Adsorption isotherms for neutral organic compounds - A hierarchy in modelling: Part V. Models for the inner layer potential difference in the presence of dipolar adsorption

The relations for the inner layer potential &fference (E) in the presence of adsorbed orgamc molecules are derived for three hterarchlcal models, m terms of molecular constants like permanent &pole moments, polarlzablhtles, etc It is shown how the experimentally observed patterns of the E vs 0 plots (hnear m all ranges of $\sigma^M$, non-linear in one or both regions of o M, etc ) can be understood in a serm-quantltatlve manner from the simplest model in our hierarchy, viz the two-state site panty version Two-state multi-site and three-state (sxte panty) models are also analysed and the slope (3E/80),,M tabulated for these also The results for the Esm-Markov effect are denved for all the models and compared with the earlier result of Parsons. A comparison with the GSL phenomenologlcal equation is presented and its molecular basis, as well as the hmltatlons, is analysed. In partxcular, two-state multa-slte and three-state (site panty) models yield E-o M relations that are more general than the "umfied" GSL equation The posslblhty of vaewlng the compact layer as a "composite medium" with an "effective dlelectnc constant" and obtaimng novel phenomenological descnptions IS also indicated.

Electrochemical Reduction of Oriented Graphene Oxide Films: An in Situ Raman Spectroelectrochemical Study

Graphene oxide (GO) is assembled on a gold substrate by a layer-by-layer technique using a self-assembled cystamine monolayer. The negatively charged GO platelets are attached to the positively charged cystamine monolayer through electrostatic interactions. Subsequently, it is shown that the GO can be reduced electrochemically using applied DC bias by scanning the potential from 0 to -1 V vs a saturated calomel electrode in an aqueous electrolyte. The GO and reduced graphene oxide (RGO) are characterized by Raman spectroscopy and atomic force microscopy (AFM). A clear shift of the G band from 1610 cm-1 of GO to 1585 cm-1 of RGO is observed. The electrochemical reduction is followed in situ by micro Raman spectroscopy by carrying out Raman spectroscopic studies during the application of DC bias. The GO and RGO films have been characterized by conductive AFM that shows an increase in the current flow by at least 3 orders of magnitude after reduction. The electrochemical method of reducing GO may open up another way of controlling the reduction of GO and the extent of reduction to obtain highly conducting graphene on electrode materials.

Highly Monodisperse Colloidal Magnesium Nanoparticles by Room Temperature Digestive Ripening

Nanoclusters of 25 nm sized Mg-THF have been prepared by the solvated metal atom dispersion method. Room-temperature digestive ripening of these nanoclusters in the presence of hexadecylamine (HDA) resulted in highly monodisperse colloidal Mg-HDA nanoparticles of 2.8 ± 0.2 nm. An insight into the room-temperature digestive ripening process was obtained by studying the disintegration of clusters for various Mg:HDA ratios. The Mg colloids are quite stable with respect to precipitation of particles under Ar atmosphere. Using this procedure, pure Mg(0) nanopowders were obtained in gram scale quantities. The Mg powder precipitated from the colloid was fully hydrided at 33 bar and 118 °C. Initial desorption of H2 from samples of MgH2 was achieved at a remarkably low temperature, 115 °C compared to >350 °C in bulk Mg, demonstrating the importance of the size on the desorption temperatures.

Design of a TDD Multisector TDM MAC for the WiFiRe Proposal for Rural Broadband Access

The WiFiRe (WiFi Rural Extension) proposal for rural broadband access is being developed under the aegis of CEWIT. The system leverages the widely available, and highly cost-reduced, WiFi chipsets. However, only the physical layer from these chipsets is retained. A single base station carries several WiFi transceivers, each serving one sector of the cell, and all operating on the same WiFi channel in a time division duplex (TDD) manner. We replace the contention based WiFi MAC with a single-channel TDD multisector TDM MAC similar to the WiMax MAC. In this paper we discuss in detail the issues in designing such a MAC for the purpose of carrying packet voice telephony and for Internet access. The problem of determining the optimal spatial reuse is formulated and the optimal spatial reuse and the corresponding cell size is derived. Then the voice and data scheduler is designed. It is shown how throughput fairness can be implemented in the data scheduler. A capacity assessment of the system is also provided.

