Hydrothermal Transformation of Wood Cellulose Crystals into Pseudo-Orthorhombic Structure by Cocrystallization

The ultrastructural transformation of wood cellulose crystals by hydrothermal treatment was followed by synchrotron and standard X-ray scattering experiments. When treated at 200 °C for 2 h in the presence of an excess of water, a significant sharpening of the equatorial reflections of crystalline cellulose was observed, and the average crystallite size, estimated from the X-ray line broadening, was twice as large as that of untreated wood cellulose. During the treatment, the cellulose structure was converted from the native monoclinic form of cellulose I into a pseudo-orthorhombic system, coined as cellulose I′, a transformation occurring only with an excess of water, above 180 °C and after more than half an hour. In situ experiments indicated that the increase of crystallite size was likely due to cocrystallization of individual crystallites rather than to the crystallization of the amorphous domains of cellulose.