A. Faivre

In situ measurements of density fluctuations and compressibility in silica glasses as a function of temperature and thermal history

In this paper, small-angle x-ray scattering measurements are used to determine the different compressibility contributions, as well as the isothermal compressibility {chi}{sub T}{sup 0} in thermal equilibrium in silica glasses having different thermal histories. Using two different methods of analysis, in the supercooled liquid and in the glassy state, we obtain, respectively, the temperature and fictive temperature dependences of {chi}{sub T}{sup 0}. The values obtained in the glass and supercooled liquid states are very close to each other. They agree with previous determinations of the literature. The compressibility in the glass state slightly decreases with increasing fictive temperature. The relaxational part of the compressibility is also calculated and compared to previous determinations. We discussed the small differences between the different determinations.

Influence of thermal aging on density fluctuations in oxide glasses measured by small-angle X-ray scattering

Small-angle X-ray measurements of the density fluctuations as a function of temperature and thermal history are performed in silica and float glass. Structural relaxation in the glass transition range is observed for the samples stabilized at high temperature. The amplitude of the density fluctuations in the glassy state depends on the thermal history for samples of same composition. It increases with fictive temperature for silica as well as for float glass. Our results are compared to previous results in oxide glasses or polymers and discussed in relation with the concept of fragility i.e. the temperature sensitivity of viscosity in the liquid state.

Characterization of the glass transition in vitreous silica by temperature scanning small-angle X-ray scattering

The temperature dependence of the X-ray scattering in the region below the first sharp diffraction peak was measured for silica glasses with low and high OH content (GE-124 and Corning 7980). Data were obtained upon scanning the temperature at 10, 40 and 80 K/min between 400 K and 1820 K. The measurements resolve, for the first time, the hysteresis between heating and cooling through the glass transition for silica glass, and the data have a better signal-to-noise ratio than previous light scattering and differential thermal analysis data. For the glass with the higher hydroxyl concentration, the glass transition is broader and at a lower temperature. Fits of the data to the Adam-Gibbs-Fulcher equation provide updated kinetic parameters for this very strong glass. The temperature derivative of the observed X-ray scattering matches that of light scattering to within 14%.

Density and concentration fluctuations in SiO2–GeO2 optical fiber glass investigated by small angle x-ray scattering

Density and concentration fluctuations have been investigated in a 3mol% GeO2 doped silica glass as a function of the fictive temperature (the temperature at which the structure of the supercooled liquid has been frozen-in to form the glass) by small angle x-ray scattering measurements. The fluctuations increase in a way is quite similar to that observed for pure silica glass as a result of density fluctuation fictive temperature dependence. Fluctuations have also been studied in glasses containing different amounts of GeO2 up to 21mol% GeO2. The fluctuations are shown to increase very strongly with germanium amount as a result of strong concentration fluctuation increase. This observation is in agreement with already observed excess losses in light scattering measurements.

Density fluctuations in oxide glasses investigated by small-angle X-ray scattering

The structure of glasses is characterized by the existence of density and composition fluctuations on the nanometre scale. We present three examples of the use of small-angle X-ray scattering to get information about these density fluctuations. The thermal history and OH content were observed to have a huge influence. The static compressibility decreases when the OH content or fictive temperature increase. We showed that temperature scanning small-angle X-ray scattering can provide an accurate description of the position, width and shape of the glass transition.

Temperature dependence of the density fluctuations of silica by small-angle X-ray scattering

Abstract Low-OH-content silica samples having fictive temperatures in the interval 1000–1500°C, have been studied by small-angle X-ray scattering using synchrotron radiations both at room temperature and from 20 to 1500deg;C. The limit for zero-angle X-ray scattering intensity is analysed in term of density fluctuations. We demonstrate that density fluctuations are strongly related to structural relaxation; both depend on thermal history (i.e. the fictive temperature) of the sample, in the temperature range below Tg.

Silica structural changes induced by thermal treatment or ionic implantation as probed by IR reflectance spectroscopy

Fourier transformed infrared microreflectance spectroscopy is used to probe and compare the consequences of thermal quenching or ionic implantation on the structure of silica. A linear change in the main structural feature associated with Si–O–Si vibration with fictive temperature (Tf) is observed up to Tf=1400 °C. Ionic implantation is shown to shift the frequency of the main IR Si–O–Si vibration toward much lower wavenumbers, for all deposited energies, indicating that a comparison can be drawn between fictive temperature and irradiation effects. Extrapolating the linear changes in the IR structural bands obtained as a function of Tf for the implanted samples, we show that two structural (νTO) and (νB) contributions are not affected by ionic implantation, as they would be by a unique very high Tf. In the case of ionic implantation, we also evidence the development of some specific structural contributions indicating a depolymerization of silica network.

Temperature scanning small angle x-ray scattering measurements of structural relaxation in type-III vitreous silica

The fictive temperature of vitreous silica containing approximately 900wtppm of hydroxyl groups was monitored with small angle x-ray scattering. The measurements were carried out during annealing and while scanning the temperature, with annealing temperatures ranging between 930 and 1330K. Fitting the data to the Adam-Gibbs-Fulcher equation by using the Tool-Narayanaswamy method yields a particularly simple thermorheological behavior for type-III vitreous silica. Unlike the general case for glass kinetics, including vitreous silica with low hydroxyl content, the relaxation time constant is nearly decoupled from the fictive temperature. This high degree of decoupling of the state of the glass and the relaxation rate agrees with the results of viscosity measurements. By improving the data analysis procedure, we have significantly increased the precision of the results, and it was possible to resolve changes of the activation energy of the relaxation processes to within 0.5%. This has made sample aging effec...

Mechanical behaviour of highly porous glasses

The mechanical behaviour of highly porous glassy materials (pore volume higher than 85%) is investigated using Hg porosimetry. Because of the small pore size of these materials, Hg liquid cannot enter their porous network and consequently induces an isostatic pressure. Due to the high compliance of the solid network of these materials, compression results in the sample shrinkage. The experiments described in this paper show that an isostatic pressure applied to highly porous glasses induces an irreversible volume shrinkage which can be associated with an unexpected plastic behaviour and structure strengthening. The magnitude of the plastic shrinkage and the increase of the associated mechanical properties depend on the starting bulk density. The irreversible compaction can be explained by siloxane bond formation between clusters constituting the porous glasses, retaining the strained structure. This densification process could offer a new way to synthesise glasses at room temperature.

Sintering of compressed aerogels

Abstract Two different ways of densification of monolithic silica aerogels have been proposed in the literature. The first one corresponds to sintering, the second one to isostatic compression using a Hg porosimeter. In this paper, we analyse a combination of these two different methods. It is shown that a first isostatic compression followed by a further heat treatment reduces considerably the time required to achieve partial to almost full densification. This ‘two steps densification-process’ is analysed in the framework of a classical sintering model.