Relation between the activation energy of oxygen diffusion and the instantaneous shear modulus in propylene carbonate near the glass transition temperature

2013 ◽  
Vol 139 (11) ◽  
pp. 114506 ◽  
Author(s):  
V. M. Syutkin
2018 ◽  
Vol 26 (2) ◽  
pp. 169-175
Author(s):  
Yaoqi Shi ◽  
Liang Wen ◽  
Zhong Xin

The crystallization activation energy (Δ E) of a polymer comprises the nucleation activation energy Δ F and the transport activation energy Δ E*. In this paper, the Δ E of poly (L-lactic acid) (PLLA) nucleated with nucleating agent p- tert-butylcalix[8]arene (tBC8) was calculated. The results showed that the Δ E of nucleated PLLA was 165.97 kJ/mol, which is higher than that of pure PLLA. The reason why Δ E of PLLA increased when incorporating nucleating agent was studied. The increment of glass transition temperature ( Tg) for nucleated PLLA revealed that the polymer chain mobility was restricted by tBC8, which was considered as the reason for the increase of Δ E*. Further, polyethylene glycol (PEG) was added to improve the chain mobility, thus eliminated the variation of the transport activation energy Δ E* caused by tBC8. Then the effect of the increment of crystallization temperature range on the increase of Δ F was also taken into consideration. It was concluded that both decreasing the mobility of chain segments and increasing the crystallization temperature range caused an increase of Δ E for PLLA/tBC8.


2016 ◽  
Vol 39 (1) ◽  
pp. 13-25
Author(s):  
Karol Monkos

Abstract The paper presents the results of viscosity determinations on aqueous solutions of ovalbumin at a wide range of concentrations and at temperatures ranging from 5°C to 55°C. On the basis of these measurements and three models of viscosity for glass-forming liquids: Avramov’s model, free-volume model and power-law model, the activation energy of viscous flow for solutions and ovalbumin molecules, at different temperatures, was calculated. The obtained results show that activation energy monotonically decreases with increasing temperature both for solutions and ovalbumin molecules. The influence of the energy of translational heat motion, protein-protein and protein-solvent interactions, flexibility and hydrodynamic radius of ovalbumin on the rate of decrease in activation energy with temperature has been discussed. One of the parameters in the Avramov’s equation is the glass transition temperature Tg. It turns out that the Tg of ovalbumin solutions increases with increasing concentration. To obtain the glass transition temperature of the dry ovalbumin, a modified Gordon-Taylor equation is used. Thus determined the glass transition temperature for dry ovalbumin is equal to (231.8 ± 6.1) K.


2007 ◽  
Vol 555 ◽  
pp. 497-502
Author(s):  
Dejan Miličević ◽  
S. Trifunović ◽  
N. Ignjatović ◽  
E. Suljovrujić

Hydroxyapatite/poly L-lactide (HAp/PLLA) is a composite biomaterial which has been widely utilized for substitution and reparation of the hard bone tissue. It is well known that gamma irradiation has been successfully employed in the modification/sterilization of such porous composites and that it has advantages over other procedures. In this study, differential scanning calorimetry (DSC) measurements were made to investigate the influence of the radiation on glass transition behavior and structural relaxation, as well as to estimate the activation energy for this process. The apparent activation energy ΔH* for structural relaxation in the glass transition region was determined on the basis of the heating rate dependence of the glass transition temperature Tg. Furthermore, the results were correlated with those obtained by gel permeation chromatography (GPC). Our findings support the fact that the radiation-induced chain scission in the PLLA phase is the main reason for the decrease of the glass transition temperature and/or activation energy with the absorbed dose.


2006 ◽  
Vol 514-516 ◽  
pp. 1462-1466
Author(s):  
Rodica M. Neagu ◽  
José N. Marat-Mendes ◽  
Eugen R. Neagu

Compensation has been reported for the relaxation parameters: the activation energy W and the pre-exponential factor τ0, determined from the Thermal Sampling of Thermally Stimulated Depolarization Current technique. Below the glass transition it is assumed that the relaxation time follows an Arrhenius equation. In the vicinity of glass transition temperature an experimental thermogram may be analyzed using the Vogel-Fulcher-Tamman-Hesse (VFTH) or the Williams- Landel -Ferry equation. In this article we use the VFTH relationship to study the compensation effect in the range of glass transition. For an elementary peak obtained by TS there is a relationship between the activation energy W, the temperature of the maximum current Tm, the VFTH temperature, the compensation temperature Tc and the compensation time τ c. We employ this relationship for a basic analysis of the compensation effect in the temperature range around Tg. By numerical simulations, and assuming parameters similar to those measured experimentally, we show that it is possible to observe a compensation point in some well defined conditions


1977 ◽  
Vol 55 (13) ◽  
pp. 2517-2522 ◽  
Author(s):  
D. Ceccaldi

A general kinetic theory is used to explain the shapes of photoionized sample luminescence curves perturbed by thermal jumps (Δ ∼ 1 K, rise time ∼ 1 s). The samples studied are photoactivated organic vitreous solutions of TMPD/MCH 10−3 M and TMPD/3-MP 10−3 M. The experiments are performed within a temperature range (63–91 K) which includes the glass transition temperature Tg. It is shown that there is a slow diffusion of the trapped electrons towards the cation and competition between thermal detrapping and tunneling. The tunneling/thermal detrapping ratio Y is not time dependent during an isothermal luminescence and is only slowly temperature dependent if T ≤ Ty. Ty is very close to Tg. For T > Ty, Y decreases rapidly with T. The activation energy for thermal detrapping shows a maximum when the temperature reaches [Formula: see text] The glass transition temperature Tg may therefore be defined empirically as:[Formula: see text]Finally we obtain a glassy matrix relaxation time, τ, which decreases with T.


2007 ◽  
Vol 555 ◽  
pp. 165-170
Author(s):  
F. Skuban ◽  
S.R. Lukić ◽  
D.M. Petrović ◽  
Mirjana Šiljegović

Transformations of glasses from the multicomponent pseudobinary system (As2Se3)100−x(SbSI)x were analyzed from the aspect of determining the glass transition temperature Tg, activation energy of the process Et, and characteristic changes of the specific heat. The established dependence of Tg on glass composition and heating rate served as the basis for determining the activation energy of glass transition process Et. An abrupt increase in the specific heat cp at the glass transition temperature was analyzed with the aim of classifying the materials according to the criterion of the so-called 'fragility'. It was found that the investigated glasses, i.e. their melts, belong to the group of thermodynamically 'strong' melts.


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