We have attempted to develop a technique to characterize the amorphous or non-crystalline regions in cellulosic materials using Fourier transform infra-red spectroscopy to monitor the deuteration process for a film sample, followed by a subsequent kinetic analysis. It is possible that the H-D exchange reaction rate for OH groups in the films may reveal the nature or extent of the amorphous regions. The morphological contribution of the film surface to the analysis was determined using atomic force microscopy for both cast and coagulated cellulose films. The results showed that the surface of cast films are much rougher than that of coagulated ones. However, during the initial 5 min of the deuteration process, both types of films gave similar values for the D2O diffusion coefficient, indicating that the differences in the cellulose film surfaces did not have a significant effect on the D2O penetration diffusion rate. Next we examined whether the OH-OD exchanging rate, which was found to exhibit pseudo-first-order kinetics, could or could not be used to comment on the nature or extent of amorphous regions present in the films. We also examined the relationship, if any, between the exchange rate and the diffusion coefficient, other amorphous cellulosic films, composed of regioselectively methylated cellulose, such as 2,3-di-O- methylcellulose (23MC) and 6-O-methylcellulose (6MC) were also studied and the results were compared with the cast and coagulated films of pure cellulose. The results indicated that the non-crystalline phase of cellulosic films are not composed solely of homogeneous domains nor are they totally amorphous but rather they were found to have a heterogeneous organization.
All Science Journal Classification (ASJC) codes
- Organic Chemistry
- Polymers and Plastics
- Materials Chemistry