High-pressure polarized Raman spectra of vitreous silica are measured up to 8 GPa in a diamond-anvil cell at room temperature. The combined use of either a non-penetrating pressurizing medium, argon, or a penetrating one, helium, allows to separate density from stress effects on the Raman frequencies. In the framework of a simple central force model, the results emphasize the distinct role played by the shrinkage of the inter-tetrahedral angle Si-O-Si and the force-constant stiffening during the compression. The polarization analysis further reveals the existence of an additional isotropic component in the high frequency wing of the Boson peak. The pressure dependence of the genuine Boson peak frequency is found to be much weaker than previously reported and even goes through a minimum around 2 GPa in a remarkable coincidence with the anomalous compressibility maximum of silica.

We investigate vitreous silica pressurized under the noble gases, He, Ne and Ar by both spectroscopic techniques and numerical simulations. We find an unexpectedhuge solubility of He and Ne at high pressure together with a large decrease of the static compressibility. We show that this relates to the open and flexible structure of the glass allowing gas atoms to distend the network, the same way a porous material deform upon fluid adsorption. This behavior can be rationalized using generalized poromechanical constitutive equations. Direct optical microscopy observations highlight the swelling of the silica network upon fluid adsorption. Very sharp diffusion front of the fluid into the silica the sample is further observed indicating non trivial kinetics of the diffusing atoms. In the Ne case, adsorption-desorption kinetics canbe tracked by Brillouin spectroscopy.

The nature of the interface between two fluids has been the subject of an extensive investigation for more than two centuries [1]. From a mechanical point of view, surface tension can be calculated as an integral of unbalanced tangential stresses over the interface thickness [2] and it is thus of no surprise that, within the assumption of temporal and local equilibrium, such a tension can be ascribed to an interface between two miscible fluids [3] and assumes a nonzero value. The idea that there are capillary forces at work in the layer between miscible liquids goes back at least to an 1871 report of J. Bosscha, cited in a paper of Korteweg [1901], who was the first [4] to introduce stresses due to concentration inhomogeneities in the Navier-Stokes equation, aiming to mimic capillarity effects between two miscible liquids. Only much more recently experimental effort has been made to investigate the existence and the nature (the sign) of such off-equilibrium tension [5-11]. In all cases the authors have pointed out that such interfacial stresses mimic a positive interfacial tension. In analogy with the surface tension of an equilibrium interface between immiscible fluids, the effective surface tension has been rationalized within an approximation of small concentration gradients via the so called square gradient model [6,8,9]. The latter predicts a quadratic dependence of such tension on the compositional mismatch between two miscible fluids.Only very recently colloids and polymer suspensions in contact with a reservoir of solvent have been considered as a model two-fluid system to study off-equilibrium surface tensions [11, 12]: indeed, diffusion is much slower in colloids and polymers as compared to atomic systems, leaving a wider temporal window for probing the transient interface between miscible fluids. In a recent work [11] we have investigated off-equilibrium surface tension between microgel suspensions and their solvent (water) showing that equation (1) holds for low concentration gradients. On the other hand we have also pointed out that the square gradient model is far to catch the volume fraction dependence of the tension for compact hard sphere-like particles [12] up to concentrations close to the maximum packing for spheres. The scenario is then currently controversial.By visualizing viscous fingering instability (VF), appearing when a solvent displaces a suspension in radial Hele-Shaw geometry, we measure interfacial tensions in function of the volume fraction of the suspended colloids or polymers, showing that the internal degrees of freedom of the particles drive the low volume fraction behavior. Our results support the existence of a positive tension between miscible fluids, confirm the quadratic scaling predicted by Korteweg [4] for long linear and crosslinked polymers and show a positive rapidly growing tension for hard sphere suspensions, whose description necessitates a theoretical framework going beyond the classic square gradient model. We rationalize our findings assuming the suspension/solvent interface in local thermodynamic equilibrium, computing explicitly the square gradient contribution to the interfacial tension for polymer/solvent and simple molecular liquid mixtures and proposing a new phenomenological model capturing the compositional dependence of the interfacial tension for large concentration gradients. In addition to that we include and analyze data reported in literature and obtained via spinning drop tensiometry, validating our approach. We conclude proposing very generally the analysis of hydrodynamic instabilities as a new tool to measure interfacial stresses in complex fluids and characterize transient interfacial tensions.

Raman spectroscopy is one of the key experimental methods for the structuralanalysis of glasses, thanks to its simple application and its sensitivity to variations ofcomposition or atomic-scale order. However, the inherent disorder of the glassystructure results to broad and overlapping peaks in the spectra, rendering theirquantitative analysis a challenging task and resulting in a mostly phenomenologicalinterpretation. This drawback can be addressed by the use of modern and accuratetheoretical tools, such as ab-initio vibrational spectroscopies. In this work we havestudied three simple sodosilicate glasses, prepared using a combined classical/ab-initio approach. For these structures, we have used density functional theory (DFT) tocalculate their vibrational density of states, as well as their Raman and IR spectra.The main advantage of the DFT calculations is that the resulting spectra can bedirectly correlated with the structural models and, most importantly, the vibrationalspectrum can be decomposed into exact contributions arising from individualstructural units. In the case of the sodosilicate glasses, we have identifiedcorrelations between spectral characteristics and stoichiometry, the effect of thepresence of bridging and non-bridging oxygens, the contributions of smaller or largerSi-O-Si angles, as well as the ones arising from the presence of the so-called Q-species. These results open the way for the study of even more complex glasses andaid in the interpretation of experimental spectra.