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Robert Hołyst

Publications and source records attributed to Robert Hołyst.

14 recordsLinked to original sources
PubMed2006

Phase separation in binary polymer/liquid crystal mixtures: network breaking and domain growth by coalescence-induced coalescence.

A small-angle light scattering (SALS) technique together with optical microscopy observation are used to investigate phase separation kinetics in films of low molecular weight thermotropic liquid crystal (4-cyano-4'-n-octyl-biphenyl, 8CB) with flexible polymer (polystyrene, PS). The growth of domains is studied as a function of time, film thickness, and film composition. The light scattering results are correlated with the images obtained by optical microscopy observation. In this paper, we study the breaking of a bicontinuous network of polymer in liquid crystal into droplets and their further growth via the coalescence-induced coalescence mechanism. The appearance of droplets in the system leads to a strong scattering at small wave vectors, while the bicontinuous network gives a peak at a nonzero wave vector. Superposition of these scattering intensities leads to the appearance of a second peak in the full scattering intensity signal, when the bicontinuous network starts to break up into disjointed elongated domains. Finally, both peaks merge into a single peak, which moves quickly toward zero wave vectors, indicating a complete transformation of elongated domains into spherical droplets of variable size. We found that the separation process does not depend on the size of the system. Irrespective of the sample thickness, the network breaks into fragments always at the same time after temperature quench. On the basis of morphological analysis, we found that the average size of the droplets which formed from the network grows with time, t, as t(alpha), alpha = 0.9 +/- 0.1, in the isotropic phase and in the nematic phase.

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PubMed2006

Movement of proteins in an environment crowded by surfactant micelles: anomalous versus normal diffusion.

Small proteins move in crowded cell compartments by anomalous diffusion. In many of them, e.g., the endoplasmic reticulum, the proteins move between lipid membranes in the aqueous lumen. Molecular crowding in vitro offers a systematic way to study anomalous and normal diffusion in a well controlled environment not accessible in vivo. We prepared a crowded environment in vitro consisting of hexaethylene glycol monododecyl ether (C(12)E(6)) nonionic surfactant and water and observed lysozyme diffusion between elongated micelles. We have fitted the data obtained in fluorescence correlation spectroscopy using an anomalous diffusion model and a two-component normal diffusion model. For a small concentration of surfactant (below 4 wt %) the data can be fitted by single-component normal diffusion. For larger concentrations the normal diffusion fit gave two components: one very slow and one fast. The amplitude of the slow component grows with C(12)E(6) concentration. The ratio of diffusion coefficients (slow to fast) is on the order of 0.1 for all concentrations of surfactant in the solution. The fast diffusion is due to free proteins while the slow one is due to the protein-micelle complexes. The protein-micelle interaction is weak since even in a highly concentrated solution (35% of C(12)E(6)) the amplitude of the slow mode is only 10%, despite the fact that the average distance between the micelles is the same as the size of the protein. The anomalous diffusion model gave the anomaly index (r(2)(t) approximately t(alpha)), alpha monotonically decreasing from alpha = 1 (at 4% surfactant) to alpha = 0.88 (at 37% surfactant). The fits for two-component normal diffusion and anomalous diffusion were of equally good quality, but the physical interpretation was only straightforward for the former.

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PubMed2006

State of hydrogen in idealized carbon slitlike nanopores at 77 K.

The purpose of this letter is to clarify recent findings and answer to the question: "What is the state of hydrogen in carbon slitlike pores at 77 K?" For this purpose, we determined the volumetric density of hydrogen in idealized carbon pores of molecular dimension at 77 K and pressure up to 1 MPa. We used quantum corrected grand canonical Monte Carlo simulation. We recognized the highest volumetric density of confined hydrogen (around 71% of hydrogen liquid at boiling point) for effective pore width 5.6 angstroms (H* = 3.04) in the considered pressure range. Our computational results are in agreement with the calculations performed by Wang and Johnson and Rzepka et al. In contrast, we did not observe the high volumetric density of hydrogen in slitlike carbon pores exceeding the density of hydrogen liquid at the boiling point as was reported by Jagiello and Thommes. Moreover, we obtained qualitative agreement between the simulation results and some experimental findings reported by Nijkamp.

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PubMed2005

Storage of hydrogen at 303 K in graphite slitlike pores from grand canonical Monte Carlo simulation.

