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Development of structure in natural silk spinning and poly(vinyl alcohol) hydrogel formation

Patricia Jeanene Willcox, University of Massachusetts Amherst


This research involves the characterization of structure and structure formation in aqueous systems. Particularly, these studies investigate the effect of various processing variables on the structure formation that occurs upon conversion from aqueous solution to fiber or hydrogel. The two processes studied include natural silk fiber spinning and physical gelation of poly(vinyl alcohol), PVOH, in water. The techniques employed combine cryogenic technology for sample preparation and direct observation by transmission electron microscopy with electron diffraction, atomic force microscopy, optical rheometry, X-ray scattering and optical microscopy. In order to explore the full range of structure formation in natural silk spinning, studies are conducted in vivo and in vitro. In vivo structural investigations are accomplished through the cryogenic quenching and subsequent microtoming of live silk-spinning animals, Nephila clavipes (spider) and Bombyx mori (silkworm). Observations made using transmission electron microscopy, electron diffraction and atomic force microscopy indicate a cholesteric liquid crystalline mesophase of aqueous silk fibroin in both species. The mechanism of structure formation in solution is studied in vitro using optical rheometry on aqueous solutions made from regenerated Bombyx mori cocoon silk. Concentrated solutions exhibit birefringence under flow, with a wormlike conformation of the silk molecules in concentrated salt solution. Changes in salt concentration and pH of the aqueous silk solutions result in differing degrees of alignment and aggregation. These results suggest that structural control in the natural silk spinning process is accomplished by chemical manipulation of the electrostatic interactions and hydrogen bonding between chains. Application of cryogenic methods in transmission electron microscopy also provides a unique look at hydration-dependent structures in gels of poly(vinyl alcohol) produced by freeze-thaw processing. Morphologies ranging from circular pores to fibrillar networks are observed in gels formed from aqueous PVOH solutions subjected to cycles of freezing and thawing. These morphologies can be directly associated with the progressive nature of the mechanism of gelation as it proceeds from liquid-liquid phase separation to crystallization with increased cycling. A comparison of the structures produced by cycling and by aging suggests that there is a similarity in structural changes, but a superposition of the effects of cycling and aging is not possible.

Subject Area

Materials science|Chemistry|Polymers

Recommended Citation

Willcox, Patricia Jeanene, "Development of structure in natural silk spinning and poly(vinyl alcohol) hydrogel formation" (1998). Doctoral Dissertations Available from Proquest. AAI9909233.