Calorimetric Studies on Cooperative Relaxation Near Tg for a Series of Glycerol Aqueous Solutions with High Concentrations

Chem. J. Chinese Universities

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Calorimetric Studies on Cooperative Relaxation Near T_g for a Series of Glycerol Aqueous Solutions with High Concentrations

GAO Cai¹*, WANG Tie-Jun¹, ZHOU Guo-Yan², HUA Ze-Zhao²

1. School of Mechanical and Automotive Engineering, Hefei University of Technology, Hefei 230009, China;
2. Institute of Cryobiology, University of Shanghai for Science and Technology, Shanghai 200093, China

Received:2006-08-25 Revised:1900-01-01 Online:2007-06-10 Published:2007-06-10
Contact: GAO Cai

Abstract

Abstract: In order to examine the validity of entropically based nonlinear Adam-Gibbs equation(AGF) on the describing of cooperative relaxation of H-bond molecular liquid, differential scanning calorimetry(DSC) was employed to obtain the specific heat capacities of glycerol aqueous solutions in the temperature range of 118—218 K. Curve fitting technology was used to obtain the AGF model parameters. The results indicate that AGF formula can be used to predict the relaxation time below (T_g+20 K). The temperature-invariant activation energies(Δμ') and the sizes of cooperatively rearranging region(z*) were analyzed via AGF model and Johari's method. Physically reasonable z* can only be obtained when larger values of configuration numbers(W*) were chosen. The values of Δμ' decreased with increasing water content in the glass. The length scales of the cooperative rearranging region(ξ_CRR) were also estimated from the temperature fluctuation theory proposed by Donth. It was found that the ξ_CRR decreased from 3.01 to 2.06 nm when the fraction of glycerol decreased from 1 to 0.6 in the solutions. The values of z* obtained by using Johari's methods is 3.47 for glycerol, which is significantly less than the number of molecules estimated by Donth' method(583) in the CRR.

Key words: Cooperative relaxation, Glycerol, Aqueous solution, Differential scanning calorimetry

CLC Number:

O642.3

TrendMD:

GAO Cai¹*, WANG Tie-Jun¹, ZHOU Guo-Yan², HUA Ze-Zhao². Calorimetric Studies on Cooperative Relaxation Near T_g for a Series of Glycerol Aqueous Solutions with High Concentrations[J]. Chem. J. Chinese Universities, doi: .

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Calorimetric Studies on Cooperative Relaxation Near T_g for a Series of Glycerol Aqueous Solutions with High Concentrations

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