Grand canonical Monte Carlo (GCMC) simulations were used for the modeling of the hydrogen adsorption in idealized graphite slitlike pores. In all simulations, quantum effects were included through the Feynman and Hibbs second-order effective potential. The simulated surface excess isotherms of hydrogen were used for the determination of the total hydrogen storage, density of hydrogen in graphite slitlike pores, distribution of pore sizes and volumes, enthalpy of adsorption per mole, total surface area, total pore volume, and average pore size of pitch-based activated carbon fibers. Combining experimental results with simulations reveals that the density of hydrogen in graphite slitlike pores at 303 K does not exceed 0.014 g/cm(3), that is, 21% of the liquid-hydrogen density at the triple point. The optimal pore size for the storage of hydrogen at 303 K in the considered pore geometry depends on the pressure of storage. For lower storage pressures, p < 30MPa, the optimal pore width is equal to a 2.2 collision diameter of hydrogen (i.e., 0.65 nm), whereas, for p congruent with 50MPa, the pore width is equal to an approximately 7.2 collision diameter of hydrogen (i.e., 2.13 nm). For the wider pores, that is, the pore width exceeds a 7.2 collision diameter of hydrogen, the surface excess of hydrogen adsorption is constant. The importance of quantum effects is recognized in narrow graphite slitlike pores in the whole range of the hydrogen pressure as well as in wider ones at high pressures of bulk hydrogen. The enthalpies of adsorption per mole for the considered carbonaceous materials are practically constant with hydrogen loading and vary within the narrow range q(st) congruent with 7.28-7.85 kJ/mol. Our systematic study of hydrogen adsorption at 303 K in graphite slitlike pores gives deep insight into the timely problem of hydrogen storage as the most promising source of clean energy. The calculated maximum storage of hydrogen is equal to approximately 1.4 wt %, which is far from the United States Department of Energy (DOE) target (i.e., 6.5 wt %), thus concluding that the total storage amount of hydrogen obtained at 303 K in graphite slitlike pores of carbon fibers is not sufficient yet.

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PubMed2005

Relaxation processes in semidilute solutions of polymers in liquid crystal solvents.

We investigate the relaxation phenomena in a polymer (polystyrene)/liquid crystal (4-cyano-4'-n-octyl-biphenyl) system, in its homogeneous isotropic phase near the isotropic-isotropic, isotropic-nematic, and isotropic-smectic coexistence curve, using both polarized and depolarized photon correlation spectroscopy (PCS). We study this system for different polystyrene molecular weights (4750, 12 500, and 65 000 g/mol), different compositions (50, 40, 30, and 10% polystyrene (PS) by weight), and different temperatures close to phase boundaries. First of all, we determine the phase diagrams of this system for the different molecular weights. The shape of the phase diagrams strongly depends on the molecular weight. However, in all cases, at low temperatures, these systems separate into an almost pure liquid crystalline (LC) phase and polystyrene-rich phase. PCS measurements show that the relaxation processes in the homogeneous phase are not affected by the proximity of the nematic, or smectic, boundaries (even at a temperature of 0.1 degrees C above the phase separation in two phases). In polarized PCS experiments, we always see three relaxation processes well separated in time: one, very fast, with a relaxation time of the order of 10(-5) s; a second one with a relaxation time within the range 10(-2)-10(-3) s; and a last one, very slow, with a relaxation time of the order of 1 s. Both the fast and slow modes are independent of the wave vector magnitude, while the intermediate relaxation process is diffusive. In depolarized PCS experiments, the intermediate mode disappears and only the fast and slow relaxation processes remain, and they are independent of the magnitude of the wave vector. The diffusive mode is the classical diffusive mode, which is associated with the diffusion of polymer chains in all polymer solutions. The fast mode is due to the rotational diffusion of 4-cyano-4'-n-octyl-biphenyl (8CB) molecules close to polystyrene chains (transient network). Finally, we assign the slowest mode to reorientational processes of small aggregates of PS chains that are not dissolved in 8CB.

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PubMed2005

Distribution of carbon nanotube sizes from adsorption measurements and computer simulation.

