In situ apparatus for the study of clathrate hydrates relevant to solar system bodies using synchrotron X-ray diffraction and Raman spectroscopy

Clathrate hydrates are believed to play a significant role in various solar system environments, e.g. comets, and the surfaces and interiors of icy satellites, however the structural factors governing their formation and dissociation are poorly understood. We demonstrate the use of a high pressure gas cell, combined with variable temperature cooling and time-resolved data collection, to the in situ study of clathrate hydrates under conditions relevant to solar system environments. Clathrates formed and processed within the cell are monitored in situ using synchrotron X-ray powder diffraction and Raman spectroscopy. X-ray diffraction allows the formation of clathrate hydrates to be observed as CO2 gas is applied to ice formed within the cell. Complete conversion is obtained by annealing at temperatures just below the ice melting point. A subsequent rise in the quantity of clathrate is observed as the cell is thermally cycled. Four regions between 100-5000cm-1 are present in the Raman spectra that carry features characteristic of both ice and clathrate formation. This novel experimental arrangement is well suited to studying clathrate hydrates over a range of temperature (80-500K) and pressure (1-100bar) conditions and can be used with a variety of different gases and starting aqueous compositions. We propose the increase in clathrate formation observed during thermal cycling may be due to the formation of a quasi liquid-like phase that forms at temperatures below the ice melting point, but which allows easier formation of new clathrate cages, or the retention and delocalisation of previously formed clathrate structures, possibly as amorphous clathrate. The structural similarities between hexagonal ice, the quasi liquid-like phase, and crystalline CO2 hydrate mean that differences in the Raman spectrum are subtle; however, all features out to 5000cm-1 are diagnostic of clathrate structure.Comment: Astronomy & Astrophysics, in press. 6 page

An Examination of the Farm Level Demand for Pecans

Demand and Price Analysis,

FARM LEVEL DEMAND FOR PECANS RECONSIDERED

Previous studies have consistently indicated the anomalous result of a price inflexible demand for pecans. However, these efforts did not have an adequate measure of pecan stocks available and, as a result, stocks were either excluded from consideration or a proxy variable was introduced. A time series of pecan stocks is now available. Use of this time series in a price dependent demand function results in a flexible farm level demand for pecans. This points out the danger of excluding an appropriate variable or using a so-called "reasonable" proxy variable.Crop Production/Industries,

Comparison of the spinels Co3O4 and NiCo2O4 as bifunctional oxygen catalysts in alkaline media

Data from experiments with both rotating disc electrodes (RDEs) and gas diffusion electrodes (GDEs) are used to investigate the properties of the spinels, Co3O4 and NiCo2O4, as bifunctional oxygen electrocatalysts. Emphasis is placed on catalyst compositions and electrode structures free of carbon. Oxygen evolution and reduction occur at surfaces where the transition metals are in different oxidation states but the surface can be repeatedly cycled between these two states without significant change. It is shown that carbon-free, NiCo2O4 catalysed GDEs can be fabricated using structures based on stainless steel cloth or nickel foam. Those based on nickel foam can be cycled extensively and allow both O2 evolution and reduction at current densities up to 100 mA cm?2

Non-aqueous formation of the calcium carbonate polymorph vaterite: astrophysical implications

We study the formation of calcium carbonate, through the solid-gas interaction of amorphous Ca-silicate with gaseous CO2, at elevated pressures, and link this to the possible presence of calcium carbonate in a number of circumstellar and planetary environments. We use in-situ synchrotron X-Ray powder diffraction to obtain detailed structural data pertaining to the formation of the crystalline calcium carbonate phase vaterite and its evolution with temperature. We found that the metastable calcium carbonate phase vaterite was formed alongside calcite, at elevated CO2 pressure, at room temperature and subsequently remained stable over a large range of temperature and pressure. We report the formation of the calcium carbonate mineral vaterite whilst attempting to simulate carbonate dust grain formation in astrophysical environments. This suggests that vaterite could be a mineral component of carbonate dust and also presents a possible method of formation for vaterite and its polymorphs on planetary surfaces.Comment: Astronomy and Astrophysics, in pres

Suicide prevention and mood disorders: Self-exclusion agreements for firearms as a suicide prevention strategy

Suicide involves a complex set of behaviors and emotions that lead up to actions that may be based on planning and forethought or the result of impulse. While there are a host of antecedent circumstances the presence of a mood disorder, primarily depression, is the most common factor in suicide. While management of depression is recognized as important prevention strategy in depression, the means by which suicide occurs must be a critical element of prevention. Policies that lower access to the means for suicide will decrease the fatality. Guns are associated with half of suicides and the case fatality rate of gun associated suicide is over 90% compared to 7% for all other means. This emphasizes the importance of offering strategies that limit access to guns to those at higher risk for suicide. A declaration of formal self-exclusion for access to firearms (guns and ammunition) offers the individual at greater risk for suicide to place themselves on an official list that would prevent them from purchasing lethal weapons. A person with depression, when well, might wish to enroll voluntarily to prevent themselves, when ill, from procuring a weapon to harm themselves or others. This recognizes the autonomy of the person and protects both the individual, the family, and society

Solvent-Annealed Crystalline Squaraine: PC 70 BM (1:6) Solar Cells

No AbstractPeer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/83478/1/184_ftp.pd

Voltammetric studies of the mechanism of the oxygen reduction in alkaline media at the spinels Co3O4and NiCo2O4

The mechanism of O2 reduction at the spinels, Co3O4 and NiCo2O4, in KOH electrolyte is probed using voltammetry at rotating disc and rotating ring-disc electrodes by examination of the rotation rate dependent limiting currents. The analysis shows that the products and mechanisms at the two spinels are quite different. At the cobalt spinel, a substantial amount of the 2e? reduction product, H2O2, is formed while at NiCo2O4 the 4e? reduction strongly predominates. In terms of both the overpotential for reduction and its limiting current density, the mixed spinel is a substantially better electrocatalyst. It is proposed that the differences arise from an enhanced rate of O-O bond cleavage early in the reduction process at NiCo2O4