Biomedical subjects

Martin Schoen

Publications and source records attributed to Martin Schoen.

14 recordsLinked to original sources

PubMed2006

Wetting of rings on a nanopatterned surface: a lattice model study.

We perform mean-field density functional theory calculations on a lattice model to study the wetting of a solid substrate decorated with a ring pattern of nanoscale dimensions. We have found three different liquid morphologies on the substrate: a ring morphology where the liquid covers the pattern, a bulge morphology where a droplet is forming on one side of the ring, and a morphology where the liquid forms a cap spanning the nonwetting disk inside the pattern. We investigate the relative stability of these morphologies as a function of the ring size, wall-fluid interaction, and temperature. The results found are in very good agreement with experiments and calculations performed on similar systems at a micrometer length scale. The bulge morphology has also been observed in Monte Carlo simulations of the lattice model. Our results show that (i) morphologies of wetting patterns previously observed on a much larger (microm) scale can also form on a nm length scale, (ii) whether or not this happens depends crucially on the size of the wettable pattern, and (iii) the wettable ring may only be partially wet by the bulge morphology of the fluid. This morphology is a result of a spontaneously broken symmetry in the system.

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PubMed2006

Mesoscale modeling of complex binary fluid mixtures: towards an atomistic foundation of effective potentials.

This paper is devoted to equilibrium molecular-dynamics (MD) simulations of a fully atomistic model of binary mixtures of water (component 1) and ethanol (component 2). We investigate ways to extract from these simulations effective, pairwise additive potentials suitable to describe the interactions between coarse-grained molecules (i.e., beads) in corresponding mesoscale dissipative particle-dynamics simulations. The fully atomistic model employed in MD simulations is mapped onto an implicit water model, where the internal degrees of freedom of ethanol and all the degrees of freedom of water are integrated out. This gives us an effective one-component system consisting only of ethanol beads. The effective interaction potential between a pair of ethanol beads, Phi(R), is approximated at three levels of sophistication. At the lowest one, we approximate Phi(R) by the potential of mean force between the centers of mass of two ethanol beads calculated in the fully atomistic MD simulations; at the second level, we take Phi(R) to be the potential linked to total and direct correlation functions in the hypernetted-chain closure of the Ornstein-Zernike equation. At the third level we approximate Phi(R) numerically by improving it iteratively through the Boltzmann inversion scheme. Our results indicate that the level-one approach works only at the lowest (8 wt %) concentration; the level-two approach works only up to intermediate ethanol concentrations (ca. 50 wt %). Only the Boltzmann inversion scheme works for all, up to the highest concentration considered (70 wt %).

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PubMed2006

Topography of phase diagrams in binary fluid mixtures: a mean-field lattice density functional study.

We employ mean-field lattice density functional theory to calculate complete phase diagrams of binary fluid mixtures composed of molecules of equal size. We consider asymmetric binary mixtures in which the attraction strength between like molecules of either species differs as well as the attractivity between a pair of unlike molecules. Focusing on the topology of phase diagrams in the space spanned by the thermodynamic fields temperature , (mean) chemical potential , and incremental chemical potential (, are chemical potentials of pure mixture components A and B, respectively), we present an argument which precludes the existence of tricritical points (TCPs) in binary mixtures in general. This is a consequence of a purely geometrical argument based upon an analysis of the number of ways in which coexistence surfaces can be joined in the (Euclidian) space of , , and . However, we show that by the same token, TCPs may exist in cases where the mixture possesses some special symmetry. These latter results are in qualitative agreement with earlier works where, however, only special cuts through the complete phase diagrams were considered so that the important relation between existence of TCPs and symmetry properties of the mixture cannot be fully appreciated.

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PubMed2005

Effect of fluid-substrate attraction and pore geometry on fluid adsorption.

