arXiv subjects

F. Schmid

Publications and source records attributed to F. Schmid.

27 records · Page 2Linked to original sources

arXiv1998

Monte Carlo simulations of interfaces in polymer blends

We review recent simulation studies of interfaces between immiscible homopolymer phases. Special emphasis is given to the presentation of efficient simulation techniques and powerful methods of data analysis, such as the analysis of capillary wave spectra. Possible reasons for polymer incompatibility and ways to relate model dependent interaction parameters to an effective Flory Huggins parameter are discussed. Various interfaces are then considered and characterised with respect to their microscopic structure and thermodynamic properties. In particular, interfaces between homopolymers of equal or disparate stiffness are studied, interfaces containing diblock copolymers, and interfaces confined in thin films. The results are related to the phase behaviour of ternary homopolymer/copolymer systems, and to wetting transitions in thin films.

cond-mat.soft↗

arXiv1998

Liquid-vapour phase behaviour of a symmetrical binary fluid mixture

Using Monte-Carlo simulation and mean field calculations, we study the liquid-vapour phase diagram of a square well binary fluid mixture as a function of a parameter $δ$ measuring the relative strength of interactions between particles of dissimilar and similar species. The results reveal a rich variety of liquid-vapour coexistence behaviour as $δ$ is tuned. Specifically, we uncover critical end point behaviour, a triple point involving a vapour and two liquids of different density, and tricritical behaviour. For a certain range of $δ$, the mean field calculations also predict a `hidden' (metastable) liquid-vapour binodal.

cond-mat.stat-mech↗

arXiv1997

Interfaces in partly compatible polymer mixtures: A Monte Carlo simulation approach

The structure of polymer coils near interfaces between coexisting phases of symmetrical polymer mixtures (AB) is discussed, as well as the structure of symmetric diblock copolymers of the same chain length N adsorbed at the interface. The problem is studied by Monte Carlo simulations of the bond fluctuation model on the simple cubic lattice, using massively parallel computers (CRAY T3D). While homopolymer coils in the strong segregation limit are oriented parallel to the interface, the diblocks form ``dumbbells'' oriented perpendicular to the interface. However, in the dilute case (``mushroom regime'' rather than ``brush regime''), the diblocks are only weakly stretched. Distribution functions for monomers at the chain ends and in the center of the polymer are obtained, and a comparison to the self consistent field theory is made.

cond-mat.soft↗

arXiv1997

Diblock copolymers at a homopolymer-homopolymer-interface: a Monte Carlo simulation

The properties of diluted symmetric A-B diblock copolymers at the interface between A and B homopolymer phases are studied by means of Monte Carlo (MC) simulations of the bond fluctuation model. We calculate segment density profiles as well as orientational properties of segments, of A and B blocks, and of the whole chain. Our data support the picture of oriented ``dumbbells'', which consist of mildly perturbed A and B Gaussian coils. The results are compared to a self consistent field theory (SCFT) for single copolymer chains at a homopolymer interface. We also discuss the number of interaction contacts between monomers, which provide a measure for the ``active surface'' of copolymers or homopolymers close to the interface.

physics.chem-ph↗

arXiv1997

Stabilization of tilt order by chain flexibility in Langmuir monolayers

Langmuir monolayers are modeled as systems of short chains, which are confined to a planar surface at one end, but free to move within the plane. The phase behavior is calculated in a mean field approximation, which combines the self consistent field method with elements of classical density functional theory. It is shown that phases with tilt order are unstable in systems of stiff chains, but can be stabilized by chain conformational entropy in systems of sufficiently flexible chains. The chain entropy is also responsible for the appearance of an additional untilted phase, the liquid expanded phase. The region of stability of the different phases is discussed, and their microscopic structure is analyzed in some detail.

physics.chem-ph↗

arXiv1996

Influence of the Head Group Size on the Direction of Tilt in Langmuir Monolayers

A model of rods with heads of variable size, which are confined to a planar surface, is used to study the influence of the head group size on tilted phases in Langmuir monolayers. Simple free energy considerations as well as exact zero temperature calculations indicate that molecules with small head groups tilt towards next nearest neighbors, and molecules with larger head groups towards nearest neighbors. This provides a possible explanation for recent experimental results, and for details of the generic phase diagram for fatty acid monolayers.

physics.chem-ph↗

arXiv1996

Grafted Rods: A Tilting Phase Transition

A tilting phase transition is predicted for systems comprising rod like molecules which are irreversibly grafted to a flat surface, so that the non interacting rods are perpendicularly oriented. The transition is controlled by the grafting density $ρ$. It occurs as $ρ$ increases as a result of the interplay between two energies. Tilt is favoured by the van-der-Waals attraction between the rods. It is opposed by the bending elasticity of the grafting functionality. The role of temperature is discussed, and the tilting mechanism is compared to other tilting transitions reported in the literature.

cond-mat↗

arXiv1996

A self consistent field approach to surfaces of compressible polymer blends

A self consistent field theory for compressible polymer mixtures is developed by introducing elements of classical density functional theory into the framework of the Helfand theory. It is then applied to study free surfaces of binary (A,B) polymer blends. Density profiles in the one- and two-phase region are calculated as well as chain end distributions and chain orientations of the minority and the majority component. In the ideally symmetric mixture, in which the individual properties of polymers A and B are the same and both have the same surface energy, polymers of the minority component segregate to the surface, where they are exposed to less polymers of the majority component. This effect can only be captured correctly, if one accounts for the fact that the monomer-monomer interaction has finite range. As a consequence, the Flory-Huggins-parameter varies in space and depends on the concentration profiles and their derivatives. The surface segregation calculated with such an ansatz, without any fit parameter, is in reasonable quantitative agreement with data from recent Monte Carlo simulations.

cond-mat↗

arXiv1995

Errors in Monte Carlo simulations using shift register random number generators

We report large systematic errors in Monte Carlo simulations of the tricritical Blume-Capel model using single spin Metropolis updating. The error, manifest as a $20\%$ asymmetry in the magnetisation distribution, is traced to the interplay between strong triplet correlations in the shift register random number generator and the large tricritical clusters. The effect of these correlations is visible only when the system volume is a multiple of the random number generator lag parameter. No such effects are observed in related models.

cond-mat↗