A rheo-optical device outfitted with a Peltier temperature control for rapid temperature changes has been constructed that allows simultaneous measurement of the optical rotation of light and the controlled-stress rheology. Optical rotation provides a direct in situ assessment of the extent of triple helix reversion in a gelatin solution undergoing physical gelation in the rheometer. Thermal gelation of gelatin was monitored over a wide range of concentrations and temperatures. Assuming dynamic scaling theory applies, viscosity data below the gel point were used to evaluate the gel point and determine the value of the viscosity exponent. Above the gel point, creep-recovery experiments are used to measure the shear modulus and determine the dynamic scaling elastic modulus exponent. During thermal gelation, the time-dependent optical rotation shows an initial rapid growth region where new helices are formed, followed by a slower growth region involving helix lengthening. For cases where the gel point occurs before the helix reversion slows appreciably, the viscosity and modulus exponents are found to be depend on gelatin concentration, but not on temperature. However, anomalous exponents are measured using the same methods at higher temperatures, where the helix reversion slows appreciable before the gel point is reached. These results suggest that extreme caution must be used in evaluating dynamic exponents from any physical gelation process. The observed concentration dependences of the dynamic scaling exponents are discussed in terms of chain overlap and entanglement. For gelatin gelation, the plethora of different, reported percolation exponents in the literature are rationalized.
All Science Journal Classification (ASJC) codes
- Organic Chemistry
- Polymers and Plastics
- Inorganic Chemistry
- Materials Chemistry