Pearling instabilities in water-dispersed copolymer cylinders with charged brushes

We investigate the structural behavior of a poly(styrene)-block-poly(acrylic acid) diblock copolymer which forms hexagonally-packed PS cylinders (C-phase) in the melt state. The water dispersion of this structure provides hairy cylinders which comprise a PAA swollen cylindrical brush with a height h tunable via its degree of ionization and the ionic strength in the solution, and a water-free, PS cylindrical core of constant radius R_C. Such system constitutes an out-of-equilibrium frustrated model system: the selective swelling of the PAA brush results in a frustration of the interface curvature, which the ratio h/R_C allows to quantify. Upon heating at a temperature higher than the glass transition temperature of the PS core, the glassiness of the core is relieved and the mechanical constraints arising from the selective swelling of the structure can be relaxed: the cylinders undergo a cylinder-to-sphere transition upon annealing at high temperature, when above a frustration threshold h/R_C 1.8. Thanks to a careful mapping of the transition diagram, an undulating cylindrical morphology (UC) is identified between unchanged cylinders ( h/R_C 1.8) and spheres ( h/R_C 2.0), which appears to result from a Rayleigh-like pearling instability of the copolymer cylinders.     

A phenomenological theory of the isotropic to chiral smectic-C phase transition

In this paper we discuss the direct isotropic to chiral smectic-C phase transition on the basis of a phenomenological theory. The model free energy is written in terms of the coupled order parameters including the spontaneous polarization. We present a detailed analysis of the different phases that can occur and analyze the question under which conditions a direct isotropic to chiral smectic-C phase transition is possible when compared to other phase transitions. On the basis of this model the isotropic-smectic-C^* transition is always of first order. The theoretical predictions are compared with the available experimental results.-1     

Symmetry-breaking transitions and dissociation of two-dimensional Plateau borders

We have experimentally studied the dissociation/coalescence of internal Plateau borders (PBs) in simple monolayer bubble clusters, as a result of changing the liquid fraction. At large liquid content, the clusters consist of n bubbles of the same size, symmetrically placed around an internal n-sided PB (n-PB). On decreasing the liquid fraction we observed symmetry-breaking transitions in the 4- and 5-bubble clusters (but not in the 3-bubble cluster), followed by dissociation of the PBs. We used the Surface Evolver to determine the various equilibrium configurations of the corresponding two-dimensional wet clusters and their surface energies. The sequence of 4-bubble cluster configurations observed on varying the liquid fraction correlates qualitatively with that predicted on the basis of Surface Evolver calculations. The same is not true of the 5-bubble cluster.     

Multi-scale analysis of the stress state in a granular slope in transition to failure

By means of contact dynamics simulations, we analyze the stress state in a granular bed slowly tilted toward its angle of repose. An increasingly large number of grains are overloaded in the sense that they are found to carry a stress ratio above the Coulomb yield threshold of the whole packing. Using this property, we introduce a coarse-graining length scale at which all stress ratios are below the packing yield threshold. We show that this length increases with the slope angle and jumps to a length comparable to the depth of the granular bed at an angle below the angle of repose. This transition coincides with the onset of dilation in the packing. We map this transition into a percolation transition of the overloaded grains, and discuss it in terms of long-range correlations and granular slope metastability.     

The role of heat-conducting walls in the measurement of heat and mass transport in transient grating experiments

We present a two-dimensional model to account for the role of heat-conducting walls in the measurement of heat transport and Soret-effect-driven mass transport in transient holographic grating experiments. Heat diffusion into the walls leads to non-exponential decay of the temperature grating. Under certain experimental conditions it can be approximated by an exponential function and assigned an apparent thermal diffusivity D_{th, app} < D_{th, s}, where D_th,s is the true thermal diffusivity of the sample. The ratio D_{th, app}/D_{th, s} depends on only three dimensionless parameters, d /l_s, κ_s/κ_w, and D_{th, s}/D_{th, w}. d is the grating period, l_s the sample thickness, κ_s and κ_w the thermal conductivities of sample and wall, respectively, and D_th,w the thermal diffusivity of the wall. If at least two measurements are performed at different d /l_s, both D_th,s and κ_s can be determined. Instead of costly solving PDEs, D_th,s can be obtained by finding the zero of an analytic function. For thin samples and large grating periods, heat conduction into the walls plays a predominant role and the concentration grating in binary mixtures is no longer one-dimensional. Nevertheless, the normalized heterodyne diffraction efficiency of the concentration grating remains unaffected and the true thermal and collective diffusion coefficient and the correct Soret coefficient are still obtained from a simple one-dimensional model.     