Analysis of recreational fish catches – dealing with highly skewed distributions with many zeros

Data from surveys of recreational anglers fishing on three estuaries in eastern Australia reveal highly skewed distributions of catches with many zeros. Such data may be analysed using a two component approach involving a binary (zero/non-zero catch) response and the non-zero catches. A truncated regression model was effective in analysing the non-zero catches. Covariates were incorporated in the modelling, and their critical assessment has led to improved measures of fishing effort for this recreational fishery.

Boundary-layer convective heat transfer in a convergent channel

In this paper the numerical solution of the heat transfer problem in a convergent channel with uniform and non-uniform wall temperatures under boundary-layer approximations has been presented. Also, a semi-analytical solution for uniform wall temperature has been obtained.

Semi-similar solution of an unsteady compressible three-dimensional stagnation point boundary layer flow with massive blowing

A semi-similar solution of an unsteady laminar compressible three-dimensional stagnation point boundary layer flow with massive blowing has been obtained when the free stream velocity varies arbitrarily with time. The resulting partial differential equations governing the flow have been solved numerically using an implicit finite-difference scheme with a quasi-linearization technique in the nodal point region and an implicit finite-difference scheme with a parametric differentiation technique in the saddle point region. The results have been obtained for two particular unsteady free stream velocity distributions: (i) an accelerating stream and (ii) a fluctuating stream. Results show that the skin-friction and heat-transfer parameters respond significantly to the time dependent arbitrary free stream velocity. Velocity and enthalpy profiles approach their free stream values faster as time increases. There is a reverse flow in the y-wise velocity profile, and overshoot in the x-wise velocity and enthalpy profiles in the saddle point region, which increase as injection and wall temperature increase. Location of the dividing streamline increases as injection increases, but as the wall temperature and time increase, it decreases.

Unsteady Incompressible Two-Dimensional and Axisymmetric Turbulent Boundary Layer Flows

The unsteady turbulent incompressible boundary-layer flow over two-dimensional and axisymmetric bodies with pressure gradient has been studied. An eddy-viscosity model has been used to model the Reynolds shear stress. The unsteadiness is due to variations in the free stream velocity with time. The nonlinear partial differential equation with three independent variables governing the flow has been solved using Keller's Box method. The results indicate that the free stram velocity distribution exerts strong influence on the boundary-layer characteristics. The point of zero skin friction is found to move upstream as time increases.

GIS-based tools for management of pine plantations, Queensland, Australia

Two examples of GIS-based multiple-criteria evaluations of plantation forests are presented. These desktop assessments use available topographical, geological and pedological information to establish the risk of occurrence of certain environmentally detrimental processes. The first case study is concerned with the risk that chemical additives (i.e. simazine) applied within the forestry landscape may reach the drainage system. The second case study assesses the vulnerability of forested areas to landslides. The subject of the first multiple-criteria evaluation (MCE) was a 4 km2 logging area, which had been recently site-prepared for a Pinus plantation. The criteria considered relevant to the assessment were proximity to creeks, slope, soil depth to the restrictive layer (i.e. potential depth to a perched water table) and soil erodability (based on clay content). The output of the MCE was in accordance with field observations, showing that this approach has the potential to provide management support by highlighting areas vulnerable to waterlogging, which in turn can trigger overland flow and export of pollutants to the local stream network. The subject of the second evaluation was an Araucaria plantation which is prone to landslips during heavy rain. The parameters included in the assessment were drainage system, the slope of the terrain and geological features such as rocks and structures. A good correlation between the MCE results and field observations was found, suggesting that this GIS approach is useful for the assessment of natural hazards. Multiple-criteria evaluations are highly flexible as they can be designed in either vector or raster format, depending on the type of available data. Although tested on specific areas, the MCEs presented here can be easily used elsewhere and assist both management intervention and the protection of the adjacent environment by assessing the vulnerability of the forest landscape to either introduced chemicals or natural hazards.

