Natural polymers, as extracted from biomass, may exhibit large macromolecular polydispersity. We investigated the impact of low molar mass chitosan (LMW, DPw~115) on the properties of chitosan fibers obtained by wet spinning of chitosan solutions with bimodal distributions of molar masses. The fiber crystallinity index (CrI) was assessed by synchrotron X-ray diffraction and the mechanical properties were obtained by uniaxial tensile tests. The LMW chitosan showed to slightly increase the crystallinity index in films which were initially processed from the bimodal molar mass chitosan solutions, as a result of increased molecular mobility and possible crystal nucleating effects. Nevertheless, the CrI remained almost constant or slightly decreased in stretched fibers at increasing content of LMW chitosan in the bidisperse chitosan collodion. The ultimate mechanical properties of fibers were altered by the addition of LMW chitosan as a result of a decrease of entanglement density and chain orientation in the solid state. An increase of crystallinity might not be expected from LMW chitosan with a still relatively high degree of polymerization (DPw ≥ 115). Instead, different nucleation agents-either smaller molecules or nanoparticles-should be used to improve the mechanical properties of chitosan fibers for textile applications.
Keywords: chitosan; crystallinity; fiber spinning; polysaccharide X-ray scattering; short polymer chains; textile applications.