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Mechanisms and Characterization of the Pulsed Electron-Induced Grafting of Styrene onto Poly(tetrafluoroethylene-co-hexafluoropropylene) to Prepare a Polymer Electrolyte Membrane.

  • Kim B a   Department of Materials Science and Engineering, University of Maryland, College Park, Maryland 20742-2115.
  • Weaver A a   Department of Materials Science and Engineering, University of Maryland, College Park, Maryland 20742-2115.
  • Chumakov M a   Department of Materials Science and Engineering, University of Maryland, College Park, Maryland 20742-2115.
  • Pazos IM a   Department of Materials Science and Engineering, University of Maryland, College Park, Maryland 20742-2115.
  • Poster DL d   National Institute of Standards and Technology, Gaithersburg, Maryland 20899.
  • Gaskell K b   Department of Chemistry, University of Maryland, College Park, Maryland 20742-2115.
  • Han DH e   School of Chemical Engineering and Technology, Yeungnam University, Gyeongsangbuk-do, Republic of Korea.
  • Scherer G f   Electrochemistry Laboratory, Paul Scherrer Institut, CH-5232 Villigen PSI, Switzerland.
  • Yandrasits MA g   3M Fuel Cell Components Program, St. Paul, Minnesota 55144.
  • Lee BC c   Korea Atomic Energy Research Institute, Daejeon, 305353, Republic of Korea.
  • Al-Sheikhly M a   Department of Materials Science and Engineering, University of Maryland, College Park, Maryland 20742-2115.
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  • 2018-06-19
Published in:
  • Radiation research. - 2018
Electrolytes
Electrons
Free Radicals
Gamma Rays
Kinetics
Membranes, Artificial
Polymerization
Polymers
Polytetrafluoroethylene
Styrene
English During the pulsed-electron beam direct grafting of neat styrene onto poly(tetrafluoroethylene-co-hexafluoropropylene) (FEP) substrate, the radiolytically-produced styryl and carbon-centered FEP radicals undergo various desired and undesired competing reactions. In this study, a high-dose rate is used to impede the undesired free radical homopolymerization of styrene and ensure uniform covalent grafting through 125-μm FEP films. This outweighs the enhancement of the undesired crosslinking reactions of carbon-centered FEP radicals and the dimerization of the styryl radicals. The degree of uniform grafting through 125-μm FEP films increases from ≈8%, immediately after pulsed electron irradiation to 33% with the subsequent thermal treatment exceeding the glass transition temperature of FEP of 39°C. On the contrary, steady-state radiolysis using 60Co gamma radiolysis, shows that the undesired homopolymerization of the styrene has become the predominant reaction with a negligible degree of grafting. Time-resolved fast kinetic measurements on pulsed neat styrene show that the styryl radicals undergo fast decays via propagation homopolymerization and termination reactions at an observed reaction rate constant of 5 × 108 l · mol-1 · s-1. The proton conductivity of 25-μm film at 80°C is 0.29 ± 0.01 s cm-1 and 0.007 s cm-1 at relative humidity of 92% and 28%, respectively. The aims of this work are: 1. electrolyte membranes are prepared via grafting initiated by a pulsed electron beam; 2. postirradiation heat-treated membranes are uniformly grafted, ideal for industry; 3. High dose rate is the primary parameter to promote the desired reactions; 4. measurement of kinetics of undesired radiation-induced styrene homopolymerization; and 5. The conductivity of prepared membranes is on par or higher than industry standards.
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  • English
Open access status
green
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https://sonar.ch/global/documents/159261
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