Thermodynamic parameters of bonds in glassy materials from viscosity-temperature relationships

Doremus's model of viscosity assumes that viscous flow in amorphous materials is mediated by broken bonds (configurons). The resulting equation contains four coefficients, which are directly related to the entropies and enthalpies of formation and motion of the configurons. Thus by fitting this viscosity equation to experimental viscosity data these enthalpy and entropy terms can be obtained. The non-linear nature of the equation obtained means that the fitting process is non-trivial. A genetic algorithm based approach has been developed to fit the equation to experimental viscosity data for a number of glassy materials, including SiO2, GeO2, B2O3, anorthite, diopside, xNa2O–(1-x)SiO2, xPbO–(1-x)SiO2, soda-lime-silica glasses, salol, and α-phenyl-o-cresol. Excellent fits of the equation to the viscosity data were obtained over the entire temperature range. The fitting parameters were used to quantitatively determine the enthalpies and entropies of formation and motion of configurons in the analysed systems and the activation energies for flow at high and low temperatures as well as fragility ratios using the Doremus criterion for fragility. A direct anti-correlation between fragility ratio and configuron percolation threshold, which determines the glass transition temperature in the analysed materials, was found

Irradiation-induced Ag nanocluster nucleation in silicate glasses: analogy with photography

The synthesis of Ag nanoclusters in sodalime silicate glasses and silica was studied by optical absorption (OA) and electron spin resonance (ESR) experiments under both low (gamma-ray) and high (MeV ion) deposited energy density irradiation conditions. Both types of irradiation create electrons and holes whose density and thermal evolution - notably via their interaction with defects - are shown to determine the clustering and growth rates of Ag nanocrystals. We thus establish the influence of redox interactions of defects and silver (poly)ions. The mechanisms are similar to the latent image formation in photography: irradiation-induced photoelectrons are trapped within the glass matrix, notably on dissolved noble metal ions and defects, which are thus neutralized (reverse oxidation reactions are also shown to exist). Annealing promotes metal atom diffusion, which in turn leads to cluster nuclei formation. The cluster density depends not only on the irradiation fluence, but also - and primarily - on the density of deposited energy and the redox properties of the glass. Ion irradiation (i.e., large deposited energy density) is far more effective in cluster formation, despite its lower neutralization efficiency (from Ag+ to Ag0) as compared to gamma photon irradiation.Comment: 48 pages, 18 figures, revised version publ. in Phys. Rev. B, pdf fil

Geology, hydrology, chemistry, and microbiology of the in situ bioremediation demonstration site

This report summarizes characterization information on the geology, hydrology, microbiology, contaminant distribution, and ground-water chemistry to support demonstration of in situ bioremediation at the Hanford Site. The purpose of this information is to provide baseline conditions, including a conceptual model of the aquifer being utilized for in situ bioremediation. Data were collected from sampling and other characterization activities associated with three wells drilled in the upper part of the suprabasalt aquifer. Results of point-dilution tracer tests, conducted in the upper 9 m (30 ft) of the aquifer, showed that most ground-water flow occurs in the upper part of this zone, which is consistent with hydraulic test results and geologic and geophysical data. Other tracer test results indicated that natural ground-water flow velocity is equal to or less than about 0.03 m/d (0.1 ft/d). Laboratory hydraulic conductivity measurements, which represent the local distribution of vertical hydraulic conductivity, varied up to three orders of magnitude. Based on concentration data from both the vadose and saturated zone, it is suggested that most, if not all, of the carbon tetrachloride detected is representative of the aqueous phase. Concentrations of carbon tetrachloride, associated with a contaminant plume in the 200-West Area, ranged from approximately 500 to 3,800 {mu}g/L in the aqueous phase and from approximately 10 to 290 {mu}g/L in the solid phase at the demonstration site. Carbon tetrachloride gas was detected in the vadose zone, suggesting volatilization and subsequent upward migration from the saturated zone

A new variational approach to the stability of gravitational systems

We consider the three dimensional gravitational Vlasov Poisson system which describes the mechanical state of a stellar system subject to its own gravity. A well-known conjecture in astrophysics is that the steady state solutions which are nonincreasing functions of their microscopic energy are nonlinearly stable by the flow. This was proved at the linear level by several authors based on the pioneering work by Antonov in 1961. Since then, standard variational techniques based on concentration compactness methods as introduced by P.-L. Lions in 1983 have led to the nonlinear stability of subclasses of stationary solutions of ground state type. In this paper, inspired by pioneering works from the physics litterature (Lynden-Bell 94, Wiechen-Ziegler-Schindler MNRAS 88, Aly MNRAS 89), we use the monotonicity of the Hamiltonian under generalized symmetric rearrangement transformations to prove that non increasing steady solutions are local minimizer of the Hamiltonian under equimeasurable constraints, and extract compactness from suitable minimizing sequences. This implies the nonlinear stability of nonincreasing anisotropic steady states under radially symmetric perturbations

Dynamical stability of infinite homogeneous self-gravitating systems: application of the Nyquist method

We complete classical investigations concerning the dynamical stability of an infinite homogeneous gaseous medium described by the Euler-Poisson system or an infinite homogeneous stellar system described by the Vlasov-Poisson system (Jeans problem). To determine the stability of an infinite homogeneous stellar system with respect to a perturbation of wavenumber k, we apply the Nyquist method. We first consider the case of single-humped distributions and show that, for infinite homogeneous systems, the onset of instability is the same in a stellar system and in the corresponding barotropic gas, contrary to the case of inhomogeneous systems. We show that this result is true for any symmetric single-humped velocity distribution, not only for the Maxwellian. If we specialize on isothermal and polytropic distributions, analytical expressions for the growth rate, damping rate and pulsation period of the perturbation can be given. Then, we consider the Vlasov stability of symmetric and asymmetric double-humped distributions (two-stream stellar systems) and determine the stability diagrams depending on the degree of asymmetry. We compare these results with the Euler stability of two self-gravitating gaseous streams. Finally, we determine the corresponding stability diagrams in the case of plasmas and compare the results with self-gravitating systems

Towards a better characterisation of deep-diving whales’ distributions by using prey distribution model outputs?

