Mercerization of cellulose. I. X‐ray diffraction evidence for intermediate structures

Abstract A study of the mercerization of ramie cellulose was begun using x‐ray diffraction, in order to determine the types of alkali–cellulose structures that occur as intermediates during the conversion of cellulose I to cellulose II. A total of five unique alkali–celluloses (Na–celluloses) could be generated reproducibly, depending only on the alkali concentration used. The reproducibility was enhanced by slowing down the mercerization process, by laterally compressing the fibers in capillary tubes. The five structures, named Na–celluloses I, IIA, IIB, III, and IV, were of two types based on their crystallographic fiber repeats. The first type was represented by Na–celluloses I, III, and IV, all exhibiting a ca. 10 Å repeat. The second type was represented by Na–celluloses IIA and IIB, with a ca. 15 Å repeat. The latter structures are possibly based on a threefold helical chain conformation, which has not been seen in crystalline celluloses. All Na–cellulose structures exhibited a reasonable degree of crystallinity and high degree of fibrous orientation. They formed a definite interconversion scheme, marked by crystalline‐to‐crystalline phase transformations.