1、raising standards worldwideNO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAWBSI Standards PublicationBS EN 14602:2012Footwear Test methods forthe assessment of ecologicalcriteriaBS EN 14602:2012 BRITISH STANDARDNational forewordThis British Standard is the UK implementation of E
2、N 14602:2012. Itsupersedes BS EN 14602:2004 which is withdrawn.The UK participation in its preparation was entrusted to TechnicalCommittee TCI/69, Footwear, leather and coated fabrics.A list of organizations represented on this committee can beobtained on request to its secretary.This publication do
3、es not purport to include all the necessaryprovisions of a contract. Users are responsible for its correctapplication. The British Standards Institution 2012. Published by BSI StandardsLimited 2012ISBN 978 0 580 76840 8ICS 61.060Compliance with a British Standard cannot confer immunity fromlegal obl
4、igations.This British Standard was published under the authority of theStandards Policy and Strategy Committee on 31 August 2012.Amendments issued since publicationDate Text affectedBS EN 14602:2012EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 14602 August 2012 ICS 61.060 Supersedes EN 14602:
5、2004English Version Footwear - Test methods for the 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 comp
6、ly with the CEN/CENELEC Internal Regulations which stipulate 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
7、 Management Centre or to any CEN member. This European 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 sa
8、me status as the official versions. CEN members are the 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
9、, Malta, Netherlands, Norway, Poland, Portugal, Romania, 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 r
10、ights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 14602:2012: EBS EN 14602:2012EN 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 Determinatio
11、n of total heavy metals content 54.1.1 General 54.1.2 Preparation of 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 o
12、f nitrosamines .94.4 Determination of phthalates .94.5 Determination 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 . 12BS EN 14602:2012EN 14602:2012 (E) 3 Foreword This document (EN 14602:2012) has b
13、een prepared by Technical Committee CEN/TC 309 “Footwear”, the secretariat 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 standa
14、rds shall be withdrawn at the latest by February 2013. 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. This document supersedes EN 146
15、02:2004. The main technical changes that have been made in this new 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; improvemen
16、t in the test methods for the determination of total heavy metals 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 Regu
17、lations, the national standards organisations of the following countries 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, I
18、taly, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom. BS EN 14602:2012EN 14602:2012 (E) 4 1 Scope This European Standard defines certain test methods necessary to issue the footwear E
19、colabel, For some criteria, this European Standard provides important 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
20、containing electrical or electronic components. The chemical 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 applicati
21、on. For dated references, only the edition cited applies. For 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 t
22、he release of N-Nitrosamines and N-Nitrosatable substances from 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 pote
23、ntially present in footwear and footwear components Determination 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 pl
24、asma mass spectrometry (ICP-MS) Part 2: Determination of 62 elements (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
25、definitions apply. 3.1 volatile organic compound VOC organic 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 compound
26、s emitted to the atmosphere to produce a pair of shoes BS EN 14602:2012EN 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
27、 consumption PEC electricity used only by the process equipment 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
28、5725-2. 4.1 Determination of total heavy metals content 4.1.1 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 environmen
29、t after disposal or incineration. There shall be no Arsenic, 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
30、composite groups of materials. NOTE The total concentration 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) Seleni
31、um (Se) Cobalt (Co) Silicon (Si) Copper (Cu) Tin (Sn) Iron (Fe) Titanium (Ti) Magnesium (Mg) Zinc (Zn) Manganese (Mn) Zirconium (Zr) BS EN 14602:2012EN 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 mater
32、ial is ground according to EN ISO 4044 or a similar test 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
33、method. NOTE Only a full grinding of the test specimen 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 HCl
34、O4, 65 % (mass fraction). 4.1.3.4 HCl, 36 % (mass fraction). 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.
35、4.3 Filter paper of 0,45 m mesh size. 4.1.4.4 Microwave 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 give
36、n in EN 1122:2001, 6.3.2, method B is to be used. 4.1.5.2 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. BS EN 14602:2012EN 14602:2012 (E) 7 4.1.5.3 Method C - Microwave digestion
37、 Prepare, according to 4.1.2, a test piece of 0,100 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.
38、4.4), add the digestion solution and then start the 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 throug
39、h a filter paper (4.1.4.3), to a volumetric flask (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 atte
40、ntion once the acid digestion is finished. 4.1.6 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, t
41、extile Hard material polymers Upper Lower components 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
42、 or 4.1.5.3 determine, within 24 h, the Cd, As, Pb 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
43、 sample is given in Table 4. BS EN 14602:2012EN 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, P
44、b, 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) can be determined by this method. Using the acid digestion (method B), if Pb is detected, the digestion procedure shall be repeated but
45、 replacing H2SO4(4.1.3.1) by HCl (4.1.3.4). 4.1.7 Test report The test report shall include at least the following information: a) reference to this method, including digestion procedure and determination method; b) complete description of the sample, including the material type and all the details
46、concerning the mass of metallic and non metallic materials; c) heavy metals content according to Table 4, 1) in mg/kg of material, for each metal Cd, Pb, As, as calculated in 4.1.6 (procedure 4.1.2.1); 2) in mg/kg of footwear, for each metal Cd, Pb, As, as calculated in 4.1.6 (procedure 4.1.2.2); d)
47、 date of testing; e) for samples containing leather, a determination of dry matter shall be reported as required by EN ISO 17072-2; f) any deviation from this test method. 4.2 Water consumption, emission in water of COD and chromium III If the footwear contains leather, it is the responsibility of t
48、he footwear manufacturer to require the water consumption and emission in water of COD and chromium III for the tanning. These information are given by the tanner. Leather is produced after several operations (beamhouse, tanning, dying, finishing) that are not always done at the same location. The c
49、onsumption figures for hides and skins shall include all the different steps. To collect all this information with a guarantee of tracability can be difficult. BS EN 14602:2012EN 14602:2012 (E) 9 NOTE In Europe, the information concerning COD (chemical oxygen demand) and chromium III in water is available in all the industry due to the application of Directive 91/271/EEC and the appropriate national regulations. 4.3 Determination of nitrosamines Separate the rubb
