Confined fluids in a Janus pore: influence of surface asymmetry on structure and solvation forces

Density distribution, fluid structure and solvation forces for fluids confined in Janus slit-shaped pores are investigated using grand canonical Monte Carlo simulations. By varying the degree of asymmetry between the two smooth surfaces that make up the slit pores, a wide variety of adsorption situations are observed. The presence of one moderately attractive surface in the asymmetric pore is sufficient to disrupt the formation of frozen phases observed in the symmetric case. In the extreme case of asymmetry in which one wall is repulsive, the pore fluid can consist of a frozen contact layer at the attractive surface for smaller surface separations (H) or a frozen contact layer with liquid-like and gas-like regions as the pore width is increased. The superposition approximation, wherein the solvation pressure and number density in the asymmetric pores can be obtained from the results on symmetric pores, is found to be accurate for H > 4 sigma(ff), where sigma(ff) is the Lennard-Jones fluid diameter and within 10% accuracy for smaller surface separations. Our study has implications in controlling stick slip and overcoming static friction `stiction' in micro and nanofluidic devices.

Influence of Hydrophilic Surface Specificity on the Structural Properties of Confined Water

The influence of chemical specificity of hydrophilic surfaces on the structure of confined water in the subnanometer regime is investigated using grand canonical Monte Carlo Simulations. The structural variations for water confined between hydroxylated silica surfaces are contrasted with water confined between mica surfaces. Although both surfaces are hydrophilic, our Study shows that hydration of potassium ions on the mica surface has a strong influence on the water Structure and solvation force response of confined water. In contrast to the disrupted hydrogen bond network observed for water confined between Mica Surfaces, water between silica surfaces retains its hydrogen bond network displaying bulklike structural features down to surface separations as small as 0.45 nm. Hydrogen bonding of all invariant contact water layer with the surface silanol groups aids in maintaining a constant number of hydrogen bonds per water molecule for the silica surfaces. As a consequence water depletion and rearrangement upon decreasing confinement is a strong function of the hydrophilic surface specificity, particularly at smaller separations. An oscillatory solvation force response is only observed for water confined between Silica surfaces, and bulklike features are observed for both Surfaces above a surface separation of about 1.2 nm. We evaluate and contrast the water density, dipole moment distributions, pi pair correlation functions, and solvation forces as a function of the surface separation.

Phase equilibria and plate-fluid interfacial tensions for associating hard sphere fluids confined in slit pores

The excess Helmholtz free energy functional for associating hard sphere fluid is formulated by using a modified fundamental measure theory [Y. X. Yu and J. Z. Wu, J. Chem. Phys. 117, 10156 (2002)]. Within the framework of density functional theory, the thermodynamic properties including phase equilibria for both molecules and monomers, equilibrium plate-fluid interfacial tensions and isotherms of excess adsorption, average molecule density, average monomer density, and plate-fluid interfacial tension for four-site associating hard sphere fluids confined in slit pores are investigated. The phase equilibria inside the hard slit pores and attractive slit pores are determined according to the requirement that temperature, chemical potential, and grand potential in coexistence phases should be equal and the plate-fluid interfacial tensions at equilibrium states are predicted consequently. The influences of association energy, fluid-solid interaction, and pore width on phase equilibria and equilibrium plate-fluid interfacial tensions are discussed.

Influence of Oxide Particle Network Morphology on Ion Solvation and Transport in ``Soggy Sand''Electrolytes

The role of oxide surface chemical composition and solvent on ion solvation and ion transport of ``soggy sand'' electrolytes are discussed here. A ``soggy sand'' electrolyte system comprising dispersions of hydrophilic/hydrophobic functionalized aerosil silica in lithium perchlorate methoxy polyethylene glycol solution was employed for the study. Static and dynamic rheology measurements show formation of an attractive particle network in the case of the composite with unmodified aerosil silica (i.e., with surface silanol groups) as well as composites with hydrophobic alkane groups. While particle network in the composite with hydrophilic aerosil silica (unmodified) were due to hydrogen bonding, hydrophobic aerosil silica particles were held together via van der Waals forces. The network strength in the latter case (i.e., for hydrophobic composites) were weaker compared with the composite with unmodified aerosil silica. Both unmodified silica as well as hydrophobic silica composites displayed solid-like mechanical strength. No enhancement in ionic conductivity compared to the liquid electrolyte was observed in the case of the unmodified silica. This was attributed to the existence of a very strong particle network, which led to the ``expulsion'' of all conducting entities from the interfacial region between adjacent particles. The ionic conductivity for composites with hydrophobic aerosil particles displayed ionic conductivity dependent on the size of the hydrophobic chemical moiety. No spanning attractive particle network was observed for aerosil particles with surfaces modified with stronger hydrophilic groups (than silanol). The composite resembled a sol, and no percolation in ionic conductivity was observed.

