Effect of moisture content on viscoelastic properties of hydrated gliadin

The effect of moisture content on the linear viscoelastic properties of gliadin hydrated to 30 and 40% moisture content [gliadin(30%) and gliadin(40%), respectively] was determined. These two moisture contents bracketed the equilibrium moisture content of gliadin, which was 37.6%. Time-temperature-superposition was used to develop master curves of the elastic modulus (G'), viscous modulus (G"), dynamic viscosity (eta'), and tan 5 (G"/G') from isothermal frequency sweep data obtained at 25-80degreesC. Smooth master curves were obtained for all of the viscoelastic functions for both gliadins. G' and G" showed a power law dependency on frequency (with G" > G') for frequencies <0.1 rad/sec for gliadin(30%) and <1 rad/sec for gliadin(40%). The low-frequency-limiting slopes on log-log coordinates for G' and G" were 0.700 and 0.646 for gliadin(30%), respectively. Corresponding values were 0.658 and 0.614 for gliadin(40%). G' crossed over G" at a frequency of approximate to0.3 rad/sec for gliadin(30%), while G' and G" for gliadin(40%) only became congruent at higher frequencies. Both gliadin samples showed appreciable frequency dependence of eta' over the entire frequency range, while eta' was greater for gliadin(30%) than for gliadin(40%) at all frequencies, but especially at the lowest frequencies. Tan 6 increased gradually from a value of approximate to1 at 0.1 rad/sec to 2 at the lowest frequency of 0.0002 rad/sec for both gliadins, but tan 6 decreased rapidly for gliadin(30%) for frequencies >0.1 rad/sec. Thus, the main difference between gliadin(30%) and gliadin(40%) was that elastic effects G' > G" and decreased tan 6 were more prominent for gliadin(30%) at the higher frequencies. In addition, the frequency dependence of G', G", eta', and tan 6 for the two gliadin samples was compared directly with two samples of poly(dimethylsiloxane) (PDMS) a linear silicone-based entangled polymer with molecular weights (MW) of 140,000 and 385,000. The substantial differences in the magnitude and overall patterns of the frequency dependence of the viscoelastic functions between the gliadin and PDMS samples was attributed to the dominant effect that noncovalent secondary associations apparently have on the linear viscoelasticity of the gliadins. The energy of activation for flow (determined from the temperature dependence of the shift factors) for the gliadin samples for the range 25-45degreesC was higher than is typical for entangled linear polymer melts. The activation energy decreased for temperatures greater than g 60degreesC for gliadin(30%) and approximate to50degreesC for gliadin(40%). Thus, hydrated gliadin cannot be considered to be a simple viscoelastic liquid.