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Modification of the fine structure of cellulose by halogen and heat treatments
Author(s) -
Lewin Menachem,
Guttmann Hilda,
Derfler David
Publication year - 1982
Publication title -
journal of applied polymer science
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.575
H-Index - 166
eISSN - 1097-4628
pISSN - 0021-8995
DOI - 10.1002/app.1982.070270902
Subject(s) - crystallization , cellulose , materials science , chemical engineering , bromine , activation energy , solvent , cellulose fiber , polymer chemistry , organic chemistry , chemistry , engineering , metallurgy
Treatment of various celluloses such as cotton, sulphite, and sulphate pulp with bromine water brings about profound changes in the fine structure of the fiber. Depending on the conditions of the treatment and on the nature of the cellulose, increases or decreases in the accessibility of the cellulose are observed, indicating crystallization and decrystallization processes. In the case of bleached sulphate pulp, similarly to rayon previously studied, an initial decrystallization proceeds the crystallization step. These changes were determined by the IR method, which was correlated previously to the bromine accessibility method. They are accompanied by highly significant changes in moisture absorption. The crystallization proceeds according to first‐order kinetics with respect to the concentration of the less‐ordered regions (LOR) of the cellulose. The rates of crystallization for the various celluloses varied in a range of 4 orders of magnitude. The activation energies of the bromide induced crystallization were found for all celluloses to be in the range of 10–15 kcal/mol, as compared to 30–40 kcal/mol obtained upon crystallizing the same celluloses by heating in the temperature range of 180–200°C. These values correspond to those of solvent and thermal crystallizations of poly(ethylene terephthalate), indicating the similarity between the crystallization mechanisms of the two polymers.