in its preparation was entrusted to Technical C
3、ommittee TCI/69, Footwear, leather and coated fabrics.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. Users are responsible for its correct application. The Brit
4、ish Standards Institution 2013. Published by BSI Standards Limited 2013ISBN 978 0 580 81935 3 ICS 61.060 Compliance with a British Standard cannot confer immunity from legal obligations.This Published Document was published under the authority of the Standards Policy and Strategy Committee on 31 Aug
5、ust 2013.Amendments issued since publicationDate Text affectedCopyright European Committee for Standardization Provided by IHS under license with CENNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-TECHNICAL SPECIFICATION SPCIFICATION TECHNIQUE TECHNISCHE SPEZIFIKAT
6、ION CEN ISO/TS 16189 July 2013 ICS 61.060 English Version Footwear - Critical substances potentially present in footwear and footwear components - Test method to quantitatively determine dimethylformamide in footwear materials (ISO/TS 16189:2013) Chaussures - Substances critiques potentiellement prs
7、entes dans la chaussure et les composants de chaussure - Mthodes dessai pour dterminer quantitativement le dimthylformamide dans les matriaux de chaussure (ISO/TS 16189:2013) Schuhe - Mglicherweise in Schuhen und Schuhbestandteilen vorhandene kritische Substanzen - Prfverfahren zur quantitativen Bes
8、timmung von Dimethylformamid in Schuhwerkstoffen (ISO/TS 16189:2013) This Technical Specification (CEN/TS) was approved by CEN on 15 July 2013 for provisional application. The period of validity of this CEN/TS is limited initially to three years. After two years the members of CEN will be requested
9、to submit their comments, particularly on the question whether the CEN/TS can be converted into a European Standard. CEN members are required to announce the existence of this CEN/TS in the same way as for an EN and to make the CEN/TS available promptly at national level in an appropriate form. It i
10、s permissible to keep conflicting national standards in force (in parallel to the CEN/TS) until the final decision about the possible conversion of the CEN/TS into an EN is reached. CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark,
11、 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 FOR
12、 STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG Management Centre: Avenue Marnix 17, B-1000 Brussels 2013 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. CEN ISO/TS 16189:2013: ECopyright European Commit
13、tee for Standardization Provided by IHS under license with CENNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-PD CEN ISO/TS 16189:2013CEN ISO/TS 16189:2013 (E) 3 Foreword This document (CEN ISO/TS 16189:2013) has been prepared by Technical Committee CEN/TC 309 “Foo
14、twear“, the secretariat of which is held by AENOR, in collaboration with Technical Committee ISO/TC 216 “Footwear“. 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 a
15、ny or all such patent rights. According to the CEN-CENELEC Internal Regulations, the national standards organizations of the following countries are bound to announce this Technical Specification: Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav
16、 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 the United Kingdom. Endorsement notice The text of ISO/TS 16189:2013 has
17、 been approved by CEN as CEN ISO/TS 16189:2013 without any modification. Copyright European Committee for Standardization Provided by IHS under license with CENNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-PD CEN ISO/TS 16189:2013ISO/TS 16189:2013(E) ISO 2013 All
18、 rights reserved iiiContents PageForeword iv1 Scope . 12 Normative references 13 Method principle 14 Reagents and solvents . 14.1 Reagents 14.2 Stock solutions 15 Equipment . 26 Preparation of sample 26.1 Sampling . 26.2 Extraction 27 Determination with GC-MS 37.1 Calibration standard 37.2 Examples
19、of instrumental method . 38 Quantification 38.1 Calibration curve . 39 Performance of the method 410 Test report . 4Annex A (informative) Suggested parameters for GC-MS determination of DMFo . 5Bibliography 6Copyright European Committee for Standardization Provided by IHS under license with CENNot f
