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On the kinetics of cellulose degradation: looking beyond the pseudo zero order rate equation
Authors:Paolo Calvini  Andrea Gorassini  Antonio Luigi Merlani
Affiliation:(1) Ministero Beni Culturali, S.B.A.P., Via Balbi 10, Genova, 16126, Italy;(2) Dipartimento di Storia e Tutela dei Beni Culturali, Università di Udine, Palazzo Caiselli – Vicolo Florio 2/B, Udine, 33100, Italy;(3) Ministero Beni Culturali, I.C.P.L., Via Milano 76, Roma, 00184, Italy
Abstract: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.
Keywords:Accelerated ageing  Acid hydrolysis  Autocatalysis  Degree of polymerisation  Kinetic models  Random degradation  Sigmoidal kinetics
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