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Applications of Ionizing Radiation in Materials Processing APPLICATIONS OF IONIZING RADIATION IN MATERIALS PROCESSING edited by Yongxia Sun and Andrzej G. Chmielewski VOLUME 2 Institute of Nuclear Chemistry and Technology Warszawa 2017 Editors Assoc. Prof. Yongxia Sun, Ph.D., D.Sc. Prof. Andrzej G. Chmielewski, Ph.D., D.Sc. Reviewer Mr. Anthony J. Berejka, Owner/President IONICORP+ Technical editor Ewa Godlewska-Para, M.Sc. Cover designer Sylwester Wojtas “Joint innovative training and teaching/learning program in enhancing develop- ment and transfer knowledge of application of ionizing radiation in materials processing” – TL-IRMP (Agreement number 2014-1-PL01-KA203-003611). This publication refl ects the views only of the author(s). Polish National Agency for the Erasmus+ Programme and the European Commission cannot be held responsible for any use which may be made of the information contained therein. Istituto per i Polimeri, Compositi e Biomateriali, Consiglio Nazionale delle Ricerche Kaunas University of Technology Institute of Nuclear Chemistry and Technology Università degli Studi di Palermo Hacettepe University Université de Reims Champagne-Ardenne “Petru Poni” Institute of Macromolecular Chemistry ISBN 978-83-933935-8-9 ISBN 978-83-946412-0-7 (Volume 2) © Copyright by the Institute of Nuclear Chemistry and Technology, Warszawa 2017. Text of the book is licensed under the Creative Commons Attribution-NonCommer- cial-NoDerivatives 3.0 License (CC BY-NC-ND 3.0). Institute of Nuclear Chemistry and Technology Dorodna 16, 03-195 Warszawa, Poland phone: +48 22 504 12 05, fax: +48 22 811 15 32 e-mail: [email protected] www.ichtj.waw.pl CONTENTS VOLUME 1 PREFACE 5 Chapter 1 BASIC RADIATION PHYSICS AND SOURCES OF RADIATION Diana Adlienė 7 Chapter 2 RADIATION INTERACTION WITH CONDENSED MATTER Diana Adlienė 33 Chapter 3 DOSIMETRY PRINCIPLES, DOSE MEASUREMENTS AND RADIATION PROTECTION Diana Adlienė, Rūta Adlytė 55 Chapter 4 RADIATION CHEMISTRY OF LIQUID SYSTEMS Krzysztof Bobrowski 81 Chapter 5 RADIATION CHEMISTRY OF ORGANIC SOLIDS Cornelia Vasile, Elena Butnaru 117 Chapter 6 RADIATION-INDUCED POLYMERIZATION Xavier Coqueret 143 Chapter 7 IONIZING RADIATION-INDUCED CROSSLINKING AND DEGRADATION OF POLYMERS Giuseppe Spadaro, Sabina Alessi, Clelia Dispenza 167 Chapter 8 RADIATION-INDUCED OXIDATION OF POLYMERS Ewa M. Kornacka 183 Chapter 9 RADIATION-INDUCED GRAFTING Marta Walo 193 Chapter 10 RELEVANT METHODOLOGIES FOR THE CHARACTERIZATION OF IRRADIATED MATERIALS Cornelia Vasile, Elena Stoleru, Sossio Cimmino, Clara Silvestre 211 VOLUME 2 Chapter 11 CROSSLINKING OF POLYMERS IN RADIATION PROCESSING Grażyna Przybytniak 249 Chapter 12 RADIATION STERILIZATION Andrzej Rafalski, Magdalena Rzepna, Urszula Gryczka, Sylwester Bułka 269 Chapter 13 RADIATION PROCESSING OF POLYMERS IN AQUEOUS MEDIA Clelia Dispenza, Sabina Alessi, Giuseppe Spadaro 291 Chapter 14 RADIATION MODIFICATION OF POLYSACCHARIDES AND THEIR COMPOSITES/NANOCOMPOSITES Krystyna A. Cieśla 327 Chapter 15 ESTABLISHED AND EMERGING APPLICATIONS OF RADIATION-INDUCED GRAFT POLYMERIZATION Olgun Güven 355 Chapter 16 FUNDAMENTAL ASPECTS OF RADIATION-INDUCED CURING OF COMPOSITES Xavier Coqueret, Guillaume Ranoux 375 Chapter 17 RADIATION METHODS AND USES IN NANOTECHNOLOGY Dagmara Chmielewska 395 Chapter 18 RADIATION USE IN PRODUCING TRACK-ETCHED MEMBRANES Wojcie ch Starosta 415 Chapter 19 RADIATION PRETREATMENT OF BIOMASS Murat Torun 447 Chapter 20 APPLICATION OF RADIATION TECHNOLOGY TO FOOD PACKAGING Clara Silvestre, Sossio Cimmino, Elena Stoleru, Cornelia Vasile 461 Chapter 21 APPLICATION OF RADIATION TECHNOLOGIES FOR THE MODIFICATION OF ELECTRONIC DEVICES Zbigniew Zimek 485 Chapter 22 FUTURE DEVELOPMENTS IN RADIATION PROCESSING Andrzej G. Chmielewski 501 Chapter 11 CROSSLINKING OF POLYMERS IN RADIATION PROCESSING Grażyna Przybytniak Institute of Nuclear Chemistry and Technology, Dorodna 16, 03-195 Warszawa, Poland 1. INTRODUCTION The fi rst signifi cant industrial use of radiation processing was implemented in the late 1950s, shortly after the discovery of the crosslinking of olefi n polymers using ionizing radiation [1, 2]. The practical applications for radiation process- ing have since grown. Now this process technology is used to manufacture many articles, e.g. heat shrinkable tubing and tapes, encapsulations for indus- trial products, polyolefi n foams, etc. [3]. The process is widely used in the wire and cable industry to crosslink the insulation and jacketing, with some formu- lations able to suppress fl ame propagation, and, being crosslinked, demonstrat- ing increased abrasion resistance and resistance to fl uids. Radiation crosslink- ing of polymeric pipes for water distribution is another product area. Controlled radiation partial crosslinking of the automobile tire plies enhances the dimen- sional stability