1、raising standards worldwideNO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAWBSI Standards PublicationDD CEN/TS 16137:2011Plastics Determination ofbio-based carbon contentDD CEN/TS 16137:2011 DRAFT FOR DEVELOPMENTNational forewordThis Draft for Development is the UK implementatio
2、n of CEN/TS 16137:2011.This publication is not to be regarded as a British Standard.It is being issued in the Draft for Development series of publications and is of a provisional nature. It should be applied on this provisional basis, so that information and experience of its practical application c
3、an be obtained.Comments arising from the use of this Draft for Development are requested so that UK experience can be reported to the international organization responsible for its conversion to an international standard. A review of this publication will be initiated not later than 3 years after it
4、s publication by the international organization so that a decision can be taken on its status. Notification of the start of the review period will be made in an announcement in the appropriate issue of Update Standards.According to the replies received by the end of the review period, the responsibl
5、e BSI Committee will decide whether to support the conversion into an international Standard, to extend the life of the T e c h n i c a l S p e c i f i c a t i o n o r t o w i t h d r a w i t . C o m m e n t s s h o u l d b e s e n t to the Secretary of the responsible BSI Technical Committee at Bri
6、tish Standards House, 389 Chiswick High Road, London W4 4AL.The UK participation in its preparation was entrusted to T e c h n i c a l C o m m i t t e e P R I / - / 1 , U K c o - o r d i n a t i o n f o r i n t e r n a t i o n a l work on plastics.A list of organizations represented on this committe
7、e 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. BSI 2011ISBN 978 0 580 71702 4ICS 83.080.01Compliance with a British Standard cannot confer immunity from legal ob
8、ligations.This Draft for Development was published under the authority of the Standards Policy and Strategy Committee on 31 July 2011.Amendments issued since publicationDate T e x t a f f e c t e dDD CEN/TS 16137:2011TECHNICAL SPECIFICATION SPCIFICATION TECHNIQUE TECHNISCHE SPEZIFIKATION CEN/TS 1613
9、7 April 2011 ICS 83.080.01 English Version Plastics - Determination of bio-based carbon content Plastiques - Dtermination de la teneur en carbone biosourc Kunststoffe - Bestimmung des biobasierten Kohlenstoffgehalts This Technical Specification (CEN/TS) was approved by CEN on 20 December 2010 for pr
10、ovisional 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 to submit their comments, particularly on the question whether the CEN/TS can be converted into a European Standard. CEN members are required to anno
11、unce 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 is permissible to keep conflicting national standards in force (in parallel to the CEN/TS) until the final decision about the possible conversion of t
12、he CEN/TS into an EN is reached. CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Port
13、ugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG Management Centre: Avenue Marnix 17, B-1000 Brussels 2011 CEN All rights of exploitation in any form and by any means
14、 reserved worldwide for CEN national Members. Ref. No. CEN/TS 16137:2011: EDD CEN/TS 16137:2011CEN/TS 16137:2011 (E) 2 Contents Page Foreword 4Introduction .51 Scope 62 Normative references 63 Terms and definitions .64 Symbols and abbreviations 74.1 Symbols 74.2 Abbreviations .85 Principle 86 Sampli
15、ng .97 Determination of the 14C content 97.1 General 97.2 Principle 97.3 Procedure for the conversion of the carbon present in the sample to a suitable sample for 14C determination 107.4 Measurements . 108 Calculation of the bio-based carbon content 108.1 General . 108.2 Correction factors . 118.3 C
16、alculation method. 119 Test report . 14Annex A (normative) Procedure for the conversion of the carbon present in the sample to a suitable sample for 14C determination 15A.1 General . 15A.2 Reagents and materials . 15A.3 Combustion of the sample in a calorimetric bomb . 16A.4 Combustion of the sample
17、 in a tube furnace or a combustion apparatus . 17A.5 Dissolution and LSC direct measurement on the polymer 17Annex B (normative) Method A - Proportional scintillation-counter method (PSM) . 18B.1 General . 18B.2 Principle . 18B.3 Reagents and materials . 18B.4 Apparatus 18B.5 Procedure 18B.6 Calcula
