Thermodynamic interactions of natural and of man-made cellulose fibers with water

The vapor pressure of water was measured for binary mixtures with cellulose containing fabrics at 37 °C by means of two complementary methods. Different types of fabrics were studied: One consisting exclusively of cellulose fibers, either of natural origin (cotton) or regenerated from solutions in the mixed solvent NMMO/water (Lyocell fibers, CLY) and another kind of fabric containing polyethylene terephthalate (PET) fibers in addition to CLY fibers. The Flory-Huggins interaction parameters χ and their composition dependence calculated from these vapor pressure data are broadly similar for cotton and for CLY, apart from the fact that water interacts somewhat more favorably with CLY than with cotton. In both cases the χ values pass successively a maximum and a minimum as the concentration of water rises. The experiments performed with the fabrics containing two types of fibers demonstrate that the water uptake of PET is negligible as compared with that of cellulose. The results for the system water/cellulose fibers obtained at 37 °C differ fundamentally from corresponding data for 80 °C, reported for cellulose films prepared from solutions in dimethylacetamide + LiCl. The maximum water uptake of cellulose is determined by its degree of crystallinity. In all cases it is possible to model the Flory-Huggins interaction parameters as a function of composition quantitatively by means of an approach subdividing the dilution process conceptually into two separate steps: Contact formation between the dissimilar components (keeping their conformation constant) and subsequent relaxation of the system into the equilibrium state. Similarities and dissimilarities of the systems water/polysaccharide are being discussed in detail.