Marketplace forces and the history of retailing : The cycle of control

This paper traces the history of store (retailer-controlled) and national (manufacture controlled)brands; identifies the key historical characteristics of the past 200 years of marketing history;describes the four main time periods of U.S. retail marketing (1800 - 2000); and comments on the most likely developments within the current phases of brand marketing. Will the future focus on technology and new forms of communications? The Internet exemplifies an unconventional retailing environment, with etailer numbers growing rapidly. The central proposition of this paper is that a "cycle of control" - a pattern of marketing developments within the history of retailing and national marketing communications - Can indicate the success of marketing strategies in the future.

Project diagnostics : assessing the condition of projects and identifying poor health combing forces

In many cases, construction projects do not achieve the objectives that the project participants set for them. If participants could better understand how their project is performing overall, at various stages of its delivery, then the opportunities to achieve project success would almost certainly be greater. This paper documents a method of assessing the status of a project, at a point in its design or construction phase, or after completion. The status is assessed in terms of up to seven (7) key success factors. Any evidence of less than adequate performance in these performance areas is scrutinised to seek out the root causes of why this situation is happening. Using these identified root causes of under performance, general suggestions can then be made as to how to return the project to good health. A software package that assists in assessing the status of the project has been developed. The package is currently being calibrated before commercial release.

The measurement of applied forces during anterior single rod correction of adolescent idiopathic scoliosis

Adolescent idiopathic scoliosis (AIS) is the most common form of spinal deformity in paediatrics, prevalent in approximately 2-4% of the general population. While it is a complex three-dimensional deformity, it is clinically characterised by an abnormal lateral curvature of the spine. The treatment for severe deformity is surgical correction with the use of structural implants. Anterior single rod correction employs a solid rod connected to the anterior spine via vertebral body screws. Correction is achieved by applying compression between adjacent vertebral body screws, before locking each screw onto the rod. Biomechanical complication rates have been reported as high as 20.8%, and include rod breakage, screw pull-out and loss of correction. Currently, the corrective forces applied to the spine are unknown. These forces are important variables to consider in understanding the biomechanics of scoliosis correction. The purpose of this study was to measure these forces intra-operatively during anterior single rod AIS correction.

Correlating vehicle forces and track profile

A research project was conducted at Queensland University of Technology on the relationship between the forces at the wheel-rail interface in track and the rate of degradation of track. Data for the study was obtained from an instrumented vehicle which ran repeatedly over a section of Queensland Rail's track in Central Queensland over a 6-month period. The wheel-rail forces had to be correlated with the elements of roughness in the test track profile, which were measured with a variety of equipment. At low frequencies, there was strong correlation between forces and profile, as expected, but diminishing correlation as frequencies increased.

AFM study of forces between silicon oil and hydrophobic - hydrophylic surfaces in aqueous solutions

An investigation has been made of the interactions between silicone oil and various solid substrates immersed in aqueous solutions. Measurements were made using an atomic force microscope (AFM) using the colloid-probe method. The silicone oil drop is simulated by coating a small silica sphere with the oil, and measuring the force as this coated sphere is brought close to contact with a flat solid surface. It is found that the silicone oil surface is negatively charged, which causes a double-layer repulsion between the oil drop and another negatively charged surface such as mica. With hydrophilic solids, this repulsion is strong enough to prevent attachment of the drop to the solid. However, with hydrophobic surfaces there is an additional attractive force which overcomes the double-layer repulsion, and the silicone oil drop attaches to the solid. A "ramp" force appears in some, but not all, of the data sets. There is circumstantial evidence that this force results from compression of the silicone oil film coated on the glass sphere.