期刊
CELLULOSE
卷 19, 期 1, 页码 297-306出版社
SPRINGER
DOI: 10.1007/s10570-011-9608-x
关键词
Phase transformation; Polymorph; Cellulose I alpha I beta II IIII IVI IVII I-HT alpha beta
资金
- Center for Direct Catalytic Conversion of Biomass to Biofuels (C3Bio), an Energy Frontier Research Center
- U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences [DE-SC0000997]
The observation that the hydrothermal conversion of cellulose I alpha to cellulose I beta is irreversible has been assumed to be due to the relative free energy of these polymorph phases. We propose an alternative explanation: when cooling the high temperature phase, the barrier to forming I beta is much smaller than the barrier to forming I alpha, so kinetics favor the formation of I beta. This explanation is consistent with all available experimental data, and is consistent with the general observation of polymer solid-solid phase transformations via metastable intermediate states. While cellulose I beta may be lower in free energy than I alpha, this has not been shown experimentally. Phase transformations of other cellulose polymorphs may be subject to similar kinetic effects when converted via metastable intermediate states.
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