Crystallite structure of cellulose

The crystallite structure of cellulose has been elucidated through analyses of the degradations of model compounds by gel-permeation chromatography. These compounds include single crystals of cellulose triacetate, regenerated cellulose from single crystals, precipitated celluloses from solutions, and commercial regenerated cellulose. The corresponding distribution profiles are found to follow the Keller transformation, which is a characteristic behavior of the folded crystals of synthetic polymers. It is also found that the leveling-off DP of cellulose is a first-order approximation of the corresponding fold length. A detailed folding chain model for the regenerated cellulose was constructed, and the various aspects of the structure are discussed. The kinetic data and the degradation products of native celluloses were also analyzed and found to obey the ruling of the chain fold model but not the conventional fringe-micellar model. In addition, an iodine-staining experiment pinpoints a minimum of 1.5% of true amorphous material; this is in quantitative agreement with the conformation analysis for the six-fold helical β-loop bonds. It is therefore suggested that the same chain-fold conformation is applicable to the native polymer. The hydrolysis of cellulose is found to be composed of a triple mode of degradation, i.e., a first-order random scission at the folds, a zero-order peeling reaction at the ends of the crystallites, and a first-order random scission on the lateral surfaces of the cellulose.