Swelling of Model Films of Cellulose Having Different Charge Densities and Comparison to the Swelling Behavior of Corresponding Fibers

Abstract

Cellulose model films with different charge densities were prepared by spin-coating dissolved cellulose in N-methylmorpholine-N-oxide onto SiO2 surfaces. The swelling of the model cellulose films due to exposure to solutions of different electrolytes and at different ionic strengths and pH values were studied using QCM-D (quartz crystal microbalance with dissipation monitoring). Results show that at pH 5, there is a swelling of the film at a low electrolyte concentration (10-4−10-2 M), whereas the deswelling of the film was observed at a high electrolyte concentration (10-1−1 M). A considerable swelling of the films is seen when they are treated with deionized water with an increasing pH. The swelling of the films is accompanied by an increase in dissipation, that is, a softening of the material, and the deswelling by a decrease in dissipation, that is, a stiffening of the material. Furthermore, exposure of the films to solutions of different electrolytes affected the swelling of the layer. In this respect, the swelling response of Na2SO4 differs from that of NaCl and CaCl2 by showing simultaneously high swelling and low dissipation values. The results also show that the rate of swelling reaches its lowest value as the electrolyte concentration reaches the detected limit for the deswelling. The QCM-D results are compared to the swelling of the corresponding carboxymethylated fibers, where a similar behavior was found. However, for the fibers a marked deswelling occurred at a high electrolyte concentration, but only a minor deswelling of the cellulose film was observed. This difference between the materials can be ascribed to noncovalent bonds within the film that will not reform when the swelling forces are decreased at high electrolyte concentrations. A direct measurement of the thickness changes was performed using atomic force microscopy, which shows that the change in frequency measured with QCM-D for the films treated with different NaCl electrolyte concentrations corresponds to changes of 1−2%.