20、or ResaleNo reproduction or networking permitted without license from IHS-,-,-PD CEN ISO/TS 16189:2013ISO/TS 16189:2013(E)ForewordISO (the International Organization for Standardization) is a worldwide federation of national standards bodies (ISO member bodies). The work of preparing International S
21、tandards is normally carried out through ISO technical committees. Each member body interested 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, als
22、o take part in the work. ISO collaborates closely with the International Electrotechnical Commission (IEC) on all matters of electrotechnical standardization.International Standards are drafted in accordance with the rules given in the ISO/IEC Directives, Part 2.The main task of technical committees
23、 is to prepare International Standards. Draft International Standards adopted by the technical committees are circulated to the member bodies for voting. Publication as an International Standard requires approval by at least 75 % of the member bodies casting a vote.In other circumstances, particular
24、ly when there is an urgent market requirement for such documents, a technical committee may decide to publish other types of normative document: an ISO Publicly Available Specification (ISO/PAS) represents an agreement between technical experts in an ISO working group and is accepted for publication
25、 if it is approved by more than 50 % of the members of the parent committee casting a vote; an ISO Technical Specification (ISO/TS) represents an agreement between the members of a technical committee and is accepted for publication if it is approved by 2/3 of the members of the committee casting a
26、vote.An ISO/PAS or ISO/TS is reviewed after three years in order to decide whether it will be confirmed for a further three years, revised to become an International Standard, or withdrawn. If the ISO/PAS or ISO/TS is confirmed, it is reviewed again after a further three years, at which time it must
27、 either be transformed into an International Standard or be withdrawn.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.ISO/TS 16189 was prepared by the
28、 European Committee for Standardization (CEN) Technical Committee CEN/TC 309, Footwear, in collaboration with ISO Technical Committee ISO/TC 216, Footwear, in accordance with the agreement on technical cooperation between ISO and CEN (Vienna Agreement).iv ISO 2013 All rights reservedCopyright Europe
29、an Committee for Standardization Provided by IHS under license with CENNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-PD CEN ISO/TS 16189:2013TECHNICAL SPECIFICATION ISO/TS 16189:2013(E)Footwear Critical substances potentially present in footwear and footwear comp
30、onents Test method to quantitatively determine dimethylformamide in footwear materials1 ScopeThis Technical Specification specifies a method to determine the amounts of dimethylformamide (DMFo) in footwear and footwear components containing polyurethane (PU) coated material.NOTE In the footwear indu
31、stry, when PU is injected (reaction moulded), this process does not require the use of DMFo. DFMo can be used for PU coated material.2 Normative referencesThe following documents, in whole or in part, are normatively referenced in this document and are indispensable for its application. For dated re
32、ferences, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies.ISO/TR 16178:2012, Footwear Critical substances potentially present in footwear and footwear components3 Method principleThe sample is cut into small pie
33、ces and extracted with methanol in a sealed vial at 70 C in an ultrasonic bath. An aliquot of the extract is analysed with GC-MS in SIM mode.ISO/TR 16178:2012, Table 1 defines which materials are concerned by this determination.4 Reagents and solvents4.1 ReagentsThe substances are given in Table 1.T
34、able 1 ReagentsNumber Substances CAS Number aPurity1 Dimethylformamide (DMFo) 68-12-2 Certificated standard2 Dimethylformamide-d7 (DMFo-d7) 4472-41-7 Certificated standard3 Methanol 67-56-1 Analytical gradeaCAS: Chemical Abstract Service.4.2 Stock solutions4.2.1 Internal standard Stock solution (1 0