Unsteady free Convection MHD Boundary Layer Flow Near a Three-Dimensional Stagnation Point

The unsteady free convection boundary layer hydromagnectic flow near a stagnation point of a three-dimensional body with applied magnetic field and time-dependent wall temperature has been studied. Both semi-semilar and self-similar cases have been considered. The equations governing the above flow have been solved numerically using an implicit finite-difference scheme due to Keller. The magnetic field is found to reduce both the heat transfer and skin friction. The effect of the variation of the wall temperature with time and of mass transfer is found to be more pronounced on the heat transfer than on the skin friction. In self-similar case, for decelerating flow, there is temperature overshoot in the presence of fmagnetic field, but in semi-similar case overshoot occurs even without magnetic field due to the unsteadiness

Unsteady laminar incompressible second-order boundary-layer flow at a three-dimensional stagnation point

The unsteadely laminar incompressible second-order boundary-layer flow at the stagnation point of a three-dimensional body has been studied for both nodal and saddle point regions. The effects of mass transfer and Prandtl number have been taken into account. The equations governing the flow have been solved numerically using an implicit finite-difference scheme. It has been found that the parameter characterizing the unsteadiness in the velocity of the free stream, the nature of the stagnation point, the mass transfer and Prandtl number strongly affect the second-order skin friction and heat transfer. The overall skin friction becomes less due to second-order effects but the heat transfer has the opposite behaviour. For large injection, the second-order skin-friction and heat-transfer results prevail over the first-order boundary layer results whereas for the case of large suction the behaviour is just the opposite.

Unsteady compressible 3-dimensional boundary-layer flow near an asymmetric stagnation point with mass transfer

The heat and mass transfer for unsteady laminar compressible boundary-layer flow, which is asymmetric with respect to a 3-dimensional stagnation point (i.e. for a jet incident at an angle on the body), have been studied. It is assumed that the free-stream velocity, wall temperature, and surface mass transfer vary arbitrarily with time and also that the gas has variable properties. The solution in the neighbourhood of the stagnation point has been obtained by series expansion in the longitudinal distance. The resulting partial differential equations have been solved numerically using an implicit finite-difference scheme. The results show that, in contrast with the symmetric flow, the maximum heat transfer does not occur at the stagnation point. The skin-friction and heat-transfer components due to asymmetric flow are only weakly affected by the mass transfer as compared to those components associated with symmetric flow. The variation of the wall temperature with time has a strong effect on the heat transfer component associated with the symmetric part of the flow. The skin friction and heat transfer are strongly affected by the variation of the density-viscosity product across the boundary layer. The skin friction responds more to the fluctuations of the free stream oscillating velocities than the heat transfer. The results have been compared with the available results and they are found to be in excellent agreement.

Incompressible boundary layer for longitudinal flow over a cylinder with an applied magnetic field

The flow, heat and mass transfer problem for a steady laminar incompressible boundary layer flow in an electrically conducting fluid over a longitudinal cylinder with an applied magnetic field has been studied. The partial differential equations governing the flow have been solved numerically using an implicit finite-difference scheme. The results are found to be strongly dependent on the magnetic field and dissipation parameter. The effect of the mass transfer is more pronounced on the skin friction than on the heat transfer. The results have been compared with those of the series solution, the asymptotic solution, the Glauert and Lighthill's solution, local similarity, local nonsimilarity and difference-differential methods. Good agreement is found with all of them, except with the results of the local similarity and series solution methods.

Absence of reptation in highly confined polymers

We present results of mechanical stress relaxation measurements on polymers confined at the air-water interface in the form of a monolayer. Systematic measurements allow, to our knowledge, for the first time, observation of the scaling of the stress relaxation time of the highly confined polymers as a function of both surface concentration and molecular weight. The observed scaling is found to be very close to that expected for motion of unentangled polymer solutions with hydrodynamic interactions. Our experimental observations thus clearly rule out the possibility of entanglement and hence reptation as a mode of relaxation in such highly confined polymeric systems.