Mechanisms and Characterization of the Pulsed Electron-Induced Grafting of Styrene onto Poly(tetrafluoroethylene-co-hexafluoropropylene) to Prepare a Polymer Electrolyte Membrane.
Radiat Res
; 190(3): 309-321, 2018 09.
Article
em En
| MEDLINE
| ID: mdl-29912620
ABSTRACT
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.
Texto completo:
1
Coleções:
01-internacional
Base de dados:
MEDLINE
Assunto principal:
Polímeros
/
Eletrólitos
/
Polimerização
/
Membranas Artificiais
Tipo de estudo:
Guideline
Idioma:
En
Revista:
Radiat Res
Ano de publicação:
2018
Tipo de documento:
Article