The method for the evaluation of the distribution of carbon nanotube sizes from the static adsorption measurements and computer simulation of nitrogen at 77 K is developed. We obtain the condensation/evaporation pressure as a function of pore size of a cylindrical carbon tube using Gauge Cell Monte Carlo Simulation (Gauge Cell MC). To obtain the analytical form of the relationships mentioned above we use Derjaguin-Broekhoff-deBoer theory. Finally, the pore size distribution (PSD) of the single-walled carbon nanohorns (SWNHs) is determined from a single nitrogen adsorption isotherm measured at 77 K. We neglect the conical part of an isolated SWNH tube and assume a structureless wall of a carbon nanotube. We find that the distribution of SWNH sizes is broad (internal pore radii varied in the range 1.0-3.6 nm with the maximum at 1.3 nm). Our method can be used for the determination of the pore size distribution of the other tubular carbon materials, like, for example, multiwalled or double-walled carbon nanotubes. Besides the applicable aspect of the current work the deep insight into the problem of capillary condensation/evaporation in confined carbon cylindrical geometry is presented. As a result, the critical pore radius in structureless single-walled carbon tubes is determined as being equal to three nitrogen collision diameters. Below that size the adsorption-desorption isotherm is reversible (i.e., supercritical in nature). We show that the classical static adsorption measurements combined with the proper modeling of the capillary condensation/evaporation phenomena is a powerful method that can be applied for the determination of the distribution of nanotube sizes.

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PubMed2005

Modeling of the hysteresis phenomena in finite-sized slitlike nanopores. Revision of the recent results by rigorous numerical analysis.

The systematic investigation of the hysteresis phenomena in finite-sized slitlike nanopores via the Aranovich-Donohue (AD) lattice density functional theory (LDFT) is presented. The new reliable quantitative modeling of the adsorption and desorption branch of the hysteresis loop, through the formation and movement of the curved meniscus, is formulated. As a result, we find that our proposal, which closely mimics the experimental findings, can reproduce a rounded shape of the desorption branch of the hysteresis loop. On the basis of the exhausted commutations, we proved that the hysteresis loop obtained in the considered finite-sized slitlike geometry is of the H1 type of the IUPAC classification. This fundamental result and the other most important results do not confirm the results of the recent studies of Sangwichien et al., whereas they fully agree with the recent lattice studies due to Monson et al. We recognize that the nature of the hysteresis loops (i.e. position, width, shape, and the multiple steps) mainly depends on the value of the energy of both the adsorbate-adsorbate and adsorbate-adsorbent interactions; however, the first one is critical for the appearance of hysteresis. Thus, for relatively small adsorbate-adsorbate interactions, the adsorption-desorption process is fully reversible in the whole region of the bulk density. We show that the strong adsorbate-adsorbent interactions produce (also observed experimentally) multiple steps within hysteresis loops. Contrary to the other studies of the hysteresis phenomena in confined geometry via the LDFT formalism, we constructed both ascending and descending scanning curves, which are known from the experimental observations. Additionally, we consider the problem of the stability of both the obtained adsorption and desorption branches of the computed hysteresis loop in finite-sized slitlike nanopores.

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PubMed2005

Chirality-biased point defects dynamics on a disclination line in a nematic liquid crystal.

Chiral additives in the nematic liquid crystal can alter the dynamics of point defects moving on a disclination line. They exert a constant force on defects, leading to the bimodal distribution of distances between them at long times. The evolution of the system of defects in the presence of chiral additives provides a very direct proof of the existence of repulsive forces between the defects at large distances. We find that addition of a sufficient amount of chiral compound removes all point defects from the system. The process is studied in the system of 8CB (4-n-octyl-4'-cyanobiphenyl) doped with the chiral compound S811 (from Merck Co.) and in the computer simulations.

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PubMed2005

Coalescence-induced coalescence and dimensional crossover during the phase separation in ternary surfactant/polymer/water mixtures.

