Title page for ETD etd-09162007-203027

Type of Document Dissertation
Author Li, Yanxiang
Author's Email Address lyxiang@vt.edu
URN etd-09162007-203027
Title The Influence of Aromatic Disulfonated Random and Block Copolymers' Molecular Weight, Composition,and Microstructure on the Properties of Proton Exchange Membranes for Fuel Cells
Degree PhD
Department Macromolecular Science and Engineering
Advisory Committee
Advisor Name Title
McGrath, James E. Committee Chair
Davis, Richey M. Committee Member
Dillard, John G. Committee Member
Riffle, Judy S. Committee Member
Taylor, Larry T. Committee Member
  • molecular weight
  • poly(arylene ether sulfone)
  • morphology
  • multiblock
  • random
  • poly(arylene ether ketone)
  • disulfonated copolymers
  • proton exchange membrane
  • fuel cell
Date of Defense 2007-08-31
Availability unrestricted

The purity of the disulfonated monomer, such as 3,3’-disulfonated-4,4’-dichlorodiphenyl sulfone (SDCDPS), was very important for obtaining high molecular weight copolymers and accurate control of the oligomer’s molecular weight. A novel method to characterize the purity of disulfonated monomer, SDCDPS, was developed by using UV-visible spectroscopy. This allowed for utiliziation of the crude SDCDPS directly in the copolymerization to save money, energy, and time. Three series of tert-butylphenyl terminated disulfonated poly(arylene ether sulfone) copolymers (BPSH35, 6FSH35, and 6FSH48) with controlled molecular weights(Mn), 20 to 50 kg•mol-1, were successfully prepared by the direct copolymerization method. The molecular weight of the copolymer was controlled by a monofunctional monomer tert-butylphenyl, and characterized by the combination of 1H NMR spectra and modified intrinsic viscosity measurements in NMP with 0.05 M LiBr, which was added to suppress the polyelectrolyte effect. The mechanical properties of the membranes, such as the modulus, strength and elongation at break, were improved by increasing the molecular weights, but water uptake and proton conductivities found insensitive to copolymers’ molecular weights.

Three series of disulfonated poly(arylene ether ketone) random copolymers have been synthesized and comparatively studied, according to their different chemical structures, for use as proton exchange membranes. The copolymers containing more flexible molecular structures had higher water uptake and proton conductivity than the rigid structures at the same ion exchange capacity. This may be due to the more flexible chemical structures being able to form better phase separated morphology and higher hydration levels.

A new hydrophobic-hydrophilic multiblock copolymer has been successfully synthesized based on the careful coupling of a fluorine terminated poly(arylene ether ketone) (6FK) hydrophobic oligomer and a phenoxide terminated disulfonated poly(arylene ether sulfone) (BPSH) hydrophilic oligomer. AFM images and the water diffusion coefficient results confirmed that the multiblock copolymer formed better proton transport channels. This multiblock copolymer showed comparable proton conductivity and fuel cell performance to the Nafion® control and had much better proton transport properties than random ketone copolymers under partially hydrated conditions. This suggested that the multiblock copolymers are promising candidates for proton exchange membranes especially for applications at high temperatures and low relative humidity.

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