Colossal photostructural changes in chalcogenide glasses. Athermal photoinduced polymerization in AsxS100-x bulk glasses revealed by near-bandgap Raman scattering

Near-bandgap Raman scattering was used to induce and study photostructural changes in AsxS100-x bulk glasses revealing a new photoinduced polymerization effect. Raman spectra were recorded also in off-resonant conditions allowing for a detailed comparison between the equilibrium glass structure and the metastable one induced by illumination. It is shown that in S-rich glasses structural changes involve the athermal scission of S8 rings and their polymerization to Sn chains. The fraction of bonds involved in this effect is surprisingly high, being one order of magnitude higher than the corresponding fractions reported up to now in photostructural studies in chalcogenide glasses

High frequency acoustic modes in vitreous Beryllium Fluoride probed by inelastic X-ray scattering

Inelastic X-ray Scattering measurements of the dynamics structure factor have bene performed on vitreous Beryllium Fluoride ({\it v-}BeF$_2$) at $T$=297 K in the momentum transfer, $Q$, range $Q$=1.5$\div$10 nm$^{-1}$. We find evidence of well defined high frequency acoustic modes. The energy position and linewidth of the excitations disperse with $Q$ as $\propto Q$ and $\propto Q^2$, respectively up to about one half of the first maximum of the static structure factor. Their magnitude compare favorably with low-frequency sound velocity and absorption data. The results indicate worth mentioning similarities of the high frequency collective dynamics of different network forming glasses such as {\it v-}B$_2$O$_3$ and {\it v-}SiO$_2$.Comment: 17 pages, 5 .ps fig

On the origin of the λ\lambda-transition in liquid Sulphur

Developing a novel experimental technique, we applied photon correlation spectroscopy using infrared radiation in liquid Sulphur around $T_\lambda$, i.e. in the temperature range where an abrupt increase in viscosity by four orders of magnitude is observed upon heating within few degrees. This allowed us - overcoming photo-induced and absorption effects at visible wavelengths - to reveal a chain relaxation process with characteristic time in the ms range. These results do rehabilitate the validity of the Maxwell relation in Sulphur from an apparent failure, allowing rationalizing the mechanical and thermodynamic behavior of this system within a viscoelastic scenario.Comment: 5 pages, 4 eps figures, accepted in Phys. Rev. Let

High frequency dynamics in a monatomic glass

The high frequency dynamics of glassy Selenium has been studied by Inelastic X-ray Scattering at beamline BL35XU (SPring-8). The high quality of the data allows one to pinpoint the existence of a dispersing acoustic mode for wavevectors ($Q$) of $1.5<Q<12.5$ nm$^{-1}$, helping to clarify a previous contradiction between experimental and numerical results. The sound velocity shows a positive dispersion, exceeding the hydrodynamic value by $\approx$ 10% at $Q<3.5$ nm$^{-1}$. The $Q^2$ dependence of the sound attenuation $\Gamma(Q)$, reported for other glasses, is found to be the low-$Q$ limit of a more general $\Gamma(Q) \propto \Omega(Q)^2$ law which applies also to the higher $Q$ region, where $\Omega(Q)\propto Q$ no longer holds.Comment: Phys. Rev. Lett. (Accepted

Stress distribution and the fragility of supercooled melts

We formulate a minimal ansatz for local stress distribution in a solid that includes the possibility of strongly anharmonic short-length motions. We discover a broken-symmetry metastable phase that exhibits an aperiodic, frozen-in stress distribution. This aperiodic metastable phase is characterized by many distinct, nearly degenerate configurations. The activated transitions between the configurations are mapped onto the dynamics of a long range classical Heisenberg model with 6-component spins and anisotropic couplings. We argue the metastable phase corresponds to a deeply supercooled non-polymeric, non-metallic liquid, and further establish an order parameter for the glass-to-crystal transition. The spin model itself exhibits a continuous range of behaviors between two limits corresponding to frozen-in shear and uniform compression/dilation respectively. The two regimes are separated by a continuous transition controlled by the anisotropy in the spin-spin interaction, which is directly related to the Poisson ratio $\sigma$ of the material. The latter ratio and the ultra-violet cutoff of the theory determine the liquid configurational entropy. Our results suggest that liquid's fragility depends on the Poisson ratio in a non-monotonic way. The present ansatz provides a microscopic framework for computing the configurational entropy and relaxational spectrum of specific substances.Comment: 11 pages, 5 figures, Final version published in J Phys Chem