We employ grand canonical ensemble Monte Carlo simulations to investigate the impact of substrate curvature on the phase behavior of an adjacent fluid. The substrates consist of a periodic sequence of grooves in the x direction; the grooves are infinitely long in the y direction. The shape of the grooves is controlled by a parameter eta. For eta = 0 the substrates are planar. If eta = 1, the grooves are wedge shaped. If eta > 1 the grooves become concave and in the limit eta = infinity rectangular. The fluid-substrate potential representing a groove consists of two contributions, namely, that of the homogeneous substrate base corresponding to a semi-infinite solid and that of a finite piece of solid with nonplanar surfaces. Whereas the former contribution can be calculated analytically, the latter needs to be evaluated numerically. For very large values of eta, that is in (almost) rectangular grooves, we observe capillary condensation of that portion of fluid located inside the grooves. As eta decreases capillary condensation gives way to continuous filling. In all cases, a nearly planar film-gas interface eventually forms in the direction normal to the surface of the substrate base and outside the grooves if one increases the chemical potential sufficiently.

Adsorption↗

PubMed2005

Phase behavior and local structure of a binary mixture in pores: mean-field lattice model calculations for analyzing neutron scattering data.

We investigate the phase behavior of an asymmetric binary liquid A-W mixture confined between two planar homogenous substrates (slit pore). Molecules of species W interact preferentially with the solid walls via a long-range potential. Assuming nearest-neighbor attractions between the liquid molecules, we employ a lattice-gas model and a mean-field approximation for the grand potential. Minimization of this potential yields the density profiles of thermodynamically stable phases for fixed temperature, chemical potentials of both species, pore width and strengths of attraction. This model is used to analyze experimental small-angle neutron-scattering (SANS) data on the microscopic structure of the binary system isobutyric acid (iBA)+heavy water (D2O) inside a mesoscopic porous matrix (controlled-pore glass of about 10 nm mean pore width). Confinement-independent model parameters are adjusted so that the theoretical liquid-liquid coexistence curve in the bulk matches its experimental counterpart. By choosing appropriate values of the pore width and the attraction strength between substrates and water we analyze the effect of confinement on the phase diagram. In addition to a depression of the liquid-liquid critical point we observe surface induced phase transitions as well as water-film adsorption near the walls. The temperature dependence of the structure of water-rich and iBA-rich phases of constant composition are discussed in detail. The theoretical predictions are consistent with results of the SANS study and assist their interpretation.

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PubMed2004

Torsion-induced phase transitions in fluids confined between chemically decorated substrates.

In this paper we investigate the phase behavior of a "simple" fluid confined to a chemically heterogeneous slit pore of nanoscopic width s(z) by means of Monte Carlo simulations in the grand canonical ensemble. The fluid-substrate interaction is purely repulsive except for elliptic regions of semiaxes A and B attracting fluid molecules. On account of the interplay between confinement (i.e., s(z)) and chemical decoration, three fluid phases are thermodynamically permissible, namely, gaslike and liquidlike phases and a "bridge phase" where the molecules are preferentially adsorbed by the attractive elliptic patterns and span the gap between the opposite substrate surfaces. Because of their lack of cylindrical symmetry, bridge phases can be exposed to a torsional strain 0<or=theta;<or=pi/2 by rotating the upper substrate while holding the lower one in position. Depending on the thermodynamic state of the confined fluid, torsion-induced first-order phase transitions are feasible during which a bridge phase may be transformed into either a gaslike (evaporation) or a liquidlike phase (condensation). Since the chemical patterns decorating the substrates are finite in size, system properties are not translationally invariant in any spatial direction. Therefore, in order to study these phase transitions, we resorted to the thermodynamic integration scheme developed earlier to calculate the grand potential Omega in a system of low symmetry.

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PubMed2004

Confinement effect on the adsorption from a binary liquid system near liquid/liquid phase separation.

The preferential adsorption of one component of a binary system at the inner surfaces of mesoporous silica glasses was studied in a wide composition range at temperatures close to liquid/liquid phase separation. Confinement effects on the adsorption were investigated by using three controlled-pore glass (CPG-10) materials of different mean pore size (10 to 50 nm). For the experimental system (2-butoxyethanol+water), which exhibits an upper miscibility gap, strong preferential adsorption of water occurs, as the coexistence curve is approached at bulk compositions, at which water is the minority component. In this strong adsorption regime the area-related surface excess amount of adsorbed water decreases with decreasing pore width, while the shift in the volume-related mean composition of the pore liquid shows an opposite trend, i.e., greatest deviation from bulk composition occurring in the most narrow pores. A simple mean-field lattice model of a liquid mixture confined by parallel walls is adopted to rationalize these experimental findings. This model reproduces the main findings of the confinement effect on the adsorption near liquid/liquid phase separation.

