On the kinetics of cellulose degradation: looking beyond the pseudo zero order rate equation

被引:135
作者
Calvini, Paolo [1 ]
Gorassini, Andrea [2 ]
Merlani, Antonio Luigi [3 ]
机构
[1] SBAP, Minist Beni Culturali, I-16126 Genoa, Italy
[2] Univ Udine, Dipartimento Storia & Tutela Beni Culturali, I-33100 Udine, Italy
[3] ICPL, Minist Beni Culturali, I-00184 Rome, Italy
关键词
accelerated ageing; acid hydrolysis; autocatalysis; degree of polymerisation; kinetic models; random degradation; sigmoidal kinetics;
D O I
10.1007/s10570-007-9162-8
中图分类号
TB3 [工程材料学]; TS [轻工业、手工业、生活服务业];
学科分类号
0805 ; 080502 ; 0822 ;
摘要
The kinetics of cellulose degradation was analysed by means of a two-stage model, characterised by an autoretardant and autocatalytic regime, later tempered by the consumption of glycosidic bonds in the amorphous regions. The proposed model explains the effects on the kinetic equations of different modes of ageing (acid hydrolysis, ageing in ventilated oven or sealed vessels), initial oxidation of cellulose and experimental procedures (with or without reduction of oxidised groups). The autoretardant branch can be analysed in a quantitative way, while the integration of the non-linear autocatalytic branch is allowed in some cases, characterised by the decrease of pH and/or emission of acid volatile organic compounds (VOCs). Most of the controversial results of the literature can be easily explained, but the proposed model offers also a guide for further studies on the kinetics of cellulose degradation.
引用
收藏
页码:193 / 203
页数:11
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