of cord placement and reduces material consumption. In medi- cal device area, radiation processing is used to manufacture hydrogels and to modify ultra-high molecular weight polyethylene (UHMWPE) for implants. Radiation processing is supported by the continued progress in electron beam (EB) accelerator development [4, 5]. A variety of electron beam para- meters, such as energy and power, scan width, etc., broadens the range of ap- plications. High power accelerators, up to 700 kW, increase the output rate and make the radiation processing cost-effective and competitive with chemical processing [6, 7]. Additionally, irradiated products require neither extra addi- tives nor thermal treatment. These benefi ts together with low power demand make radiation process a green technology [8, 9]. The practical aspects of radiation crosslinking demonstrate many product benefi ts [10-12]. The generation of intermolecular bonds between polymeric chains improves various product features, such as: mechanical properties, re- 250 Applications of ionizing radiation in materials processing sistance to corrosive substances, thermal stability, processability, etc. Radiation processing can lead to an improvement in product quality and usefulness. In the summary the innovative applications and trends in radiation tech- nologies are discussed. 2. RADIATION PROCESSING IN INDUSTRY AND MEDICAL APPLICATIONS 2.1. ELECTRICAL WIRE AND CABLE In January 1957, Paul Cook founded Raytherm Wire and Cable to take advantage of electron beam induced crosslinking of polyethylene (PE) [13]. Since then, the wire and cable industry has continued to adopt this type of production. The growing demand for crosslinked products stems from their higher quality compared to standard cables and their improved capability to withstand degrading environments [14, 15]. The uses of crosslinked wire and cable are found in various industries, such as: aerospace, automotive, railway, miniaturized electronic equipment and even solar panels. A key challenge was the development of a non-toxic, low smoke, halogen free insulation and jacketing formulation [16, 17]. Radiation crosslinked wire and cable jacketing is thinner and lighter than competitive materials and, thus, occupies smaller space which is needed in cars, planes and other means of transport. Additionally, the crosslinked, three-dimensional polymer structure does not allow the polymer to melt at elevated temperatures which supports fl ame propagation resistance. The composition of wire and cable jacketing varies and uses a wide range of polymers: polyolefi ns, as polyethylene (PE), blends of PE, ethylene-propyl- ene rubber (EPR) or ethylene-propylene-diene modifi ed elastomers (EPDM), ethylene-vinyl acetate copolymers (EVA), chlorosulfonated polyethylene (CSPE), poly(vinylidene fl uoride) (PVDF), and ethylene tetrafl uoroethylene (ETFE). The second major component is a fl ame retardant usually in the form of aluminum hydroxide (Al(OH)3) or magnesium hydroxide (Mg(OH)2). There are also many other additives: antioxidants, plasticizers, lubricants, colorants, stabilizers, inorganic fi llers, zinc oxide, etc. During irradiation, the interfacial effects between the conductor made of copper or aluminum and the insulation should be considered since: • Irradiation is usually accompanied by some low molecular weight gaseous by-products, such as hydrogen in the case of polyethylene. If not diffused through the jacketing, the released molecules could disrupt the adhesion Chapter 11 251 (a) (b) (c) Fig.1. (a) Scheme of fi gure eight arrangement of under beam facility for radiation processing of cables. (b) Cross-section of wire illustrating penetration of EB by thick- ness of insulation varying in the range of W-2A. (c) Quasi multi-sided crosslinking during under beam cable transportation. 252 Applications of ionizing radiation in materials processing between the polymer and the conductor, thus impairing the functionality of the wire. • Since the specifi c heat of metals is much lower than that of polymers, the heat generated as a result of radiation deposition is transferred from the metal conductor to the polymeric insulation what might undermine the in- tegrity of the insulation. • Some metals, particularly copper, are very effi cient catalysts for redox reac- tions. In contact with polymeric insulation, such metals can prompt oxida- tive degradation by stimulating decomposition of peroxide structures and subsequent radical induced processes. These adverse effects can be eliminated by controlling the parameters of the electron beam and by suitable cable under beam transport systems and, if needed, supplemented with a cooling system. Important parameters in characterizing the appropriateness of the radia- tion crosslinking process are the dose and the homogeneity
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