Glasses activation energies

Diffusion of the molecular gases can be compHcated by reactions with the glass network, especially at the sites of stmctural defects. The diffusion coefficient of water, for example, shows a distinct break around 550°C (110). Above 550°C, the activation energy is approximately 80 kj /mol (19 kcal/mol), but below 550°C, it is only 40 kJ/mol (9.5 kcal/mol). Proposed explanations for the difference cite the fact that the reaction between water and the sihca network to form hydroxyls is not in equiUbrium at the lower temperatures. 

The viscosity of liquid silicates such as drose containing barium oxide and silica show a rapid fall between pure silica and 20 mole per cent of metal oxide of nearly an order of magnitude at 2000 K, followed by a slower decrease as more metal oxide is added. The viscosity then decreases by a factor of two between 20 and 40 mole per cent. The activation energy for viscous flow decreases from 560 kJ in pure silica to 160-180kJmol as the network is broken up by metal oxide addition. The introduction of CaFa into a silicate melt reduces the viscosity markedly, typically by about a factor of drree. There is a rapid increase in the thermal expansivity coefficient as the network is dispersed, from practically zero in solid silica to around 40 cm moP in a typical soda-lime glass. 

As an example the experimental results on heterogeneous recombination of CH3 radicals on glass at different temperatures are plotted on Fig. 4.1. The experimental conditions in this case are chosen in such a way that inequality (4.3) is satisfied (A < 1 cm, y is about 1(H, r = 3 cm). Thus, formula (4.1) holds in this experiment. This conclusion is supported by the fact that for all experimental series the results obtained at different temperatures of the reaction vessel walls are satisfactorily approximated by the same straight line. This means that methyl radicals on glass substrate undergo recombination governed by the first-order kinetics, and the activation energy is close to zero. 

For an oxidized surface, the value of y is 10" - 1.7-10 and it decreases with increasing the experimental temperature. In this case the activation energy of a change in yis 2.1 kcal/mole. From these data it can be inferred that the heterogeneous de-excitation of singlet oxygen proceeds in terms of the physical adsorption mechanism similar to that described for glass. 

The increase in the length of the side chain results normally in an internal plasticization effect caused by a lower polarity of the main chain and an increase in the configurational entropy. Both effects result in a lower activation energy of segmental motion and consequently a lower glass transition temperature. The modification of PPO with myristoyl chloride offers the best example. No side chain crystallization was detected by DSC for these polymers. 

Table 2 Apparent activation energies for each stage of the induction period of glass crystallization just above Tg for PET, PEN, sPS, and iPS [15]... 

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