18、tion of the results . 20Annex C (normative) Method B - Beta-ionisation (BI) 21C.1 General . 21C.2 Principle . 21C.3 Reagents and materials . 21C.4 Apparatus 22C.5 Procedure 22C.6 Calculation of the results . 23Annex D (normative) Method C - Accelerator Mass Spectrometry (AMS) 24D.1 General . 24D.2 P
19、rinciple . 24D.3 Reagents and materials . 24DD CEN/TS 16137:2011CEN/TS 16137:2011 (E) 3 D.4 Apparatus . 24D.5 Procedure . 25D.6 Calculation of the results 25Bibliography 26DD CEN/TS 16137:2011CEN/TS 16137:2011 (E) 4 Foreword This document (CEN/TS 16137:2011) has been prepared by Technical Committee
20、CEN/TC 249 “Plastics”, the secretariat of which is held by NBN. 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 has been
21、 prepared under a mandate given to CEN by the European Commission and the European Free Trade Association. According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are bound to announce this European Standard: Austria, Belgium, Bulgaria, Croa
22、tia, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and the United Kingdom. DD CEN/TS 16137:2011CEN/TS 1
23、6137:2011 (E) 5 Introduction This Technical Specification specifies the calculation method for the determination of bio-based carbon content in monomers, polymers, plastics materials and products using the 14C method. This calculation method using the 14C method is based on the well established anal
24、ytical test methods used for the determination of the age of objects containing carbon. This Technical Specification provides the reference test methods for laboratories, producers, suppliers and purchasers of bio-based polymer materials and products. It can be also useful for authorities and inspec
25、tion organizations. NOTE 1 This Technical Specification is based on EN 15440 4 prepared by CEN/TC 343, Solid recovered fuels. NOTE 2 The analytical test methods specified in this Technical Specification are compatible with those described in ASTM D6866 - 10 9. DD CEN/TS 16137:2011CEN/TS 16137:2011 (
26、E) 6 1 Scope This Technical Specification specifies a calculation method for the determination of the bio-based carbon content in monomers, polymers and plastic materials and products, based on the 14C content measurement. It also specifies three test methods to be used for the determination of the
27、14C content from which the bio-based carbon content is calculated: Method A: Proportional scintillation-counter method (PSM); Method B: Beta-ionisation (BI); Method C: Accelerator mass spectrometry (AMS). The bio-based carbon content is expressed by a fraction of sample mass, as a fraction of the to
28、tal carbon content or as a fraction of the total organic carbon content. This calculation method is applicable to any polymers containing organic carbon, including biocomposites. NOTE This Technical Specification does not provide the methodology for the calculation of the biomass content of a sample
29、. 2 Normative references The following referenced documents are indispensable for the application of this document. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies. CEN/TR 15932:2010, Plast
30、ics Recommendation for terminology and characterisation of biopolymers and bioplastics 3 Terms and definitions For the purposes of this document, the terms and definitions given in CEN/TR 15932:2010 and the following apply. 3.1 bio-based carbon content amount of carbon in a sample that is of recent
31、origin, as evidenced by its 14C isotope content 3.2 biomass content mass fraction of bio-based material in a sample 3.3 organic material material containing carbon-based compound in which the element carbon is attached to other carbon atoms, hydrogen, oxygen, or other elements in a chain, ring, or t
32、hree-dimensional structure 3.4 organic carbon carbon from organic material 3.5 isotope abundance fraction of atoms of a particular isotope of an element DD CEN/TS 16137:2011CEN/TS 16137:2011 (E) 7 3.6 percentage modern carbon pmC percent modern carbon relative to the N.I.S.T.1)oxalic acid radiocarbo
33、n standard reference material SRM 4990B NOTE In 1950, the internationally accepted radiocarbon dating reference value is 95 % of this activity of this NBS oxalic acid SRM 4990b. In 2010, the value of 100 % bio-based carbon is set at 105 pmC. 3.7 laboratory sample sub-quantity of a sample suitable fo
34、r laboratory tests 3.8 sample quantity of material, representative of a larger quantity for which the property is to be determined 3.9 sample preparation actions taken to obtain representative analyses samples or test portions from the original sample 3.10 particle electron emitted during radioactiv
