Permanently densified SiO2 glasses: a structural approach.

Densified silica can be obtained by different pressure and temperature paths and for different stress conditions, hydrostatic or including shear. The density is usually the macroscopic parameter used to characterize the different compressed silica samples. The aim of our present study is to compare structural modifications for silica glass, densified from several routes. For this, densified silica glasses are prepared from cold and high temperature (up to 1020 °C) compressions. The different densified glasses obtained in our study are characterized by micro-Raman spectroscopy. Intertetrahedral angles from the main band relative to the bending mode decrease and their values are larger for densified samples from high temperature compression than those samples from cold compression. The relative amount of 3-membered rings deduced from the D2 line area increases as a function of density for cold compression. The temperature increase during the compression process induces a decrease of the 3 fold ring population. Moreover, 3 fold rings are more deformed and stressed for densified samples at room temperature at the expense of those densified at high temperature. Temperature plays a main role in the reorganization structure during the densification and leads to obtaining a more relaxed structure with lower stresses than glasses densified from cold compression. The role of hydrostatic or non-hydrostatic applied stresses on the glass structure is discussed. From the Sen and Thorpe central force model, intertetrahedral angle average value and their distribution are estimated.

Elastic moduli of permanently densified silica glasses.

Modelling the mechanical response of silica glass is still challenging, due to the lack of knowledge concerning the elastic properties of intermediate states of densification. An extensive Brillouin Light Scattering study on permanently densified silica glasses after cold compression in diamond anvil cell has been carried out, in order to deduce the elastic properties of such glasses and to provide new insights concerning the densification process. From sound velocity measurements, we derive phenomenological laws linking the elastic moduli of silica glass as a function of its densification ratio. The found elastic moduli are in excellent agreement with the sparse data extracted from literature, and we show that they do not depend on the thermodynamic path taken during densification (room temperature or heating). We also demonstrate that the longitudinal sound velocity exhibits an anomalous behavior, displaying a minimum for a densification ratio of 5%, and highlight the fact that this anomaly has to be distinguished from the compressibility anomaly of a-SiO2 in the elastic domain.

In situ Brillouin study of sodium alumino silicate glasses under pressure.

The in situ elastic and plastic behaviors of sodium aluminosilicate glasses with different degrees of depolymerization were analyzed using Brillouin spectroscopy. The observed elastic anomaly progressively vanished with depolymerization. The densification process appears to be different from that observed in pure silica glass. In the plastic regime of densified glasses hysteresis loops were observed and related to modification of the local silicon environment facilitated by the addition of sodium.

Permanent densification of compressed silica glass: a Raman-density calibration curve.

Raman scattering experiments have been carried out to study persistent densification in SiO(2) glass following hydrostatic compression at room temperature. A new relationship linking selective Raman parameters to the degree of densification in the glass has been developed here. This approach will allow quantification of the residual densification in silica following microindentation experiments, with the goal being the development of a constitutive law for amorphous silica.

Hysteretically reversible phase transition in a molecular glass.

Pressure induced densification in a molecular arsenic sulfide glass is studied at ambient temperature using x-ray scattering, absorption and Raman spectroscopic techniques in situ in a diamond anvil cell. The relatively abrupt changes in the position of the first sharp diffraction peak, FSDP, and the pressure-volume equation of state near ∼2 GPa suggest a phase transition between low- and high-density amorphous phases characterized by different densification mechanisms and rates. Raman spectroscopic results provide clear evidence that the phase transition corresponds to a topological transformation between a low-density molecular structure and a high-density network structure via opening of the constituent As(4)S(3) cage molecules and bond switching. Pressure induced mode softening of the high density phase suggests a low dimensional nature of the network. The phase transformation is hysteretically reversible, and therefore, reminiscent of a first-order phase transition.

Progressive transformations of silica glass upon densification.

The elastic and plastic behaviors of silica glasses densified at various maximum pressure reached (12 GPa, 15 GPa, 19 GPa, and 22 GPa), were analyzed using in situ Raman and Brillouin spectroscopies. The elastic anomaly was observed to progressively vanish up to a maximum pressure reached of 12 GPa, beyond which it is completely suppressed. Above the elastic anomaly the mechanical behavior of silica glass, as derived from Brillouin measurements, is interpreted in terms of pressure induced transformation of low density amorphous silica into high density amorphous silica.

Correlation between boson peak and anomalous elastic behavior in GeO2 glass: an in situ Raman scattering study under high-pressure.

We present low-frequency Raman scattering of pure GeO(2) glass under pressure up to 4 GPa, corresponding to an elastic transformation. Intensity variation and frequency shift of the boson peak are analysed and compared to the Debye model. The decrease of the boson peak intensity scaled by the Debye energy is correlated to the elastic anomalous properties under pressure up to 1.5 GPa, and interpreted as an elastic homogenisation process at the local scale. We emphasize similarities between a-GeO(2) and a-SiO(2) behavior under pressure, and compare our results to other experiments, numerical studies, and predictions of several models concerning amorphous systems.

Structural heterogeneity and pressure-relaxation in compressed borosilicate glasses by in situ small angle X-ray scattering.