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PubMed2004

Aspects of prewetting at nonplanar surfaces.

We employ Monte Carlo simulations in the grand canonical ensemble (GCEMC) to investigate the impact of nonplanarity of a solid substrate on the locus of the prewetting phase transition. The substrate is modelled as a periodic sequence of furrows of depth D and periodicity sx in the x direction; the furrows are infinitely long in the y direction. Our results indicate that a necessary prerequisite for a prewetting transition is the formation of a(n approximately) planar interface between molecularly thin films and an adjacent (bulk) gas. Thus, in general the prewetting transition is shifted to larger chemical potentials because the formation of a planar film-gas interface is more difficult next to a nonplanar compared with a planar solid surface. However, this shift turns out to be nonmonotonic depending on D on account of subtle packing effects manifested in the deviation of the local density Deltarho(x,Deltaz;D) at the nonplanar solid surface from that at a planar substrate. If D becomes sufficiently large prewetting as a discontinuous phase transition is suppressed because inside the furrow a highly ordered film forms that prevents a planar film-gas interface from forming.

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PubMed2004

Wetting of a selective solid surface by an asymmetric binary mixture.

We consider a lattice-gas model of an asymmetric binary mixture in which the attraction between a pair of molecules of species A exceeds that between a pair of molecules of species B. The interaction between two molecules of species A and B is chosen to promote the formation of demixed A-rich liquid bulk phases. Molecules interact with a selective solid wall, preferentially adsorbing molecules of species B. Positions of molecules are restricted to sites on a simple-cubic lattice. We invoke a mean-field representation of the Hamiltonian governing all intermolecular interactions and assume only nearest-neighbor attractions. Minimizing the grand-potential functional of the lattice gas numerically, phase diagrams for films wetting the solid substrate are obtained. One of our key findings concerns B-rich mixed or demixed films forming in the vicinity of the solid surface and coexisting with demixed A-rich films. The formation of B-rich films can be understood as a result of the competition between the asymmetry of the (bulk) mixture and the selectivity of the solid surface. The concentration of component B in B-rich mixed films shows a peculiar temperature dependence. It first increases with temperature T until an "inversion" temperature T(inv) is reached, and then declines for T>or=T(inv) until the critical point between (demixed) A- and B-rich films is reached.

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PubMed2004

Phase behavior of liquid crystals confined by smooth walls.

Monte Carlo simulations for a simple model liquid crystal are presented. The influence of flat walls on the phase behavior is analyzed for two different anchoring mechanisms, one favoring homeotropic alignment and one simulating a twisted nematic cell without external fields, e.g., two walls with different homogeneous planar alignment. The simulations are performed in the constant pressure ensemble. The box volume may change in the directions perpendicular to the wall normal. The isotropic-nematic phase transition in the bulk system is first studied for different isobars. For the weak first order transition we do not observe any hysteresis down to a temperature accuracy of deltaT=0.001. The isotherm T=1 is then studied in the bulk as well as in the confined geometries. The walls stabilize the positional order in the systems due to the formation of layers. The orientational order is weakly stabilized.

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PubMed2003

Nanoscopic liquid bridges exposed to a torsional strain.

In this paper we investigate the response to a torsional strain of a molecularly thin film of spherically symmetric molecules confined to a chemically heterogeneous slit pore by means of Monte Carlo simulations in the grand canonical ensemble. The slit pore comprises two identical plane-parallel solid substrates, the fluid-substrate interaction is purely repulsive except for elliptic regions attracting fluid molecules. Under favorable thermodynamic conditions the confined film consists of fluid bridges where the molecules are preferentially adsorbed by the attractive elliptic regions, and span the gap between the opposite substrate surfaces. By rotating the upper substrate while holding the lower one in position, bridge phases can be exposed to a torsional strain 0< or =theta< or =pi/2 and the associated torsional stress T(theta) of the (fluidic) bridge phases can be calculated from molecular expressions. The obtained stress curve T(theta)(theta) is qualitatively similar to the one characteristic of sheared confined films: as the torsion strain increases, T(theta) rises to a maximum (yield point) and then decays monotonically to zero. By changing the ellipses' aspect ratio while keeping their area constant, we also investigate the influence of the attractive elliptic patterns' shape on T(theta)(theta).