35、e decay 3.11 total carbon TC quantity of carbon present in a sample in the form of organic, inorganic and elemental carbon EN 13137:2001 3.12 total organic carbon TOC quantity carbon that is converted into carbon dioxide by combustion and which is not liberated as carbon dioxide by acid treatment EN
36、 13137:2001 4 Symbols and abbreviations 4.1 Symbols C symbol for element carbon 14C carbon isotope with an atomic mass of 14 xTCtotal carbon content, expressed as a percentage of the mass of the sample xTOCtotal organic carbon content, expressed as a percentage of the mass of the sample xBbio-based
37、carbon content by mass, expressed as a percentage of the mass of the sample 1) National Institute of Standards and Technology - Gaithersburg, Maryland, USA. DD CEN/TS 16137:2011CEN/TS 16137:2011 (E) 8 TCBx bio-based carbon content by total carbon content, expressed as a percentage of the total carbo
38、n content TOCBx bio-based carbon content by total organic carbon content, expressed as a percentage of the total organic carbon content pmC(s) measured value, expressed in pmC, according to AMS method, of the sample REF reference value, expressed in pmC, of 100 % bio-based carbon depending on the or
39、igin of organic carbon m mass of a sample expressed in grams 4.2 Abbreviations AMS accelerator mass spectroscopy BI beta-ionisation Bq Bequerel (desintegrations per second) cpm counts per minute CV coefficient of variation dpm disintegrations per minute GM Geiger-Mller LLD lower limit of detection L
40、SC liquid scintillation-counter or liquid scintillation-counting MOP 3-methoxy 1-propyl amine PE polyethylene PLA poly(lactic acid) pmC percentage of modern carbon PSM proportional scintillation-counter method TC total carbon TOC total organic carbon 5 Principle The 14C present in chemicals is origi
41、nating from recent atmospheric CO2. Due to its radioactive decay, it is almost absent from fossil products older than 20 000 years to 30 000 years. The 14C content may thus be considered as a tracer of chemicals recently synthesized from atmospheric CO2and particularly of recently produced bio-produ
42、cts. The determination of the biomass content is based on the measurement of 14C in bio-based polymers which allows the calculation of the bio-based carbon fraction. DD CEN/TS 16137:2011CEN/TS 16137:2011 (E) 9 A large experience in 14C determination and reference samples are available from dating of
43、 archaeological objects, on which the three methods described in this technical specification are based: Method A: Proportional scintillation-counter method (PSM), Method B: Beta-ionisation (BI), or Method C: Accelerator mass spectrometry (AMS). NOTE The advantages and disadvantages of these test me
44、thods are given in Table 1. Table 1 Advantages and disadvantages of the methods Method Technical level Additional requests Duration needed for measurement Relative standard deviation Instrumental costs Method A (PSM) Simple Normal laboratory 4 h to 12 h 2 % to 10 % Low Method B (BI) Complex - Low ba
45、ckground laboratory - Gas purification device 8 h to 24 h 0,2 % to 5 % Low Method C (AMS) Very complex - Large installation - Graphite conversion device 10 min to 30 min 0,2 % to 2 % High 6 Sampling If there is a standard sampling procedure for the material or product to be evaluated that is widely
46、accepted by the different parties, such a procedure may be used and the details of sampling recorded. For any sampling procedure, the samples shall be representative of the material or product and the quantity or mass of sample shall be accurately established. 7 Determination of the 14C content 7.1
47、General A general sample preparation and three test methods for the determination of the 14C content are described in this Technical Specification. With this modular approach it will be possible for normally equipped laboratories to prepare samples for the 14C content, and determine the 14C content
48、with own equipment or to outsource the determination of the 14C content to laboratories that are specialized in this technique. For the collection from the sample of the 14C content, generally accepted methods for the conversion of the carbon present in the sample to CO2are described. For the measur
49、ement of the 14C content, methods are selected, that are already generally accepted as methods for the determination of the age of objects. 7.2 Principle The amount of bio-based carbon in the bio-based polymer is proportional to this 14C content. Complete combustion (see Annex A) is carried out in a way to comply with the requirements of the subsequent measurement of the 14C content and shall provide the quantitative recovery of all carbon present DD C