In habitat modelling, environmental variables are assumed to be proxies of lower trophic levels distribution and by extension, of marine top predator distributions. More proximal variables, such as potential prey fields, could refine relationships between top predator distributions and their environment. In situ data on prey distributions are not available over large spatial scales but, a numerical model, the Spatial Ecosystem And POpulation DYnamics Model (SEAPODYM), provides simulations of the biomass and production of zooplankton and six functional groups of micronekton at the global scale. Here, we explored whether generalised additive models fitted to simulated prey distribution data better predicted deepdiver densities (here beaked whales Ziphiidae and sperm whales Physeter macrocephalus) than models fitted to environmental variables. We assessed whether the combination of environmental and prey distribution data would further improve model fit by comparing their explanatory power. For both taxa, results were suggestive of a preference for habitats associated with topographic features and thermal fronts but also for habitats with an extended euphotic zone and with large prey of the lower mesopelagic layer. For beaked whales, no SEAPODYM variable was selected in the best model that combined the two types of variables, possibly because SEAPODYM does not accurately simulate the organisms on which beaked whales feed on. For sperm whales, the increase model performance was only marginal. SEAPODYM outputs were at best weakly correlated with sightings of deep-diving cetaceans, suggesting SEAPODYM may not accurately predict the prey fields of these taxa. This study was a first investigation and mostly highlighted the importance of the physiographic variables to understand mechanisms that influence the distribution of deep-diving cetaceans. A more systematic use of SEAPODYM could allow to better define the limits of its use and a development of the model that would simulate larger prey beyond 1,000 m would probably better characterise the prey of deep-diving cetaceans.En prens

The kinetic fragility of liquids as manifestation of the elastic softening

We show that the fragility $m$, the steepness of the viscosity and relaxation time close to the vitrification, increases with the degree of elastic softening, i.e. the decrease of the elastic modulus with increasing temperature, in universal way. This provides a novel connection between the thermodynamics, via the modulus, and the kinetics. The finding is evidenced by numerical simulations and comparison with the experimental data of glassformers with widely different fragilities ($33 \le m \le 115$), leading to a fragility-independent elastic master curve extending over eighteen decades in viscosity and relaxation time. The master curve is accounted for by a cavity model pointing out the roles of both the available free volume and the cage softness. A major implication of our findings is that ultraslow relaxations, hardly characterised experimentally, become predictable by linear elasticity. As an example, the viscosity of supercooled silica is derived over about fifteen decades with no adjustable parameters.Comment: 7 pages, 6 figures; Added new results, improved the theoretical sectio

Climate Change Meets the Law of the Horse

The climate change policy debate has only recently turned its full attention to adaptation - how to address the impacts of climate change we have already begun to experience and that will likely increase over time. Legal scholars have in turn begun to explore how the many different fields of law will and should respond. During this nascent period, one overarching question has gone unexamined: how will the legal system as a whole organize around climate change adaptation? Will a new distinct field of climate change adaptation law and policy emerge, or will legal institutions simply work away at the problem through unrelated, duly self-contained fields, as in the famous Law of the Horse? This Article is the first to examine that question comprehensively, to move beyond thinking about the law and climate change adaptation to consider the law of climate change adaptation. Part I of the Article lays out our methodological premises and approach. Using a model we call Stationarity Assessment, Part I explores how legal fields are structured and sustained based on assumptions about the variability of natural, social, and economic conditions, and how disruptions to that regime of variability can lead to the emergence of new fields of law and policy. Case studies of environmental law and environmental justice demonstrate the model’s predictive power for the formation of new distinct legal regimes. Part II applies the Stationarity Assessment model to the topic of climate change adaptation, using a case study of a hypothetical coastal region and the potential for climate change impacts to disrupt relevant legal doctrines and institutions. We find that most fields of law appear capable of adapting effectively to climate change. In other words, without some active intervention, we expect the law and policy of climate change adaptation to follow the path of the Law of the Horse - a collection of fields independently adapting to climate change - rather than organically coalescing into a new distinct field. Part III explores why, notwithstanding this conclusion, it may still be desirable to seek a different trajectory. Focusing on the likelihood of systemic adaptation decisions with perverse, harmful results, we identify the potential benefits offered by intervening to shape a new and distinct field of climate change adaptation law and policy. Part IV then identifies the contours of such a field, exploring the distinct purposes of reducing vulnerability, ensuring resiliency, and safeguarding equity. These features provide the normative policy components for a law of climate change adaptation that would be more than just a Law of the Horse. This new field would not replace or supplant any existing field, however, as environmental law did with regard to nuisance law, and it would not be dominated by substantive doctrine. Rather, like the field of environmental justice, this new legal regime would serve as a holistic overlay across other fields to ensure more efficient, effective, and just climate change adaptation solutions