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Stuart M Clarke

Publications and source records attributed to Stuart M Clarke.

7 recordsLinked to original sources

Adsorption and mixing behavior of ethers and alkanes at the solid/liquid interface.

The behavior of binary mixtures of linear symmetrical ethers and alkanes adsorbed to a graphite surface from the bulk liquid mixtures is described on the basis of differential scanning calorimetry (DSC) data. Both the ethers and the alkanes are found to form solid monolayers when adsorbed from the liquid. In addition, the monolayer mixing behavior is addressed. The results indicate that there is good, essentially ideal, mixing in the monolayers for ethers and alkanes of the same overall chain length, where the chain length is equal to the total number of carbon and oxygen atoms in the molecule. However, a difference in chain length of more than one atom results in a variation of mixing behavior from nonideal mixing (for long pairs) to phase separation (for short pairs) on the graphite surface. Hence, we conclude that it is the relative chain lengths that control mixing behavior. The results are quantified using a regular solution model with a correction for preferential adsorption. The phase behavior of the mixed monolayers is also compared to the behavior of the bulk. Interestingly, we observe mixtures where the bulk and monolayer behavior are quite different, for example, phase separation in the bulk but essentially ideal mixing in the monolayer for mixtures of ethers and alkanes with the same chain lengths. At present, we attribute this mixing in the monolayer to dilution of the unfavorable ether oxygen-ether oxygen lone pair interactions by the coadsorbed alkanes. In addition, we find evidence for the preferential adsorption of the alkane over the ether. For example, heptane is preferentially adsorbed over dibutyl ether even though it contains two fewer atoms in the molecular chain. This contrasts with the preferential adsorption of alcohols over alkanes reported previously (Messe, L.; Perdigon, A.; Clarke, S. M.; Inaba, A.; Arnold, T. Langmuir 2005, 21, 5085-5093).

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Thermal and UV shape shifting of surface topography.

The confinement of LCE materials into surface monodomains via micropatterning leads to the formation of reversible, shape-shifting surface patterns. The individual features are liquid crystalline monodomains, and by switching to an isotropic state using light or heat, the features switch between imprinted circular features and anisotropic liquid crystalline features.

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Adsorption of gelatin to a polystyrene/water interface as a function of concentration, pH, and ionic strength.

The technique of neutron reflection has been used to investigate the adsorption of alpha-enriched gelatin from aqueous solution onto spun polystyrene substrates. Neutron reflection can provide information about the distribution of material perpendicular to an interface as well as total adsorbed amounts. The adsorbed layers were found to have maximum density at the surface, decaying with distance into solution. The adsorbed amount, layer thickness, and density were all seen to increase with solution concentration. Temperature was found to have little effect on adsorption. Thicker, less dense layers were observed at high pH and thinner, denser layers were observed at low pH, but the total adsorbed amount did not change significantly. The presence of sodium chloride had little effect on the adsorbed layers. The results are discussed in the context of other studies and the known amino acid sequence of alpha-gelatin.

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Preferred orientation in filtercakes of kaolinite.

The orientational order parameter of dense colloidal dispersions of plate-like particles as a function of volume fraction is measured using neutron diffraction. This non-invasive experimental approach directly provides the full particle orientation distribution from which the order parameters can be calculated. The orientation parameters are shown to be linked to the solids fractions of the cakes and the macroscopic permeability of the samples. However, this study suggests that, although orientation can be relevant for a given system, other factors can have a stronger influence, for example, the degree of dispersion or colloidal stability of the clay and may be the principle factor that controls permeability. In addition, we report enhanced ordering of these materials under the influence of an external cross-flow field.

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Alkane/Alcohol mixed monolayers at the solid/liquid interface.

In this work, we present the behavior of solid monolayers of binary mixtures of alkanes and alcohols adsorbed on the surface of graphite from their liquid mixtures. We demonstrate that solid monolayers form for all the combinations investigated here. Differential scanning calorimetry (DSC) is used to identify the surface phase behavior of these mixtures, and elastic neutron incoherent scattering has been used to determine the composition of the mixed monolayers inferred by the calorimetry. The mixing behavior of the alcohol/alkane monolayer mixtures is compared quantitatively with alkane/alkane and alcohol/alcohol mixtures using a regular solution approach to model the incomplete mixing in the solid monolayer with preferential adsorption determining the surface composition. This analysis indicates the preferential adsorption of alcohols over alkanes of comparable alkyl chain length and even preferential adsorption of shorter alcohols over longer alkanes, which contrasts strongly with mixtures of alkane/alkane and alcohol/alcohol of different alkyl chain lengths where the longer homologue is always found to preferentially adsorb over the shorter. The alcohol/alkane mixtures are all found to phase separate to a significant extent in the adsorbed layer mixtures even when molecules are of a similar size. Again, this contrasts strongly with alkane/alkane and alcohol/alcohol mixtures where, although phase separation is found for molecules of significantly different size, good mixing is found for similar size species.

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Shape-memory nanoparticles from inherently non-spherical polymer colloids.

Samples of polymeric materials generally have no intrinsic shape; rather their macroscopic form is determined by external forces such as surface tension and memory of shear (for example, during extrusion, moulding or embossing). Hence, in the molten state, the thermodynamically most stable form for polymer (nano)particles is spherical. Here, we present the first example of polymer nanoparticles that have an intrinsic non-spherical shape. We observe the formation of high-aspect-ratio ellipsoidal polymer nanoparticles, of controlled diameter, made from main-chain liquid crystalline polymers using a mini-emulsion technique. The ellipsoidal shape is shown to be an equilibrium (reversible) characteristic and a direct result of the material shape memory when a liquid crystal nanoparticle is in its monodomain form.

Colloids↗

Layer-by-layer surface freezing of linear alcohols at the graphite/liquid interface.

Differential scanning calorimetry (DSC), incoherent elastic neutron scattering, and neutron diffraction are used to demonstrate the presence of adsorbed solid multilayers of linear alcohols at the graphite-liquid alcohol interface. All alcohols studied (C(5)-C(18)) are found to form at least one monolayer. In addition all the even alcohols investigated (C(6)OH to C(18)OH) show multilayer formation. However, only the short odd alcohols (C(5)OH to C(11)OH) clearly exhibit additional features indicating multilayer formation.

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