1、October 2012 Translation by DIN-Sprachendienst.English price group 9No part of this translation may be reproduced without prior permission ofDIN Deutsches Institut fr Normung e. V., Berlin. Beuth Verlag GmbH, 10772 Berlin, Germany,has the exclusive right of sale for German Standards (DIN-Normen).ICS
2、 61.060!$*:“1920723www.din.deDDIN EN 14602Footwear Test methods for the assessment of ecological criteria;English version EN 14602:2012,English translation of DIN EN 14602:2012-10Schuhe Prfverfahren zur Beurteilung kologischer Kriterien;Englische Fassung EN 14602:2012,Englische bersetzung von DIN EN
3、 14602:2012-10Chaussure Mthodes dessai pour lvaluation de critres cologiques;Version anglaise EN 14602:2012,Traduction anglaise de DIN EN 14602:2012-10SupersedesDIN EN 14602:2005-02www.beuth.deDocument comprises 16 pagesIn case of doubt, the German-language original shall be considered authoritative
4、.10.12 2 A comma is used as the decimal marker. National foreword This standard has been prepared by Technical Committee CEN/TC 309 “Footwear” (Secretariat: AENOR, Spain). The responsible German body involved in its preparation was the Normenausschuss Materialprfung (Materials Testing Standards Comm
5、ittee), Working Committee NA 062-04-52 AA Schuhe. The DIN Standard corresponding to the International Standard referred to in this document is as follows: ISO 5725-2 DIN ISO 5725-2 Amendments This standard differs from DIN EN 14602:2005-02 as follows: a) normative references have been updated; b) th
6、e former Clause 4 “Preparation of samples” has been deleted; c) the determination of Cr(VI) has been deleted; d) the determination of the total heavy metals content has been modified; e) the determination of partially hydrolysable formaldehyde has been deleted; f) the determination of pentachlorophe
7、nol has been deleted; g) the determination of azo-dyes has been deleted; h) the determination of chloroalcanes has been deleted; i) the determination of cadmium in polymeric materials has been deleted; j) the determination of organotin compounds has been deleted; k) a new Subclause 4.2 “Water consum
8、ption, emission in water of COD and chromium III” has been included. Previous editions DIN EN 14602: 2005-02 DIN EN 14602:2012-103 National Annex NA (informative) Bibliography DIN ISO 5725-2, Accuracy (trueness and precision) of measurement methods and results Part 2: Basic method for the determinat
9、ion of repeatability and reproducibility of a standard measurement method DIN EN 14602:2012-104 This page is intentionally blank DIN EN 14602:2012-10EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 14602 August 2012 ICS 61.060 Supersedes EN 14602:2004 English Version Footwear Test methods for th
10、e assessment of ecological criteria Chaussure Mthodes dessai pour lvaluation de critres cologiques Schuhe Prfverfahren zur Beurteilung kologischer Kriterien This European Standard was approved by CEN on 13 July 2012. CEN members are bound to comply with the CEN/CENELEC Internal Regulations which sti
11、pulate the conditions for giving this European Standard the status of a national standard without any 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
12、 Standard exists in three official versions (English, French, German). A version in any other language 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 th
13、e national standards bodies of 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, Portugal, Romani
14、a, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG Management Centre: Avenue Marnix 17, B-1000 Brussels 2012 CEN All rights of exploitation in any form and by any means res
15、erved worldwide for CEN national Members. Ref. No. EN 14602:2012: E EN 14602:2012 (E) 2 Contents Page Foreword 31 Scope 42 Normative references 43 Terms and definitions .44 Test methods associated to the Criteria .54.1 Determination of total heavy metals content 54.1.1 General 54.1.2 Preparation of
16、the samples .64.1.3 Reagents .64.1.4 Apparatus and materials .64.1.5 Digestion .64.1.6 Determination of heavy metals content 74.1.7 Test report 84.2 Water consumption, emission in water of COD and chromium III .84.3 Determination of nitrosamines .94.4 Determination of phthalates .94.5 Determination
17、of the VOC emissions 94.5.1 General 94.5.2 Procedure .94.5.3 Test report . 104.6 Determination of the electrical energy consumption 10Bibliography . 12DIN EN 14602:2012-10EN 14602:2012 (E) 3 Foreword This document (EN 14602:2012) has been prepared by Technical Committee CEN/TC 309 “Footwear”, the se