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PubMed2003

Collective dynamics near fluid phase transitions.

By means of molecular dynamics simulations, we calculate the intermediate scattering function F(k(axially),t) where k(||) is the wave number and t is the time. We focus on thermodynamic states in the vicinity of a fluid phase transition in bulk and confined systems which we locate in parallel Monte Carlo simulations in the grand canonical ensemble. As one approaches the limit of stability of the fluid (i.e., its spinodal) from either low- or high-density branches of a subcritical isotherm, F(k(axially),t) becomes increasingly long-range. The apparent lack of decorrelation in the metastable regime can be understood within the framework of a simple mean-field theory that links the long-range nature of F(k(axially),t) to a divergence of the ratio of isostress and isochoric heat capacities gamma. Our results suggest that as one approaches the spinodal the dynamic structure factor S(k(axially),omega) (omega frequency), which is related to F(k(axially),t) through a Laplace transformation, should undergo a qualitative change from the usual triplet of Brillouin and Rayleigh lines to a singlet (delta-function-like peak) centered at omega=0 for states directly at the spinodal. This qualitative change in S(k(axially),omega) should be measurable in scattering experiments thereby promoting more detailed insight into the phase behavior and thermodynamic stability of confined and bulk fluids.

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PubMed2003

Phase behavior of confined symmetric binary mixtures.

We employ mean-field lattice density functional theory to investigate the phase behavior of a binary (A-B) mixture confined to nanoscopic slit pores with chemically homogeneous walls. We consider only nearest-neighbor interactions in symmetric mixtures, where epsilon(AA)=epsilon(BB) not equal epsilon(AB) and epsilon is a measure of attraction between molecules of like (subscripts AA and BB) and unlike species (subscript AB), respectively. In addition, molecules are exposed to short-range attraction by the substrates separated by z lattice planes where epsilon(W) is the relevant coupling parameter. Moreover, the chemical potentials of both components are the same, that is, mu(A)=mu(B)=mu. In thermodynamic equilibrium (for fixed temperature T and chemical potential mu) the grand-potential density omega[rho,m] (rho identical with [rho(1),...,rho(z)], m identical with [m(1),...,m(z)]) assumes a global minimum which we find by minimizing omega numerically with respect to the order parameters rho(l) identical with rho(A)(l)+rho(B)(l) (total local density) and m(l) identical with (rho(A)(l)-rho(B)(l))/rho(l) (local "miscibility") at lattice plane l parallel to the pore walls. By varying epsilon(AB) three generic types of bulk phase diagrams are observed. On account of confinement (i.e., by varying epsilon(W) as well as z) one may switch between these different types of phase diagrams. This may have profound practical repercussions for experimental nanophase separation since depending on pore width and chemical nature of its walls a bulk gas mixture may undergo capillary condensation and form either a stable mixed or demixed liquid phase.

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PubMed2002

Propagating hydrodynamic modes in confined fluids.

In molecular dynamics simulations in the microcanonical ensemble (MEMD) we calculate the intermediate scattering function F(k(||),t) for a "simple" fluid confined to nanoscopic slit pores with chemically homogeneous, planar substrate surfaces. Since system properties are translationally invariant in the x-y plane, we focus on the propagation of density modes parallel with the confining substrates by choosing a two-dimensional wave vector |k(||)|=k(||)=(k(x),k(y)) for our analysis. Within the framework of classical hydrodynamics, we develop conservation laws for z-averaged fluxes of heat and momentum. Using in-plane versions of the macroscopic stress tensor and internal-energy current as constitutive equations we derive an expression for F(k(||),t) in the hydrodynamic limit depending on the thermal diffusivity D(T), the sound attenuation coefficient Gamma, the in-plane adiabatic velocity of sound v(||), and the ratio of heat capacities at constant transverse stress and volume gamma. Through a fit of F(k(||),t) in the hydrodynamic limit and its associated memory function M(k(||),t) to MEMD data, reliable values for the set [D(T),Gamma,v(||),gamma] of material coefficients can be obtained. Variations in [D(T),Gamma,v(||),gamma] with s(z) may be correlated with variations in the solvation pressure -tau(zz)-P(b) with s(z) (tau(zz) is the stress exerted by the fluid along the surface normal and P(b) is the bulk pressure) and therefore linked to stratification of the confined fluid.

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