Nanometer-sized metal and semiconductor particles possess novel properties. To fully realize their potential, these nanoparticles need to be fabricated into ordered arrays or predesigned structures. A promising nanoparticle fabrication method is coupled surface passivation and self-assembly of surfactant-coated nanoparticles. Due to the empirical procedure and partially satisfactory results, this method still represents a major challenge to date and its refinement can benefit from fundamental understanding. Existing evidences suggest that the self-assembly of surfactant-coated nanoparticles is induced by surfactant-modified interparticle interactions and follows an intrinsic road map such that short one-dimensional (1D) chain arrays of nanoparticles occur first as a stable intermediate before further assembly takes place to form higher dimensional close-packed superlattices. Here we report a study employing fundamental analyses and Brownian dynamics simulations to elucidate the underlying pair interaction potential that drives the nanoparticle self-assembly via 1D arrays. We find that a pair potential which has a longer-ranged repulsion and reflects the effects of surfactant chain interdigitation on the dynamics is effective in producing and stabilizing nanoparticle chain arrays. The resultant potential energy surface is isotropic for dispersed nanoparticles but becomes anisotropic to favor the growth of linear chain arrays when self-assembly starts.
Sorption of vapors in polymer membranes in the vicinity of and below the glass transition temperatures do not follow the Fickian (classical) diffusion. The reasons have been attributed to the molecular relaxation which affects both diffusivities and solubilities.A time‐ and memory‐dependent diffusion coefficient has been evaluated in Part I, in a form which is analogous to the treatment in the rheology of such materials. Together with a time‐dependent solubility, the conservation equation for the sorption process has been solved. Two special cases are considered, where the relaxation times are short and where they are long. The results explain the anomalous behavior observed in the experiments. Comparison with the experiments has been made.
It is known that the spreading rates of small liquid
drops over a solid surface exhibit a
strong dependence on the viscosity of the liquid. These
observations have led us to study the spreading
behavior of polymer solutions on high- and low-energy substrates to
determine what role complex rheology
plays in wetting kinetics. We did not observe any effects of
non-Newtonian (nonlinear) behavior, nor
were any obvious signs of viscoelasticity (memory) visible.
Instead, we observed a most intriguing
phenomenon that polymer solutions, despite having low surface energies,
do not wet high-energy
substrates. In addition, nonwetting drops spread to an equilibrium
configuration by either one of two
distinct mechanisms. In the first case, they spread as a wetting
Newtonian liquid and then stopped,
that is, equilibrated, abruptly. In the second, they equilibrated
continuously. We offer some possible
molecular and continuum arguments to explain the differences between
these two mechanisms.
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