18、cretariat of which is held by AENOR. 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 February 2013, and conflicting national standards shall be withdrawn at the latest by February 2013. Attention
19、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. This document supersedes EN 14602:2004. The main technical changes that have been made in this n
20、ew edition of EN 14602 are the following ones: changes in the general organisation of the standard; all the criteria for the Ecolabel for footwear that are already covered by European standards are removed from this edition; improvement in the test methods for the determination of total heavy metals
21、 content; criteria on COD an Cr III have been introduced; new reference test method the determination of phthalates; new test method for the determination of the electrical energy consumption. According to the CEN/CENELEC Internal Regulations, the national standards organisations of the following co
22、untries are bound 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,
23、Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom. DIN EN 14602:2012-10EN 14602:2012 (E) 4 1 Scope This European Standard defines certain test methods necessary to issue the footwear Ecolabel, For some criteria, this European Standard provides i
24、mportant clarification or gives a test method to assess the ecological criteria. NOTE The footwear Ecolabel has been published in the Official Journal of July 28th, 2009. This European Standard applies to any kind of footwear except those containing electrical or electronic components. The chemical
25、analysis of the metallic components is outside of the scope of this European Standard. 2 Normative references The following documents, in whole or in part, are normatively referenced in this document and are indispensable for its application. For dated references, only the edition cited applies. For
26、 undated references, the latest edition of the referenced document (including any amendments) applies. EN 1122:2001, Plastics Determination of cadmium Wet decomposition method EN 12868, Child use and care articles Methods for determining the release of N-Nitrosamines and N-Nitrosatable substances fr
27、om elastomers or rubber teats and soothers EN ISO 11885, Water quality Determination of selected elements by inductively coupled plasma optical emission spectrometry (ICP-OES) (ISO 11885) CEN ISO/TS 16181, Footwear Critical substances potentially present in footwear and footwear components Determina
28、tion of phthalates in footwear materials (ISO/TS 16181) EN ISO 17072-2:2011, Leather Chemical determination of metal content Part 2: Total metal content (ISO 17072-2:2011) EN ISO 17294-2, Water quality Application of inductively coupled plasma mass spectrometry (ICP-MS) Part 2: Determination of 62 e
29、lements (ISO 17294-2) ISO 8288, Water quality Determination of cobalt, nickel, copper, zinc, cadmium and lead Flame atomic absorption spectrometric methods 3 Terms and definitions For the purposes of this document, the following terms and definitions apply. 3.1 volatile organic compound VOC organic
30、compound that has, at 293,15 K, a vapour pressure of 0,01 KPa or more, or that has a corresponding volatility under the particular conditions of use 3.2 volatile organic compounds emissions VOC emissions amount of volatile organic compounds emitted to the atmosphere to produce a pair of shoes DIN EN
31、 14602:2012-10EN 14602:2012 (E) 5 3.3 test period Tp consecutive test period during which: the production of the shoe or a group of shoes being analysed is well known; the consumption of chemical preparations is well known 3.4 process electric consumption PEC electricity used only by the process equ
32、ipment used to manufacture the footwear 4 Test methods associated to the criteria NOTE The uncertainty of measurement for each test method described in this European Standard can be assessed according to the methods described ENV 13005 or ISO 5725-2. 4.1 Determination of total heavy metals content 4
33、.1.1 General The total concentration of heavy metals in a product is considered as a relevant criterion regarding the end of life disposal. This test method identifies the main chemicals of potential hazard which may contaminate the environment after disposal or incineration. There shall be no Arsen
34、ic, Cadmium and Lead in the materials used for the product assembly or in the final product. Presence of heavy metals shall be established by either: testing the materials individually; or testing the upper and lower components of the shoe as composite groups of materials. NOTE The total concentrati
