Abstract
EPR application to polymers has been closely related to the research and development of polymer modification by radiation processing. The free radicals induced in polymer chains by irradiation can initiate chemical reactions at rather low temperature ranges, therefore, the radical reactions can be followed by EPR measurement. EPR studies of polymers were applied mainly for the analysis of graft polymerization by the pre-irradiation method and the analysis of radiation crosslinking, which contributed to the development of polymer materials by radiation processing. For graft polymerization, the radicals trapped in the crystalline regions of polymers migrate to the surface and initiate the graft reaction. The concentration of the trapped radicals and their rate of decay are closely related to the graft yield and rate of the grafting reaction. As the radical migration rate in the crystalline part, namely the decay rate of the trapped radicals, is determined by the temperature, the graft polymerization is much affected by the temperature. And also the trapped radicals in any polymers can be conserved for a long time by cooling the irradiated polymers even in air. Therefore, the irradiation and the graft-polymerization can be separated in place and in time. For the crosslinking of polymers, polytetrafluoroethylene (PTFE), polyacrylonitrile (PAN) fiber and polycarbosilane (PCS) fiber were selected for a specific application. The PAN fiber is a precursor of carbon fiber formation and PCS fiber is the precursor of SiC ceramic fiber. Especially the EPR studies for PCS fiber and the pyrolysis were useful for the development of radiation processing. The process of pyrolysis of PCS fiber at a high temperature involves radical reactions and could be followed by EPR measurements. A knowledge of the radical reaction mechanism contributed much to the development of a new method for SiC fiber synthesis.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
References
Dole M (1973) The radiation chemistry of macromolecules, I and II. Academic, Boston
Ranby B, Rabek J-F (1977) ESR spectroscopy in polymer research (Polymers/properties and application). Springer, Berlin
Lund A, Shiotani M, Shimsda T (2010) Principles and applications of ESR spectroscopy. Springer, Berlin
Hill DJT, Thurecht KJ, Whittaker AK (2003) A study of the radiation chemistry of poly(chlorotrifluoro-ethylene) by ESR spectroscopy. Radiat Phys Chem 68:857–864
Gamage NJW, Hill DJT, Lukey CA, Pomery PJ (2004) The use of high energy radiation as a probe for the characterization of polyester melamine coating matrices. Radiat Phys Chem 69:487–493
Singh A, Silverman J (1991) Radiation processing of polymers. Hanser Publishers, New York
Tutiya M (1972) Nuclear magnetic resonance absorption of polytetrafluoroethylene γ-irradiated at high temperature. Jpn J Appl Phys 11:1542–1546
Sun J, Zhan Y, Zhong X (1994) Radiation crosslinking of polytetrafluoroethylene. Polymer 35:2881–2883
Oshima A, Seguchi T, Tabata Y (1994) Radiation induced crosslinking of polytetrafluoroethylene and its properties. Proceedings of 14th international symposium on fluorine chemistry, 31 July–5 Aug (Yokohama, Japan)
Oshima A, Tabata Y, Kudoh H, Seguchi T (1995) Radiation induced crosslinking of polytetrafluoroethylene. Radiat Phys Chem 45:269–273
Lappan U, Geissler U, Uhlmann S (2000) Changes in the chemical structure of polytetrafluoroethylene induced by electron beam irradiation in the molten state. Radiat Phys Chem 59:317–322
Tanso S, Okamoto J, Ishigaki I, Sugo T, Murata K, Takayama T (1983) A new alkaline battery separator made by pre-irradiation graft polymerization. Yuasa-Jiho (GS-Yuasa Co. Ltd.) 54:57–67
Takeda T, Tamada M, Seko N, Ueki Y (2010) Ion exchange fabric synthesized by graft polymerization and its application to ultra-pure water production. Radiat Phys Chem 79:223–226
Sugo T (1998) Development of separation membrane by radiation induced graft polymerization. Chemical Industry (in Japanese) 7:53–60
Seko N, Tamada M, Yoshii F (2005) Current status of adsorbent for metal ions with radiation grafting and crosslinking techniques. Nucl Instrum Methods B 236:21–29
Waterman DC, Dole M (1970) Radiation chemistry of polyethylene. X. Kinetics of the conversion of alkyl to ally free radicals. J Phys Chem 74:1913–1918
Shimada S, Kashiwabara H, Sohma J (1970) ESR studies of the photodegradation of polyethylene containing trapped allylic free radicals. J Polym Sci (Part A-2) 8:1291–1298