We report on Brillouin and in situ small angle X-ray scattering (SAXS) analyses of topological heterogeneity in compressed sodium borosilicate glasses. SAXS intensity extrapolated to very low angular regimes, I(q = 0), is related to compressibility. From Brillouin scattering and analyses of the elastic properties of the glass, the Landau-Placzek ratio is determined and taken as a direct reflection of the amplitude of frozen-in density fluctuations. It is demonstrated that with increasing fictive pressure, topological (mid- and long-range) homogeneity of the glass increases significantly. Heating and cooling as well as isothermal scans were performed to follow the evolution of density fluctuations upon pressure recovery. For a sample with a fictive pressure p(f) of 470 MPa, complete recovery to p(f) = 0.1 MPa was observed to occur close to the glass transition temperature. The values of fictive and apparent fictive temperature, respectively, as obtained via the intersection method from plots of I(q = 0) vs. temperature were found in good agreement with previous calorimetric analyses. Isothermal scans suggest that mid- and long-range recovery govern macroscopic density relaxation.

Soda-lime silicate glass under hydrostatic pressure and indentation: a micro-Raman study.

Raman micro-spectroscopy is used to analyse the plastic behaviour of window glass (a soda-lime silicate glass) under high hydrostatic pressure and Vickers indentation. We show pressure-induced irreversible structural changes, notably an increase of Q(2) species at the expense of Q(3). For the first time, a very accurate [Formula: see text] calibration curve has been established. Local density variations of a Vickers indented window glass have been characterized by micro-Raman mapping using a high spatial resolution device. The effects of glass depolymerization on indentation and hydrostatic compression are discussed. Differences between window glass and pure SiO(2) glass behaviour under high stresses are also highlighted and analysed at a local scale.

Non-Debye normalization of the glass vibrational density of states in mildly densified silicate glasses.

The evolution of the boson peak with densification at medium densification rates (up to 2.3%) in silicate glasses was followed through heat capacity measurements and low frequency Raman scattering. It is shown that the decrease of the boson peak induced by densification does not conform to that expected from a continuous medium; rather it follows a two step behaviour. The comparison of the heat capacity data with the Raman data shows that the light-vibration coupling coefficient is almost unaffected in this densification regime. These results are discussed in relation to the inhomogeneity of the glass elastic network at the nanometre scale.

In situ Raman spectroscopy of pressure-induced changes in LaBGeO(5) glass: hysteresis and plastic deformation.

In situ micro-Raman spectroscopy was performed on lanthanum borogermanate (LBG) glasses, compressed in a diamond anvil cell at ambient temperature. Up to 5.6 GPa the structural changes are reversible, whereas experiments performed at 10 GPa and higher are characterized by hysteresis loops. A noticeable change of evolution of the main Raman band at 800 cm(-1) has been evidenced around 8 GPa. Indeed, at such a pressure, this Raman band is shifted in the opposite direction while the pressure is still increasing. This change of slopes may be the sign of a pressure-induced coordination number change. Upon decompression the Raman shift of this band follows a different path from the one during compression. When the sample is returned to ambient pressure, it shows a shifted and lightly modified Raman spectrum, suggesting that a new amorphous phase for LBG glass is reached under high pressure and still exists at atmospheric pressure. However, a comparison with LaBGeO(5) crystals with the same composition shows that this material has a full elastic behaviour in the same pressure range.

Influence of fictive temperature and composition of silica glass on anomalous elastic behaviour.

In order to determine the influence of the thermal history (fictive temperature) and OH content on the elastic properties of silica glass, we have investigated high resolution in situ Brillouin experiments on SiO(2) glass from room temperature to the supercooled liquid at 1773 K across the glass transition. The well known anomalous increase of elastic modulus in the glassy state and in the supercooled liquid regime is observed. No change in the slope of the elastic moduli of silica appears as a characteristic of the glass transition, in contrast to what happens in various other glasses. We show that thermal history has a weak effect on elastic moduli in the glass transition regime for silica glass. The effect of the water content in silica glass is greater than the fictive temperature effect and gives larger changes in the amplitude of the elastic modulus for the same thermal dependence. A singular decrease above 1223 K is also observed in the shear moduli for hydrated samples. Different models explaining the temperature dependence of the elastic properties in relationship with frozen-in density fluctuations or with the structure are discussed.

[Use of talc and sarcoidosis - pathogenic role of cutaneous talc exposure in sarcoidosis]. / Application cutanée de talc et sarcoïdose. A propos de deux cas.

INTRODUCTION: We report on two patients with sarcoidosis with disseminated nodes, who used talc on irritated cutaneous areas. CASE REPORT: A histologic examination with intense polarised light showed up cristalline bi-refringent particles within vessels in contact with granulomatous areas. Microdissection followed by an electronic microscopy study and microanalysis was realised. In situ microanalysis allowed us to identify bi-refringent particles with a size of roughly 0.25microm as silica or silicate coming possibly from talc. We consequently studied a brand name talc. The diffraction spectrum showed that this product not only contained talc but also chlorite and quartz. Electron microscopy examination showed particles of all sizes even smaller than 0.25microm. These infra-microscopic particles, visible in a vessel only when agglomerated, could be invisible under optic microscopy (resolution: roughly 0.5microm) inside the granuloma even though they are responsible for it. Moreover, at this level of size of particles, they may escape mineralogic analyses which use methods involving the destruction of organic material, the mineral residue collecting on cellulose filter with a diameter generally of 0.45microm. CONCLUSION: Two recent epidemiologic studies confirm the possible role of mineral exposure in sarcoidosis. Some sarcoidosis could be caused by mineral overload on genetically predisposed patients. Some cases could be related to mineral powder application. Among different types of mineral exposure, applications of cosmetic products may induce disseminated granulomatous reaction on genetically predisposed patients. Such applications have to be considered in epidemiologic studies.