35、on of other heavy metals (see Table 1) can be determined using this method. Table 1 Possible heavy metals determined Aluminium (Al) Mercury (Hg) Antimony (Sb) Molybdenum (Mo) Barium (Ba) Nickel (Ni) Boron (B) Potassium (K) Chromium (Cr) Selenium (Se) Cobalt (Co) Silicon (Si) Copper (Cu) Tin (Sn) Iro
36、n (Fe) Titanium (Ti) Magnesium (Mg) Zinc (Zn) Manganese (Mn) Zirconium (Zr) DIN EN 14602:2012-10EN 14602:2012 (E) 6 4.1.2 Preparation of the samples 4.1.2.1 Testing the materials for the product assembly Test each material individually. Each material is ground according to EN ISO 4044 or a similar t
37、est method. NOTE Textile materials do not need to be ground. 4.1.2.2 Testing the final product Separate the upper and the lower components of the footwear. Fully grind each group of components separately according to EN ISO 4044 or a similar test method. NOTE Only a full grinding of the test specime
38、n will ensure the reproducibility of the test results. 4.1.3 Reagents WARNING Violent reactions may be produced with perchloric acid (HClO4) on an organic matrix. 4.1.3.1 H2SO4, 96 % (mass fraction). 4.1.3.2 HNO3, 65 % (mass fraction). 4.1.3.3 HClO4, 65 % (mass fraction). 4.1.3.4 HCl, 36 % (mass fra
39、ction). 4.1.3.5 Demineralised water. 4.1.4 Apparatus and materials Standard laboratory apparatus and glassware, together with the following: 4.1.4.1 A suitable heating device (for the acid digestion only). 4.1.4.2 Volumetric flask, of 100 ml. 4.1.4.3 Filter paper of 0,45 m mesh size. 4.1.4.4 Microwa
40、ve reactor (for the microwave digestion only), capable of working at maximum 100 bars (or 1 450 psi). 4.1.5 Digestion 4.1.5.1 Method A acid digestion Prepare, according to 4.1.2, a test piece of (0,500 0,005) g of ground sample. The digestion given in EN 1122:2001, 6.3.2, method B is to be used. 4.1
41、.5.2 Method B acid digestion Prepare, according to 4.1.2, a test piece of (1,000 0,005) g of ground sample. The digestion given in EN ISO 17072-2:2011, 6.5.1 is to be used. DIN EN 14602:2012-10EN 14602:2012 (E) 7 4.1.5.3 Method C - Microwave digestion Prepare, according to 4.1.2, a test piece of 0,1
42、00 g to 0,500 g of ground sample. Prepare a digestion solution by mixing 5 ml of demineralised water (4.1.3.5) and 5 ml of the following mixture: HNO3, 65 % (4.1.3.2) and HCl, 36 % (4.1.3.4) (1/3:2/3). Put the test piece in the microwave reactor (4.1.4.4), add the digestion solution and then start t
43、he digestion cycles (see for example a programme in Table 2). Table 2 Cycles of digestion Time (min) 2,5 2,5 5 10 5 2,5 2,5 5 5 Power (W) 250 0 350 500 0 250 0 350 550 When the cycles are completed, transfer the resulting solution, filtering it through a filter paper (4.1.4.3), to a volumetric flask
44、 (4.1.4.2) and adjust the volume to 100 ml with demineralised water (4.1.3.5). One blank (acid solution) is treated at the same time and a validation with this reference solution is carried out. The digestion vessels shall be cleaned with special attention once the acid digestion is finished. 4.1.6
45、Determination of heavy metals content Table 3 defines the recommended options for the determination of heavy metals in footwear. Table 3 Test method for heavy metals determination Testing the materials Testing the final productSoft material leather, textile Hard material polymers Upper Lower compone
46、nts of the footwear Method A possible Recommended (especially for PVC) possible Recommended (especially for PVC) Method B possible possible possible possible Method C possible possible possible possible From the solution obtained in 4.1.5.1 or 4.1.5.2 or 4.1.5.3 determine, within 24 h, the Cd, As, P
47、b content by atomic absorption spectroscopy (AAS) as specified in ISO 8288, or by inductively coupled plasma atomic emission spectroscopy (ICP) as specified EN ISO 11885 or EN ISO 17294-2 (see EN ISO 17072-2). NOTE 1 The quantification limit for a 1 g sample is given in Table 4. DIN EN 14602:2012-10
48、EN 14602:2012 (E) 8 Table 4 Test method for heavy metals determination Metal Limit of quantificationin the liquid extraction g/l Limit of quantification mg/kg As 20 5 Cd 5 1 Pb 20 5 Results shall be expressed as: in mg/kg of material for each metal (Cd, Pb, and As) for the procedure in 4.1.2.1; in mg/kg of footwear sample for each metal (Cd, Pb, and As) for the procedure in 4.1.2.2. NOTE 2 Other metals (see Table 1)