Seguchi T, Tamura N (1974) Electron spin resonance studies on radiation graft copolymerization in polyethylene. I. Grafting by alkyl radicals trapped in irradiated polyethylene. J Polym Sci Poly Chem Ed 12:167–1682
Seguchi T, Tamura N (1974) Electron spin resonance studies on radiation graft copolymerization in polyethylene. II. Grafting by allyl radicals trapped in irradiated polyethylene. J Polym Sci Poly Chem Ed 12:1953–1964
Seguchi T, Tamura N (1973) Mechanism of decay of alkyl radicals in irradiated polyethylene on exposure to air as studied by electron spin resonance. J Phys Chem 77:40–44
Ishigaki I, Sugo T, Senoo K, Takayama T, Machi S, Okamoto J, Okada T (1981) Synthesis of ion exchange membrane by radiation grafting. Radiat Phys Chem 18:899–905
Ishigaki I, Sugo T, Senoo K, Okada T, Okamoto J, Machi S (1982) Graft polymerization of acrylic acid onto polyethylene film by preirradiation method. I. Effects of preirradiation dose, monomer concentration, reaction temperature, and film thickness. J Appl Polym Sci 27:1033–1041
Ishigaki I, Sugo T, Senoo K, Takayama T, Okada T, Okamoto J, Machi S (1982) Graft polymerization of acrylic acid onto polyethylene film by preirradiation method. II. Effects of oxygen at irradiation, storage time after irradiation, Mohr’s salt, and ethylene dichloride. J Appl Polym Sci 27:1043–1051
Aymes-Chodur C, Esnouf S, LeMoel A (2001) ESR studies in γ-irradiated and PS-radiation-grafted poly(vinylidene fluoride). J Polym Sci Part B: Polym Phys 39:1437–1448
Chen J, Yang L, Wu M, Xi Q, He S, Li Y, Nho Y (2000) Preparation of interpenetrating polymer networks by two times grafting of monomers onto pre-irradiated polypropylene film. Radiat Phys Chem 59:313–316
Shah J M, Fuzail M (2007) Examination of the long-lived, oxygen-induced radicals in irradiated ultra-high molecular weight polyethylene. Nucl Instrum Methods Phys (Part B) 265:67–71
Kasser M J, Silverman J, Al-Sheikhly M (2010) EPR simulation of polyenyl radicals in ultrahigh molecular weight polyethylene. Macromolecules 43:8262–8867
Zhao Y, Wang M, Tang Z, Wu G (2010) ESR study of free radicals in UHMW-PE fiber irradiated by gamma rays. Radiat Phys Chem 79:429–433
Kusano H, Asai T, Setogawa A, Nishi H, Yamamoto Y (2001) Development of crosslinked PTFE and the applied products. Hitachi Cable Rev 20:153–158
Tang Z, Wang M, Zhao Y, Wu G (2010) Tribological properties of radiation crosslinked polytetrafluoroethylene sheets. Wear 269:485–490
Oshima A, Ikeda S, Seguchi T, Tabata Y (1997) Improvement of radiation resistance for polytetrafluoroethylene (PTFE) by radiation crosslinking. Radiat Phys Chem 49:279–284
Oshima A, Seguchi T, Tabata Y (1997) ESR study on free radicals trapped in crosslinked polytetrafluoroethylene (PTFE). Radiat Phys Chem 50:601–606
Oshima A, Seguchi T, Tabata Y (1999) ESR study on free radicals trapped in crosslinked polytetrafluoroethylene (PTFE)–II radical formation and reactivity. Radiat Phys Chem 55:61–71
Tamura N (1962) Temperature dependence of ESR spectra of irradiated polytetrafluoroethylene. J Phys Chem 37:479–484
Iwasaki M (1971) Electron spin resonance of irradiated fluorine compounds. Fluorine Chem Rev 5:1–10
Yamaki T, Asano M, Maekawa Y, Morita Y, Suwa T, et al (2003) Radiation grafting of styrene into crosslinked PTFE films and subsequent sulfonation for fuel cell applications. Radiat Phys Chem 67:403–407
Sato K, Ikeda M, Oshima A, Tabata Y, Washio M (2003) Study on polyelectrolyte membrane of crosslinked PTFE by radiation-grafting. Nucl Instrum Methods B 208:424–428
Lappan U, Geissler U, Uhlmann S (2005) Radiation-induced grafting of styrene into radiation-modified fluoropolymer films. Nucl Instrum Methods B 236:413–419
Hasegawa S, Takahashi S, Maekawa Y, et al (2011) Radiation-induced graft polymerization of functional monomer into poly(ether-ether ketone) film and structure-property analysis of the grafted membrane. Polymer 52:98–106
Liu W, Wang M, Xing Z, Wu G (2012) The free radical species in polyacrylonitrile fibers induced by γ-irradiation and their decay behaviors. Radiat Phys Chem 81:835–839
Liu W, Wang M, Xing Z, Wu G (2014) Radiation oxidation and subsequent thermal curing of polyacrylonitrile. Radiat Phys Chem 94:9–13
Yajima S, Hayashi J, Omori M (1975) Continuous silicon carbide fiber of high tensile strength. Chem Lett 9:931–934
Yajima S, Okamura K, Hayashi J, Omori M (1976) Synthesis of continuous SiC fibers with high tensile strength. J Am Ceram Soc 59:324–327
