Date of Award

12-2011

Document Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Legacy Department

Chemical Engineering

Advisor

Thies, Mark C

Committee Member

Bruce , David A

Committee Member

Kitchens , Christopher L

Committee Member

Lickfield , Gary C

Abstract

Although researchers have previously investigated the effect of precursor differences on the final properties of activated carbon fibers (ACFs), those precursors were not well-characterized. In particular, detailed information about their molecular composition and anisotropy was not available.
In this study, seven oligomeric fractions, each of well-defined composition and molecular weight (mol wt) distribution, were isolated from a commercially produced isotropic petroleum pitch (i.e., Marathon M–50) and used for the production of ACFs. Four of these precursors of varying oligomeric composition were fully isotropic and three contained different levels of mesophase, so that the effects of molecular composition and molecular order were successfully isolated from each other. After the precursors were melt–spun into fibers and stabilized, they were processed by so–called “direct activation”, whereby carbonization and activation occurred simultaneously. Separate carbonization tests were also carried out in order to separate out the effects of carbonization vs. activation.
Carbonization weight loss was found to be higher for fibers prepared from lower average mol wt (480–550 Da) precursors. The presence of mesophase per se did not affect weight loss during carbonization. On the other hand, activation weight loss (∼28 percent) was found to be essentially independent of precursor mol wt for all isotropic fibers. (Activation weight loss for mesophase–containing fibers was much lower.)
The micropore volume of the ACFs was found to increase with decreasing precursor mol wt. However, the ratio of pores smaller than 7 Å (i.e., the desired pore size for hydrogen storage) to the total pore volume (3.9–30 Å) was found to be essentially constant for all isotropic precursors, suggesting that a similar activation mechanism occurred for all of these materials, with both new pore formation and pore widening proceeding at similar rates. For mesophase–containing precursors, on the other hand, this pore volume ratio significantly decreased with increasing mesophase content, indicating that pore widening dominates over new pore formation for this morphology.
In conclusion, this study showed that the lowest mol wt precursor (i.e., a 99 percent dimer cut with a mol wt of 480 Da) attained the highest narrow micropore (≤7 Å) volume required for hydrogen storage.

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