Molecular dynamics studies of the stability of water/n-heptane interfaces with adsorbed naphthenic acids

The mechanism by which naphthenic acids stabilize water/oil interfaces has received extensive attention because of its industrial relevancy. In this work, we employed a molecular dynamics simulation to study its molecular origin. Two models were adopted, wherein naphthenic acid coverage of water/n-heptane interfaces, both spherical and flat, was hypothesized, respectively. It was found that the coalescence of two water clusters is entirely attributed to the diffusional motion of the components involved which requires the initial departure of the naphthenic acid molecules from the interface so that a water bridge can form. The naphthenic acids not only act as a steric barrier but also reduce the mobility of the water and n-heptane molecules making the formation of the water bridge rather difficult. In fact, our results show that the coalescence of two water clusters fully covered by naphthenic acid molecules is a low-probability event even at evaluated temperatures. In addition, the results from the flat interface models suggest that the emulsion stability is weakly dependent on the molecular weight of the naphthenic acids utilized. Order parameter calculations reveal liquid-crystal-like ordering of naphthenic acids at the water/n-heptane interfaces. All these observations are consistent with the corresponding experimental observations. The present work also suggests that the mobility of naphthenic acids is considerably enhanced with more n-heptane molecules present outside a water droplet. However, in such a case, coalescence could not occur as the water clusters are far apart from each other.     

Hybrid fluorescent nanoparticles from quantum dots coupled to cellulose nanocrystals

Carboxylated cellulose nanocrystals (CNCs) were decorated with CdSe/ZnS quantum dots (QDs) using a carbodiimide chemistry coupling approach. The one-step covalent modification was supported by nanoscale imaging, which showed QDs clustered on and around the CNCs after coupling. The QD–CNC hybrid nanoparticles remained colloidally stable in aqueous suspension and were fluorescent, exhibiting the broad excitation and narrow emission profile characteristic of the QDs. QD–CNCs in nanocomposite films imparted strong fluorescence within CNC-compatible matrices at relatively low loadings (0.15 nmol QDs/g of dry film), without altering the overall physical properties or self-assembly of the CNCs. The hybrid QD–CNCs may find applications in nanoparticle tracking, bio-imaging, optical/sensing devices, and anti-counterfeit technologies.     

Polymer Nanocomposites for Emulsion‐Based Coatings and Adhesives

Emulsion‐based coatings and adhesives are in growing demand due to an increased awareness of health and safety issues arising from solvent‐based polymer manufacturing processes. However, emulsion‐based techniques often require additional development to achieve equal or better application performance compared to solvent‐based processes. The inclusion of nanoparticles in emulsion‐based coatings and adhesives can be considered as a promising means to enhance performance. This paper reviews the current progress on the synthesis of emulsion‐based nanocomposites for coating and adhesive applications and addresses the principles and techniques for nanoparticle dispersions and their inclusion into polymer latexes. The effects of nanoparticle shape and size on the enhancement of nanocomposite properties are also highlighted. Among the reinforcing nanoparticles such as nanoclays, carbon nanotubes, and cellulose nanocrystals (CNCs), CNCs are promising due to their abundance, nontoxicity, and accessible surface hydroxyl groups, which facilitate their compatibility with polymer latexes via physical and chemical treatments.     

Ionic liquid nanotribology: stiction suppression and surface induced shear thinning

The friction and adhesion between pairs of materials (silica, alumina, and polytetrafluoroethylene) have been studied and interpreted in terms of the long-ranged interactions present. In ambient laboratory air, the interactions are dominated by van der Waals attraction and strong adhesion leading to significant frictional forces. In the presence of the ionic liquid (IL) ethylammonium nitrate (EAN) the van der Waals interaction is suppressed and the attractive/adhesive interactions which lead to "stiction" are removed, resulting in an at least a 10-fold reduction in the friction force at large applied loads. The friction coefficient for each system was determined; coefficients obtained in air were significantly larger than those obtained in the presence of EAN (which ranged between 0.1 and 0.25), and variation in the friction coefficients between systems was correlated with changes in surface roughness. As the viscosity of ILs can be relatively high, which has implications for the lubricating properties, the hydrodynamic forces between the surfaces have therefore also been studied. The linear increase in repulsive force with speed, expected from hydrodynamic interactions, is clearly observed, and these forces further inhibit the potential for stiction. Remarkably, the viscosity extracted from the data is dramatically reduced compared to the bulk value, indicative of a surface ordering effect which significantly reduces viscous losses.     

The radial part of Brownian motion II. Its life and times on the cut locus

Summary This paper is a sequel to Kendall (1987), which explained how the Itô formula for the radial part of Brownian motionX on a Riemannian manifold can be extended to hold for all time including those times a whichX visits the cut locus. This extension consists of the subtraction of a correction term, a continuous predictable non-decreasing processL which changes only whenX visits the cut locus. In this paper we derive a representation onL in terms of measures of local time ofX on the cut locus. In analytic terms we compute an expression for the singular part of the Laplacian of the Riemannian distance function. The work uses a relationship of the Riemannian distance function to convexity, first described by Wu (1979) and applied to radial parts of -martingales in Kendall (1993).The first author's research was supported by a visiting fellowship awarded by the UK Science and Engineering Council, by travel funds provided by a European Community SCIENCE initiative, by the Max-Planck-Institute of Bonn, and by a grant from NSA     

Lifetime of conditioned Brownian motion in Lipschitz domains

Summary If D- ^d , d3, is bounded and has Lipschitz boundary then the expected lifetime of any Brownian h-path process in D is finite.     

Brooks' Theorem and Beyond

We collect some of our favorite proofs of Brooks' Theorem, highlighting advantages and extensions of each. The proofs illustrate some of the major techniques in graph coloring, such as greedy coloring, Kempe chains, hitting sets, and the Kernel Lemma. We also discuss standard strengthenings of vertex coloring, such as list coloring, online list coloring, and Alon–Tarsi orientations, since analogs of Brooks' Theorem hold in each context. We conclude with two conjectures along the lines of Brooks' Theorem that are much stronger, the Borodin–Kostochka Conjecture and Reed's Conjecture.     

A Central Limit Theorem for isotropic flows

We establish that the image of a measure, which satisfies a certain energy condition, moving under a standard isotropic Brownian flow will, when properly scaled, have an asymptotically normal distribution under almost every realization of the flow. We derive the same result for an initial point mass moved by an isotropic Kraichnan flow.