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Vincent S J Craig

Publications and source records attributed to Vincent S J Craig.

8 recordsLinked to original sources

Physical properties of phase-change emulsions.

Phase-change emulsions (PCE) are important in a variety of applications, from ultrasound imaging to the explosive material used in the mining industry, but until now there has been no adequate theory to describe their activation properties. The PCE consists of a low-boiling-point liquid, known as the volatile phase, dispersed in an aqueous phase. The volatile phase boils as a result of an increase in the temperature of the emulsion. The volume of the emulsion will increase during this phase transition, with the transition temperature and final volume of the emulsion highly dependent on the initial radius of the liquid droplets. Here a description of the change in boiling point and freezing point of the volatile phase, as well as the volume change of a droplet in the emulsion as a function of the initial droplet radius, is presented. The influence of volatile phase solubility, liquid-liquid interfacial tension, and final temperature are explored, accounting for the influence of confinement on the properties of the volatile phase. Beyond this, a means by which the diffusivity of the gas in the continuous liquid phase can be measured is derived.

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The origin of surface stress induced by adsorption of iodine on gold.

The cantilever technique for the measurement of film stress on both macroscopic and microscopic cantilevers is validated, then applied to the experimental determination of film stress induced by the adsorption of a monolayer of iodine onto a gold substrate. A model is proposed that relates the change in the interatom potential upon chemisorption of iodine onto gold to the measured film stress. Excellent agreement is found with the experimentally determined value. This result gives insight into the origins of film stress that is observed in all thin film and coating applications.

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Physical properties of nanobubbles on hydrophobic surfaces in water and aqueous solutions.

In recent years there has been an accumulation of evidence for the existence of nanobubbles on hydrophobic surfaces in water, despite predictions that such small bubbles should rapidly dissolve because of the high internal pressure associated with the interfacial curvature and the resulting increase in gas solubility. Nanobubbles are of interest among surface scientists because of their potential importance in the long-range hydrophobic attraction, microfluidics, and adsorption at hydrophobic surfaces. Here we employ recently developed techniques designed to induce nanobubbles, coupled with high-resolution tapping-mode atomic force microscopy (TM-AFM) to measure some of the physical properties of nanobubbles in a reliable and repeatable manner. We have reproduced the earlier findings reported by Hu and co-workers. We have also studied the effect of a wide range of solutes on the stability and morphology of these deliberately formed nanobubbles, including monovalent and multivalent salts, cationic, anionic, and nonionic surfactants, as well as solution pH. The measured physical properties of these nanobubbles are in broad agreement with those of macroscopic bubbles, with one notable exception: the contact angle. The nanobubble contact angle (measured through the denser aqueous phase) was found to be much larger than the macroscopic contact angle on the same substrate. The larger contact angle results in a larger radius of curvature and a commensurate decrease in the Laplace pressure. These findings provide further evidence that nanobubbles can be formed in water under some conditions. Once formed, these nanobubbles remain on hydrophobic surfaces for hours, and this apparent stability still remains a well-recognized mystery. The implications for sample preparation in surface science and in surface chemistry are discussed.

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Sensing cantilever beam bending by the optical lever technique and its application to surface stress.

Cantilever beams, both microscopic and macroscopic, are used as sensors in a great variety of applications. An optical lever system is commonly employed to determine the deflection and thereby the profile of the cantilever under load. The sensitivity of the optical lever must be calibrated, and this is usually achieved by application of a known load or deflection to the free end of the cantilever. When the sensing operation involves a different type of load or a combination of types of loadings, the calibration and the deflection values derived from it become invalid. Here we develop a master equation that permits the true deflection of the cantilever to be obtained simply from the measurement of the apparent deflection for uniformly distributed loadings and end-moment loadings. These loadings are relevant to the uniform adsorption or application of material to the cantilever or the application of a surface stress to the cantilever and should assist experimentalists using the optical lever, such as in the atomic force microscope, to measure cantilever deflections in a great variety of sensing applications. We then apply this treatment to the experimental evaluation of surface stress. Three forms of Stoney's equation that relate the apparent deflection to the surface stress, which is valid for both macroscopic and microscopic experiments, are derived. Analysis of the errors arising from incorrect modeling of the loading conditions of the cantilever currently applied in experiments is also presented. It is shown that the reported literature values for surface stress in microscopic experiments are typically 9% smaller than their true value. For macroscopic experiments, we demonstrate that the added mass of the film or coating generally dominates the measured deflection and must be accounted for accurately if surface stress measurements are to be made. Further, the reported measurements generally use a form of Stoney's equation that is in error, resulting in an overestimation of surface stress by a factor >5.

