Journal of Polymer Science Part B: Polymer Physics, Vol.34, No.1, 57-64, 1996
The Microfibrillar Network in Gels of Poly(Gamma-Benzyl-L-Glutamate) in Benzyl Alcohol
The gelation and gel-melting phenomena in semidilute isotropic solutions of poly(gamma-benzyl-L-glutamate) (PBLG) in benzyl alcohol were studied by small-angle neutron scattering measurements, using a deuterated solvent, and by cryotransmission electron microscopy. The reversible gels are formed when the solution is cooled below the gelation temperature, and the gels melt upon heating. Hysteresis, of about 15 degrees C, is observed between gelation and melting temperatures. In the isotropic solution, PBLG exists as isolated helices. Gelation is apparent as a large increase in the intensity scattered at low angles, signifying the heterogeneous microstructure of the gel. Direct visualization by electron microscopy of vitrified gel samples shows the formation of a microfibrillar network. The dimension of the observed microfibrils is about 10 nm. Upon melting, microstructural changes appear in a temperature range of about 10 degrees C. The unique feature of the gel melting is that initially only the intensity in the mid-angle range decreases. This is interpreted as thickening of the microstructure due to melting of the thinner microfibrils. The final stage marks the melting of the thicker microfibrils.
Keywords:RIGID ROD POLYMER;CONCENTRATION FLUCTUATION;ISOTROPIC-PHASE;STIFF POLYMERS;L-GLUTAMATE) SOLUTIONS;MOLECULAR AGGREGATION;SEMIFLEXIBLE POLYMERS;ELECTRON-MICROSCOPY;GELATION;SYSTEM