We studied the separation process in the ternary mixtures of nonionic surfactant (C(12)E(6), hexaethylene glycol monododecyl ether), polymer (PEG = poly(ethylene glycol)), and water. The separation process of PEG/water rich domains from the surfactant rich matrix was observed by the optical microscopy. From the morphological analysis, we determined the size of the domains as a function of time. On this basis we identified a dominating mechanisms of domains growth, that is the coalescence-induced coalescence mechanism. The coalescence (collision) event of two droplets induces a flow or a change of concentration distribution around droplets which pushes other droplets together inducing further growth. We also observed the evaporation-condensation (Lifshitz-Slyozov) mechanism of growth, but it did not affect the growth of large domains appreciably. We determined two regimes of the coalescence-induced coalescence associated with the dimensionality of the system. When the domains were smaller or comparable in size to the sample thickness we observe a three-dimensional growth. When the domains became larger than the sample thickness, a two-dimensional growth was observed. In the first regime, the size of the domains, L(t), grew linearly with t, while in the second regime, L(t) approximately t(0.3). In the binary, surfactant/water system, water domains grew by the geometrical coalescence-induced coalescence as L(t) approximately t in three dimensions.

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PubMed2004

The unphysical pinning of the domain growth during the separation of homopolymer blends near the spinodal.

We simulate model B of mesoscopic dynamic with the Flory-Huggins free energy for the homopolymer blend. We concentrate the study on the rescaling of the spatial coordinates in the model. We show that the commonly used rescaling of the spatial coordinates, by the function vanishing at the spinodal, leads to the unphysical freezing of the domains. We study the evolution of the system in two different processes: One is the growth process induced by the temperature quench to the metastable or unstable region of the phase diagram and the second is the quench-jump process in which we first allow the system to separate below the spinodal and next heat it up below or above the spinodal. The proper rescaling avoiding the unphysical pinning of the domain growth at the spinodal is proposed.

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PubMed2004

Minimization of the Renyi entropy production in the stationary states of the Brownian process with matched death and birth rates.

We analyze the Fleming-Viot process. The system is confined in a box, whose boundaries act as a sink of Brownian particles. The death rate at the boundaries is matched by the branching (birth) rate in the system and thus the number of particles is kept constant. We show that such a process is described by the Renyi entropy whose production is minimized in the stationary state. The entropy production in this process is a monotonically decreasing function of time irrespective of the initial conditions. The first Laplacian eigenvalue is shown to be equal to the Renyi entropy production in the stationary state. As an example we simulate the process in a two-dimensional box.

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PubMed2002

Morphological changes during the order-disorder transition in the two- and three-dimensional systems of scalar nonconserved order parameters.

The order-disorder transition is studied in a system of a scalar nonconserved order parameter. We use this well studied system to show that the application of the methods of topology and geometry reveals that our knowledge of the kinetic pathways by which the order-disorder transition proceeds is far from being complete. We show that in two-dimensional (2D) and 3D systems there are three dynamical regimes in the evolution of the system: early, intermediate, and late. In the intermediate regime two length scales govern the behavior of the system, whereas in the early and intermediate regime there is only one length scale. The size distribution of the domain area indicates the pathway by which the domains change their size. There are only two types of domains in a 2D system: circular and elongated with well defined characteristics (scaling of the area with the contour length) which in the late regime do not depend on time after rescaling by the average area and contour in the system. The elongated domains continuously change into circular domains reducing in this way the overall dissipation in the system. In order to reach a Lifshitz-Cahn-Allen (LCA) late stage regime the number of elongated domains must be strongly reduced. In the intermediate regime the number of elongated domains is large and simple LCA scaling does not hold. In a 3D symmetric system we always have a bicontinuous structure that evolves by cutting small connections. The late stage regime seems to be associated with the appearance of the preferred nonzero mean curvature. The early-intermediate regime crossover is associated with the saturation of the order parameter inside the domains, while the intermediate-late stage regime crossover is related to the global breaking of the +/- order parameter symmetry (marked by the appearance of the nonzero mean curvature but still zero average magnetization). The times for the occurrence of these crossovers do not depend on the size of the system.

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PubMed2002

Morphology from the maximum entropy principle: domains in a phase ordering system and a crack pattern in broken glass.

The maximum entropy principle is applied to study the morphology of a phase ordering two-dimensional system below the critical point. The distribution of domain area A is a function of ratio of the area to contour length L, R=A/L(A), and is given by exp(-lambda R(mu)) with exponent mu=2, which follows from the Lifshitz-Cahn-Allen theory. A and L are linked through the relation L approximately A(nu). We find two types of domain in the system: large of elongated shape (nu=0.88) and small of circular shape (nu=0.5). A crack pattern in broken glass belongs to the same morphology class with mu=1 and nu=0.72.

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