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Atomic force microscopy study of the interaction between adsorbed poly(ethylene oxide) layers: effects of surface modification and approach velocity.

The interaction forces between layers of the triblock copolymer Pluronic F108 adsorbed onto hydrophobic radio frequency glow discharge (RFGD) thin film surfaces and hydrophilic silica, in polymer-free 0.15 M NaCl solution, have been measured using the atomic force microscope (AFM) colloid probe technique. Compression of Pluronic F108 layers adsorbed on the hydrophobic RFGD surfaces results in a purely repulsive force due to the steric overlap of the layers, the form of which suggests that the PEO chains adopt a brush conformation. Subsequent fitting of these data to the polymer brush models of Alexander-de Gennes and Milner, Witten, and Cates confirms that the adsorbed Pluronic F108 adsorbs onto hydrophobic surfaces as a polymer brush with a parabolic segment density profile. In comparison, the interaction between Pluronic F108 layers adsorbed on silica exhibits a long ranged shallow attractive force and a weaker steric repulsion. The attractive component is reasonably well described by van der Waals forces, but polymer bridging cannot be ruled out. The weaker steric component of the force suggests that the polymer is less densely packed on the surface and is less extended into solution, existing as polymeric isolated mushrooms. When the surfaces are driven together at high piezo ramp velocities, an additional repulsive force is measured, attributable to hydrodynamic drainage forces between the surfaces. In comparing theoretical predictions of the hydrodynamic force to the experimentally obtained data, agreement could only be obtained if the flow profile of the aqueous solution penetrated significantly into the polymer brush. This finding is in line with the theoretical predictions of Milner and provides further evidence that the segment density profile of the adsorbed polymer brush is parabolic. A velocity dependent additional stepped repulsive force, reminiscent of a solvation oscillatory force, is also observed when the adsorbed layers are compressed under high loads. This additional force is presumably a result of hindered drainage of water due to the presence of a high volume fraction of polymer chains between the surfaces.

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Floc strength characterization technique. An insight into silica aggregation.

This paper tests an approach to the estimation of relative particle bond strength based on the nondimensional floc and aggregation factors. The strength of flocs formed by aggregating nanosized silica particles with the addition of potassium chloride (KCl) or cationic surfactants, alkyltrimethylammonium bromide (mixture of CTAB, DTAB, and MTAB) was analyzed. The bonding force of the flocs formed in surfactant compared to that formed in the KCl system was estimated using the new dimensional analysis approach. This force ratio was then compared to that obtained by atomic force microscopy.

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Determination of coupled solvent mass in quartz crystal microbalance measurements using deuterated solvents.

A simple method is described for determining of the contribution of hydrodynamically coupled solvent to the adsorbed film mass determined in a quartz crystal microbalance (QCM) when operated in liquid. The method requires no additional apparatus and utilizes the change in QCM resonant frequency response between measurements made in non-deuterated and deuterated solvents. The mass of coupled water in a polymer film has been determined and is found to agree with that determined by XPS analysis of the dried polymer film.

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Surface roughness and hydrodynamic boundary slip of a newtonian fluid in a completely wetting system.

The influence of surface roughness on the boundary condition for the flow of a Newtonian fluid near a hard wall has been investigated by measurement of the hydrodynamic drainage force. The degree of slip is found to increase with surface roughness. This leads to the conclusion that in most practical situations boundary slip takes place, leading to a reduction of the drainage force.

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