Entrepreneurial sons, patriarchy and the Colonels' experiment in Thessaly, rural Greece

Existing studies within the field of institutional entrepreneurship explore how entrepreneurs influence change in economic institutions. This paper turns the attention of scholarly inquiry on the antecedents of deinstitutionalization and more specifically, the influence of entrepreneurship in shaping social institutions such as patriarchy. The paper draws from the findings of ethnographic work in two Greek lowland village communities during the military Dictatorship (1967–1974). Paradoxically this era associated with the spread of mechanization, cheap credit, revaluation of labour and clear means-ends relations, signalled entrepreneurial sons’ individuated dissent and activism who were now able to question the Patriarch’s authority, recognize opportunities and act as unintentional agents of deinstitutionalization. A ‘different’ model of institutional change is presented here, where politics intersects with entrepreneurs, in changing social institutions. This model discusses the external drivers of institutional atrophy and how handling dissensus (and its varieties over historical time) is instrumental in enabling institutional entrepreneurship

Complex dynamics in nanoscale phase separated supercooled liquids

The relaxation properties of supercooled AsxS100−x liquids are investigated using a combination of infrared photon correlation spectroscopy and topological constraint theory. Results reveal two channels of relaxation for sulfur-rich compositions that manifest by an unusual profile in the density-density autocorrelation function involving two typical timescales. This indicates a reduced temperature-dependent dynamics for one of the channels associated with a sulfur-rich segregated nanoscale phase that furthermore displays a low liquid fragility. Conversely, the dynamics of the emerging cross-linked As-S network is associated with a growth of the glass transition temperature with As content. These results can be quantitatively understood from topological constraint theory applied to a phase separated network for which a dedicated constraint enumeration must be achieved. The vanishing of this peculiar behavior occurs close to the reported isostatic reversibility window observed at the glass transition

Effect of cluster size of chalcogenide glass nanocolloidal solutions on the surface morphology of spin-coated amorphous films

Amorphous chalcogenide thin film deposition can be achieved by a spin-coating technique from proper solutions of the corresponding glass. Films produced in this way exhibit certain grain texture, which is presumably related to the cluster size in solution. This paper deals with the search of such a correlation between grain size of surface morphology of as-deposited spin-coated As33S67 chalcogenide thin films and cluster size of the glass in butylamine solutions. Optical absorption spectroscopy and dynamic light scattering were employed to study optical properties and cluster size distributions in the solutions at various glass concentrations. Atomic force microscopy is used to study the surface morphology of the surface of as-deposited and thermally stabilized spin-coated films. Dynamic light scattering revealed a concentration dependence of cluster size in solution. Spectral-dependence dynamic light scattering studies showed an interesting athermal photo-aggregation effect in the liquid state.Comment: 15 pages, 8 figure

Recurrent governance challenges in the implementation and alignment of flood risk management strategies: a review

In Europe increasing flood risks challenge societies to diversify their Flood Risk Management Strategies (FRMSs). Such a diversification implies that actors not only focus on flood defence, but also and simultaneously on flood risk prevention, mitigation, preparation and recovery. There is much literature on the implementation of specific strategies and measures as well as on flood risk governance more generally. What is lacking, though, is a clear overview of the complex set of governance challenges which may result from a diversification and alignment of FRM strategies. This paper aims to address this knowledge gap. It elaborates on potential processes and mechanisms for coordinating the activities and capacities of actors that are involved on different levels and in different sectors of flood risk governance, both concerning the implementation of individual strategies and the coordination of the overall set of strategies. It identifies eight overall coordination mechanisms that have proven to be useful in this respect