Electrospinning atactic polystyrene: A neutron scattering study

Electrospinning is a method used to produce nanoscale to microscale sized polymer fibres. In this study we electrospin 1:1 blends of deuterated and hydrogenated atactic-Polystyrene from N,N-Dimethylformamide for small angle neutron scattering experiments in order to analyse the chain conformation in the electrospun fibres. Small angle neutron scattering was carried out on randomly orientated fibre mats obtained using applied voltages of 10kV-15kV and needle tip to collector distances of 20cm and 30cm. Fibre diameters varied from 3mm - 20mm. Neutron scattering data from fibre samples were compared with bulk samples of the same polymer blend. The scattering data indicates that there are pores and nanovoiding present in the fibres; this was confirmed by scanning electron microscopy. A model that combines the scattering from the pores and the labelled polymer chains was used to extract values for the radius of gyration. The radius of gyration in the fibres is found to vary little with the applied voltage, but varies with the initial solution concentration and fibre diameter. The values for the radius of gyration in the fibres are broadly equivalent to that of the bulk state.

A review of the theoretical basis for bulk mass flux convective parameterization

Most parameterizations for precipitating convection in use today are bulk schemes, in which an ensemble of cumulus elements with different properties is modelled as a single, representative entraining-detraining plume. We review the underpinning mathematical model for such parameterizations, in particular by comparing it with spectral models in which elements are not combined into the representative plume. The chief merit of a bulk model is that the representative plume can be described by an equation set with the same structure as that which describes each element in a spectral model. The equivalence relies on an ansatz for detrained condensate introduced by Yanai et al. (1973) and on a simplified microphysics. There are also conceptual differences in the closure of bulk and spectral parameterizations. In particular, we show that the convective quasi-equilibrium closure of Arakawa and Schubert (1974) for spectral parameterizations cannot be carried over to a bulk parameterization in a straightforward way. Quasi-equilibrium of the cloud work function assumes a timescale separation between a slow forcing process and a rapid convective response. But, for the natural bulk analogue to the cloud-work function (the dilute CAPE), the relevant forcing is characterised by a different timescale, and so its quasi-equilibrium entails a different physical constraint. Closures of bulk parameterization that use the non-entraining parcel value of CAPE do not suffer from this timescale issue. However, the Yanai et al. (1973) ansatz must be invoked as a necessary ingredient of those closures.

Temperature- and Pressure-induced Proton Transfer in the 1:1 Adduct Formed between Squaric Acid and 4,4 '-Bipyridine

We have applied a combination of spectroscopic and diffraction methods to study the adduct formed between squaric acid and bypridine, which has been postulated to exhibit proton transfer associated with a single-crystal to single-crystal phase transition at ca. 450 K. A combination of X-ray single-crystal and very-high flux powder neutron diffraction data confirmed that a proton does transfer from the acid to the base in the high-temperature form. Powder X-ray diffraction measurements demonstrated that the transition was reversible but that a significant kinetic energy barrier must be overcome to revert to the original structure. Computational modeling is consistent with these results. Modeling also revealed that, while the proton transfer event would be strongly discouraged in the gas phase, it occurs in the solid state due to the increase in charge state of the molecular ions and their arrangement inside the lattice. The color change is attributed to a narrowing of the squaric acid to bipyridine charge-transfer energy gap. Finally, evidence for the possible existence of two further phases at high pressure is also presented.

Moving towards a more mechanistic approach in the determination of soil heat flux from remote measurements - I. A universal approach to calculate thermal inertia

In this paper we pledge that physically based equations should be combined with remote sensing techniques to enable a more theoretically rigorous estimation of area-average soil heat flux, G. A standard physical equation (i.e. the analytical or exact method) for the estimation of G, in combination with a simple, but theoretically derived, equation for soil thermal inertia (F), provides the basis for a more transparent and readily interpretable method for the estimation of G; without the requirement for in situ instrumentation. Moreover, such an approach ensures a more universally applicable method than those derived from purely empirical studies (employing vegetation indices and albedo, for example). Hence, a new equation for the estimation of Gamma(for homogeneous soils) is discussed in this paper which only requires knowledge of soil type, which is readily obtainable from extant soil databases and surveys, in combination with a coarse estimate of moisture status. This approach can be used to obtain area-averaged estimates of Gamma(and thus G, as explained in paper II) which is important for large-scale energy balance studies that employ aircraft or satellite data. Furthermore, this method also relaxes the instrumental demand for studies at the plot and field scale (no requirement for in situ soil temperature sensors, soil heat flux plates and/or thermal conductivity sensors). In addition, this equation can be incorporated in soil-vegetation-atmosphere-transfer models that use the force restore method to update surface temperatures (such as the well-known ISBA model), to replace the thermal inertia coefficient.

Moving towards a more mechanistic approach in the determination of soil heat flux from remote measurements - II. Diurnal shape of soil heat flux

For vegetated surfaces, calculation of soil heat flux, G, with the Exact or Analytical method requires a harmonic analysis of below-canopy soil surface temperature, to obtain the shape of the diurnal course of G. When determining G with remote sensing methods, only composite (vegetation plus soil) radiometric brightness temperature is available. This paper presents a simple equation that relates the sum of the harmonic terms derived for the composite radiometric surface temperature to that of belowcanopy soil surface temperature. The thermal inertia, Gamma(,) for which a simple equation has been presented in a companion paper, paper I, is used to set the magnitude of G. To assess the success of the method proposed in this paper for the estimation of the diurnal shape of G, a comparison was made between 'remote' and in situ calculated values from described field sites. This indicated that the proposed method was suitable for the estimation of the shape of G for a variety of vegetation types and densities. The approach outlined in paper I, to obtain Gamma, was then combined with the estimated harmonic terms to predict estimates of G, which were compared to values predicted by empirical remote methods found in the literature. This indicated that the method proposed in the combination of papers I and II gave reliable estimates of G, which, in comparison to the other methods, resulted in more realistic predictions for vegetated surfaces. This set of equations can also be used for bare and sparsely vegetated soils, making it a universally applicable method. (C) 2007 Elsevier B.V. All rights reserved.

Remote estimation of thermal inertia and soil heat flux for bare soil

A method is presented which allows thermal inertia (the soil heat capacity times the square root of the soil thermal diffusivity, C(h)rootD(h)), to be estimated remotely from micrometeorological observations. The method uses the drop in surface temperature, T-s, between sunset and sunrise, and the average night-time net radiation during that period, for clear, still nights. A Fourier series analysis was applied to analyse the time series of T-s . The Fourier series constants, together with the remote estimate of thermal inertia, were used in an analytical expression to calculate diurnal estimates of the soil heat flux, G. These remote estimates of C(h)rootD(h) and G compared well with values derived from in situ sensors. The remote and in situ estimates of C(h)rootD(h) both correlated well with topsoil moisture content. This method potentially allows area-average estimates of thermal inertia and soil heat flux to be derived from remote sensing, e.g. METEOSAT Second Generation, where the area is determined by the sensor's height and viewing angle. (C) 2003 Elsevier B.V. All rights reserved.