Chitosan crystallization, performed by simple drying of an oligomer or poly
mer solution on a glass or mica surface, was studied at room temperature. P
olarizing microscopy revealed the formation of two-dimensional spherulites
that were shown to have a negative birefringence. After metal shadowing, el
ectron microscopy investigations allowed the molecular arrangements of thes
e structures to be described more precisely. X-ray and selected area electr
on diffraction experiments led to the identification of the crystalline str
ucture which corresponds to the monoclinic chitosan hydrochloride. The pres
ence of water in the crystalline lattice was also revealed.