Yajima S, Okamura K, Matsuzawa T, Hasegawa Y, Shishido T (1979) Anomalous characteristics of the microcrystalline state of SiC fibers. Nature 279:706–707
Yajima S et al (1978) United States Patent, 4,100,233, July 11
Yajima S, (1985) Handbook of composites, vol 1, Strong fibers. North Holland, Amsterdam, pp 201–237
Okamura K, Shimoo T, Suzuya K, Suzuki K (2006) SiC-based ceramic fibers prepared via organic-to-inorganic conversion process—a review. J Ceram Soc Jpn 114:445–454
Okamura K, Matsuzawa T, Hasegawa Y (1985) γ-ray irradiation curing on polycarbosilane fibers as the precursor of SiC fibers. J Mater Sci Lett 4:55–57
Sato M, Okamura K, Kawanishi S, Seguchi T (1988) Radiation effects of polycarbosilane as precursor of ceramic fiber. J Jpn Soc Powder Powder Metal 35:679–682
Okamura K, Sato M, Seguchi T, Kawanishi S (1988) SiC fiber and Si3N4 fiber obtained from electron irradiated polycarbosilane. J Jpn Soc Powder Powder Metal 35:170–173
Taki T, Okamura K, Sato M, Seguchi T, Kawanishi S (1988) A study on the electron irradiation curing mechanism of polycarbosilane fibers by solid-state 29Si high-resolution nuclear magnetic resonance spectroscopy. J Mater Sci Lett 7:209–211
Sato M, Yamamura T, Seguchi T, Okamura K (1995) Behavior of radicals on radiation crosslinking of polycarbosilane as SiC fiber precursor. Chem Soc Jpn 5:554–556
Okamura K, Seguchi T (1992) Application of radiation curing in the preparation of polycarbosilane-derived SiC fibers. J Inorg Organomet Polym 2:171–179
Seguchi T, Sugimoto M, Okamura K (1996) Radiation application for silicon carbide fiber synthesis from polycarbosilane fiber with controlled Oxygen content. Adv Mater Mech ICAM 96:221–225
Takeda M, Imai Y, Ichikawa H, Ishikawa T, Seguchi T, Okamura K (1991) Properties of the low oxygen content SiC fiber on high temperature heat treatment. Ceram Eng Sci Proc 12(7–8):1007–1018
Takeda M, Imai Y, Ichikawa H, Ishikawa T, Kasai N, Seguchi T, Okamura K (1992) Thermal stability of the low oxygen silicon carbide fibers derived from polycarbosilane. Ceram Eng Sci Proc 13(7–8):209–217
Seguchi T, Okamura K (1993) Radiation application for ceramic fiber synthesis from the precursor fiber. Kobunnshi Kakou (Japanese) 42(4):163–168
Seguchi T, Sugimoto M, Okamura K (1993) Heat resistant SiC fiber synthesis and reaction mechanisms from radiation cured polycarbosilane fiber. HT-CMC (I):51–57 (Woodhead Publishing) ed. by Naslain R, Lamon J, Doumeingts D (Bordeaux)
Sugimoto M, Shimoo T, Okamura K, Seguchi T (1995) Reaction mechanisms of silicon carbide fiber synthesis by heat treatment of polycarbosilane fibers cured by radiation: I, Evolved gas analysis. J Am Ceram Soc 78(4):1013–1017
Sugimoto M, Shimoo T, Okamura K, Seguchi T (1995) Reaction mechanisms of silicon carbide fiber synthesis by heat treatment of polycarbosilane fibers cured by radiation: II, Free radical reaction. J Am Ceram Soc 78(7):1849–1852
Narisawa M, Shimoda M, Okamura K, Seguchi T (1995) Reaction mechanism of the pyrolysis of polycarbosilane and polycarbosilazane as ceramic precursors. Bull Chem Soc Jpn 68:1098–1104
Kashiwabara H, Seguchi T (1992) Radiation-induced oxidation of plastics. In: Singh A, Silverman J (eds) Radiation processing of polymers. Hanser, New York
Sugimoto M, Idesaki A, Tanaka S, Okamura K (2003) Development of silicon carbide micro-tube from precursor polymer by radiation oxidation. Key Eng Mater 247:133–136
Taki T, Inui M, Okamura K, Sato M, Seguchi T (1991) A study of nitridation process of polycarbosilane fibers by solid state high resolution NMR. Appl Mag Res 2:61–68
Kamimura S, Seguchi T, Okamura K (1999) Development of silicon nitride fiber from Si-containing polymer by radiation curing and its application. Radiat Phys Chem 54:575–581
Author information
Authors and Affiliations
Corresponding author
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2014 Springer International Publishing
About this chapter
Cite this chapter
Seguchi, T. (2014). EPR Application to Polymers: Radiation Induced Crosslinking and Graft Polymerization. In: Lund, A., Shiotani, M. (eds) Applications of EPR in Radiation Research. Springer, Cham. https://doi.org/10.1007/978-3-319-09216-4_10
Download citation
DOI: https://doi.org/10.1007/978-3-319-09216-4_10
Published:
Publisher Name: Springer, Cham
Print ISBN: 978-3-319-09215-7
Online ISBN: 978-3-319-09216-4
eBook Packages: Chemistry and Materials ScienceChemistry and Material Science (R0)