35、00 mg/l)10 mg of DMFo-d7 is weighted with an accuracy of 0,1 mg in a 10 ml volumetric flask and filled up to the mark with methanol. The content is further transferred in an amber 10 ml vial with PTFE stopcock and keep at 4 C. ISO 2013 All rights reserved 1Copyright European Committee for Standardiz
36、ation Provided by IHS under license with CENNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-PD CEN ISO/TS 16189:2013ISO/TS 16189:2013(E)4.2.2 Internal standard Working solution (200 mg/l)The solution is prepared by 1:5 dilution of the stock solution (4.2.1) with me
37、thanol.4.2.3 Target compound Stock solution (1 000 mg/l)10 mg of DMFo is weighed with an accuracy of 0,1 mg in in a 10 ml volumetric flask and filled up to the mark with methanol. The content is further transferred in an amber 10 ml vial with PTFE stopcock and keep at 4 C.4.2.4 Target compound Worki
38、ng solution (200 mg/l)The solution is prepared by 1:5 dilution of the stock solution (4.2.3) with methanol.5 EquipmentUsual laboratory equipment, in addition to the following.5.1 Analytical balance (precision at least 0,1 mg).5.2 Glass vial which can be tightly sealed, 20 ml.5.3 Ultrasonic bath with
39、 adjustable temperature.5.4 PTFE-membrane filter pore width 0,45 m.5.5 2 ml sample vials with PTFE-capped.5.6 Volumetric flask, 10ml.5.7 Amber vessels.5.8 Micropipettes, 20 l to 10 ml.5.9 Gas chromatograph with mass selective detector (GC-MS).6 Preparation of sample6.1 SamplingSamples of PU coated m
40、aterials are cut into pieces up to 3 mm edge length.A maximum of three PU coated materials (equal in mass) can be mixed together.6.2 ExtractionA test sample of 1 g 0,001 g is weighed (ms) with the analytical balance (5.1) in a 20 ml glass vial (5.2). Then 9 ml of methanol and 1 ml of the internal st
41、andard working solution (4.2.2) are added and the vial is sealed.The sample is extracted at 70 C for 1 h in an ultrasonic bath.After cooling to room temperature the solution is filtered (if necessary) through a PTFE membrane filter (5.4). An aliquot of the extract is transferred to a GC-MS vial and
42、sealed with a PTFE-cap (5.5).2 ISO 2013 All rights reservedCopyright European Committee for Standardization Provided by IHS under license with CENNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-PD CEN ISO/TS 16189:2013ISO/TS 16189:2013(E)7 Determination with GC-MS7
43、.1 Calibration standardSix calibration points are used to establish the calibration curve. They are all prepared in 10 ml volumetric flasks, as given in Table 2.Table 2 Preparation of calibrationStandard L1 L2 L3 L4 L5 L6Volume of target compound working solution (4.2.4)25 l 50 l 100 l 250 l 500 l 1
44、 000 lConcentration of target compound in the cali-bration solutions (mg/l)0,5 1 2 5 10 20Volume of the methanol working solution of internal standard (4.2.2)1 000 l 1 000 l 1 000 l 1 000 l 1 000 l 1 000 lConcentration of the internal standard (mg/l) 20 20 20 20 20 20NOTE Filled to the mark with met
45、hanol.7.2 Examples of instrumental methodAn example is given in Annex A.8 Quantification8.1 Calibration curveSet up the linear regression function by using the ratio (Ae/Ais) and (Ce/Cis) with the help of the formula:AAaCCbeiseis=+ whereAeis the area of the peak of dimethylformamide;Aisis the area o
46、f the peak of dimethylformamide-D7;Ceis the concentration of dimethylformamide in the calibration standard in milligrams per litre (mg/l);Cisis the concentration of dimethylformamide-D7 in the calibration standard in milligrams per litre (mg/l);a is the slope of the linear function;b is the ordinate
47、 intercept of the calibration curve (the units depend on the evaluation). ISO 2013 All rights reserved 3Copyright European Committee for Standardization Provided by IHS under license with CENNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-PD CEN ISO/TS 16189:2013IS
48、O/TS 16189:2013(E)The content of DMFo is calculated according to the following equation as a mass fraction w in mg/kg:WVmAAbaC=( ) echisiswhereW is the content of the dimethylformamide in the specimen (mg/kg);V is the volume of the solvent used for the extraction (ml) (in most cases this value will be equal to 10 ml);m is the mass of the tested specimen (g);Aechis the area of the peak of dimethylformamide in the sample;Aisis the area of the peak of dimethylformamide-D7 in the sample;Cisis the concentration of dimethylforma