Depletion from a hard wall induced by aggregation and gelation

Diffusion-limited cluster aggregation and gelation of hard spheres is simulated using off-lattice Monte Carlo simulations. A comparison is made of the wall-particle correlation function with the particle-particle correlation function over a range of volume fractions, both for the initial system of randomly distributed spheres and for the final gel state. For randomly distributed spheres the correlation functions are compared with theoretical results using the Ornstein-Zernike equation and the Percus-Yevick closure. At high volume fractions (φ > 40%) gelation has little influence on the correlation function, but for φ < 10% it is a universal function of the distance normalized by correlation length (ξ) of the bulk. The width of the depletion layer is about 0.5ξ. The concentration increases as a power law from the wall up to r ≈ ξ, where it reaches a weak maximum before decreasing to the bulk value.     

Quantum-chemical study of the interface formed by carboxylic species on TiO<Subscript>2</Subscript> nanoparticles. 1. Nanoparticle surface

The current paper presents results of a quantum-chemical study of the surface structure of nanoparticles of both rutile and anatase crystallographic modifications. Different stages of the surface relaxation are discussed. Water adsorption is considered. The calculations were performed in the spd-basis by using semi-empirical quantum-chemical codes, both sequential and parallel. The results are mainly addressed to the study of the interface formed by titania nanoparticles and a set of carboxylated species, namely, benzoic, bi-isonicotinic acids as well as tris-(2,2′-dcbipyridine) Fe(II) complex placed on the surface of either rutile or anatase polymorphs.This revised version was published online in August 2005 with a corrected issue number.     

Influence of silicon and carbon excesses on the aqueous dispersion of SiC nanocrystals for optical application

The dispersion behaviour of laser-synthesized silicon carbide nanoparticles (npSiC) in water is investigated by photon correlation spectroscopy (PCS). With regard to previous studies and due to an application in the processing of optical materials, this paper concerns low npSiC contents (from 0.05 to 10 wt.%). The role played by the particle surface state is be pointed out through the consideration of stochiometric (C/Si = 1), carbon-rich (C/Si > 1) and silicon-rich (C/Si < 1) nanopowders. Suspensions made from stoichiometric and silicon-rich nanopowders are easily dispersed and stable with time. The PCS measurements reveal in this case more than 95% of isolated nanoparticles, pointing out the key role of the oxidized layer covering the grain of silicon-rich samples. At the opposite, the carbon-rich powders are hardly dispersed in pure water, correlated with the presence of a relatively inert graphitic carbon layer at the grain surface. However, by addition of a commercial polymeric dispersant, all nanopowders induce high quality suspensions. In particular, the carbon-rich samples are easily dispersed, and possible dispersion mechanisms of npSiC in presence of a polymeric surfactant are discussed. The influence of the npSiC loading and the time evolution of the suspension are also presented. By considering stoichiometric, as well as carbon- and silicon-rich samples, this paper demonstrates the possibility to achieve high quality dispersions of SiC nanoparticles, whatever the chemical composition of the powder, as an easy step for optical material processing.This revised version was published online in August 2005 with a corrected issue number.     

Polymer-assisted complexing controlled orientation growth of ZnO nanorods

The growth of the oriented zinc oxide (ZnO) nanorods on silicon substrates based on a simple novel chemical transformation and thermal hydrolysis by using polyvinyl alcohol (PVA) as self-assembling complex polymer was introduced in this paper. All the polymers were removed after chemical oxidation and only the carbonized grid backbones remained that confines the ZnO nanorod’s diameter and enhance the absorption and diffusion of ZnO at the tips of the nanorods during growth. The ZnO nanorods are investigated by FTIR, XRD and FE-SEM. The results indicated that these nanorods have fine hexagonal wurtzite crystal structure and their diameter varies from 20 to 90 nm and the length up to about 1 μm. A polymer-localized ZnO growth model is proposed, which well explains the growth behavior of ZnO nanorods.This revised version was published online in August 2005 with a corrected issue number.     

Synthesis of In<Subscript>2</Subscript>O<Subscript>3</Subscript>nanoparticles by thermal decomposition of a citrate gel precursor

This paper describes the synthesis of indium oxide by a modified sol–gel method, and the study of thermal decomposition of the metal complex in air. The characterization of the intermediate as well as the final compounds was carried out by thermogravimetry, differential thermal analysis, Fourier transform infrared spectroscopy, X-ray diffraction, transmission electron microscopy, and small angle X-ray scattering. The results show that the indium complex decomposes to In₂O₃ with the formation of an intermediate compound. Nanoparticles of cubic In₂O₃ with crystallite sizes in the nanosize range were formed after calcination at temperatures up to 900°C. Calcined materials are characterized by a polydisperse distribution of spherical particles with sharp and smooth surfaces.This revised version was published online in August 2005 with a corrected issue number.