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Register a new userSolvent Mediated Assembly of Nanoparticles Confined in Mesoporous Alumina
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The controlled self-assembly of thiol stabilized gold nanocrystals in a mediating solvent and confined within mesoporous alumina was probed in situ with small angle x-ray scattering. The evolution of the self-assembly process was controlled reversibly via regulated changes in the amount of solvent condensed from an undersaturated vapor. Analysis indicated that the nanoparticles self-assembled into cylindrical monolayers within the porous template. Nanoparticle nearest-neighbor separation within the monolayer increased and the ordering decreased with the controlled addition of solvent. The process was reversible with the removal of solvent. Isotropic clusters of nanoparticles were also observed to form temporarily during desorption of the liquid solvent and disappeared upon complete removal of liquid. Measurements of the absorption and desorption of the solvent showed strong hysteresis upon thermal cycling. In addition, the capillary filling transition for the solvent in the nanoparticle-doped pores was shifted to larger chemical potential, relative to the liquid/vapor coexistence, by a factor of 4 as compared to the expected value for the same system without nanoparticles.
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The filling behavior of a room temperature solvent, perfluoromethylcyclohexane, in approximately 20 nm nanoporous alumina membranes was investigated in situ with small angle x-ray scattering. Adsorption in the pores was controlled reversibly by varying the chemical potential between the sample and a liquid reservoir via a thermal offset, $Delta$T. The system exhibited a pronounced hysteretic capillary filling transition as liquid was condensed into the nanopores. These results are compared with Kelvin-Cohan theory, with a modified Derjaguin approximation, as well as with predictions by Cole and Saam.
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We studied the dependence of solid deposit shape obtained by free drying of sessile drops on the particles concentration and Derjaguin-Landau-Verwey-Overbeek (DLVO) particle/substrate interaction. In contrast to previous contributions using pH as a control parameter of interactions, we investigated an unprecedentedly wide range of concentrations and particle/substrate DLVO forces by modifying the nature of the substrate and particles as well as their size and surface chemistry whereas long-distance repulsive interactions between particles were maintained for most of the drying time. Our main result is that the different shapes of deposits obtained by modifying the particle concentration are the same in the different regimes of concentration regardless of particle/substrate interaction in the studied range of DLVO forces and particle concentrations. The second result is that, contrary to expectations, the dominant morphology of dry patterns at low particle concentration always shows a dot-like pattern for all the studied systems.
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