Pedro Manuel Alves Patrício

Capillary bridging and long-range attractive forces in a mean-field approach

When a mixture is confined, one of the phases can condense out. This condensate, which is otherwise metastable in the bulk, is stabilized by the presence of surfaces. In a sphere-plane geometry, routinely used in atomic force microscope and surface force apparatus, it can form a bridge connecting the surfaces. The pressure drop in the bridge gives rise to additional long-range attractive forces between them. By minimizing the free energy of a binary mixture we obtain the force-distance curves as well as the structural phase diagram of the configuration with the bridge. Numerical results predict a discontinuous transition between the states with and without the bridge and linear force-distance curves with hysteresis. We also show that similar phenomenon can be observed in a number of different systems, e.g., liquid crystals and polymer mixtures.

Colloidal interactions in two-dimensional nematics

Abstract:The interaction between two disks immersed in a 2D nematic is investigated i) analytically using the tensor order parameter formalism for the nematic configuration around isolated disks and ii) numerically using finite-element methods with adaptive meshing to minimize the corresponding Landau-de Gennes free energy. For strong homeotropic anchoring, each disk generates a pair of defects with one-half topological charge responsible for the 2D quadrupolar interaction between the disks at large distances. At short distance, the position of the defects may change, leading to unexpected complex interactions with the quadrupolar repulsive interactions becoming attractive. This short-range attraction in all directions is still anisotropic. As the distance between the disks decreases, their preferred relative orientation with respect to the far-field nematic director changes from oblique to perpendicular.

Interaction of colloids with a nematic-isotropic interface

The Landau-de Gennes free energy is used to calculate the interaction between long cylindrical colloids and the nematic-isotropic (NI) interface. This interaction has two contributions: one is specific of liquid crystals and results from the deformation of the director field close to the particles or to the interface, while the other is generic and results from wetting and surface tension effects. Deep in the nematic phase the director field of long cylindrical colloids, with strong homeotropic anchoring, exhibits two half-integer defect lines. As the colloid moves towards the interface, the director configuration changes through a series of discontinuous transitions, where one or two of the defects are annihilated. In addition, the NI interface bends towards the colloid in order to minimize the elastic free energy in the nematic. In the isotropic phase, the colloid is surrounded by a thin nematic layer that reduces the surface free energy under favorable wetting conditions. The interaction has a well-defined minimum near the interface. In this region the director and interfacial structures are complex and cannot be described analytically. Using the numerical results for the Landau-de Gennes free energy in the harmonic region, we obtained simple scaling laws for the (linear) force on the colloid.

Forces between elongated particles in a nematic colloid

Using molecular dynamics simulations we study the interactions between elongated colloidal particles (length to breath ratio >>1) in a nematic host. The simulation results are compared to the results of a Landau-de Gennes elastic free energy. We find that depletion forces dominate for the sizes of the colloidal particles studied. The tangential component of the force, however, allows us to resolve the elastic contribution to the total interaction. We find that this contribution differs from the quadrupolar interaction predicted at large separations. The difference is due to the presence of nonlinear effects, namely, the change in the positions and structure of the defects and their annihilation at small separations.

Undulation Instabilities in the Meniscus of Smectic Membranes

Using optical microscopy, phase shifting interferometry, and atomic force microscopy, we characterize the undulated structures which appear in the meniscus of freestanding ferroelectric smectic-C* films. We demonstrate that these periodic structures correspond to undulations of the smectic-air interface. The resulting striped pattern disappears in the untilted smectic-A phase. The modulation amplitude and wavelength of the instability both depend on meniscus thickness. We study the temperature evolution and propose a model that qualitatively accounts for the observations.

Geometrically-controlled twist transitions in nematic cells

We study geometrically controlled twist transitions of a nematic confined between a sinusoidal grating and a flat substrate. In these cells, the transition to the twisted state is driven by surface effects. We have identified the mechanisms responsible for the transition analytically and used exact numerical calculations to study the range of surface parameters where the twist instability occurs. Close to these values, the cell operates under minimal external fields or temperature variations.

Colloidal dipolar interactions in 2D smectic C films

Abstract:We use a two-dimensional (2D) elastic free energy to calculate the effective interaction between two circular disks immersed in smectic-C films. For strong homeotropic anchoring, the distortion of the director field caused by the disks generates topological defects that induce an effective interaction between the disks. We use finite elements, with adaptive meshing, to minimize the 2D elastic free energy. The method is shown to be accurate and efficient for inhomogeneities on the length scales set by the disks and the defects, that differ by up to 3 orders of magnitude. We compute the effective interaction between two disk-defect pairs in a simple (linear) configuration. For large disk separations, D, the elastic free energy scales as ∼D-2, confirming the dipolar character of the long-range effective interaction. For small D the energy exhibits a pronounced minimum. The lowest energy corresponds to a symmetrical configuration of the disk-defect pairs, with the inner defect at the mid-point between the disks. The disks are separated by a distance that is twice the distance of the outer defect from the nearest disk. The latter is identical to the equilibrium distance of a defect nucleated by an isolated disk.

Electro-rheology study of a series of liquid crystal cyanobiphenyls: experimental and theoretical treatment

In this work we study the electro-rheological behaviour of a series of four liquid crystal (LC) cyanobiphenyls with a number of carbon atoms in the alkyl group, ranging from five to eight (5CB–8CB). We present the flow curves for different temperatures and under the influence of an external electric field, ranging from 0 to 3 kV mm−1, and the viscosity as a function of the temperature, for the same values of electric field, obtained for different shear rates. Theoretical interpretation of the observed behaviours is proposed in the framework of the continuum theory of Leslie–Ericksen for low molecular weight nematic LCs. In our analysis, the director alignment angle is only a function of the ratio between the shear rate and the square of the electric field – boundary conditions are neglected. By fitting the theoretical model to the experimental data, we are able to determine some viscosity coefficients and the dielectric anisotropy as a function of temperature. To interpret the behaviour of the flow curves near the nematic–isotropic transitions, we apply the continuum theory of Olmsted–Goldbart, which extends the theory of Leslie–Ericksen to the case where the degree of alignment of the LC molecules can also vary.

Hierarchical wrinkling on elastomeric Janus spheres

Hierarchical wrinkling on elastomeric Janus spheres is permanently imprinted by swelling, for different lengths of time, followed by drying the particles in an appropriate solvent. First-order buckling with a spatial periodicity (λ11) of the order of a few microns and hierarchical structures comprising of 2nd order buckling with a spatial periodicity (λ12) of the order of hundreds of nanometers have been obtained. The 2nd order buckling features result from a Grinfeld surface instability due to the diffusion of the solvent and the presence of sol molecules.

Elliptical soft colloids in smectic- C films

We investigate theoretically the elliptical shapes of soft colloids in freely standing smectic- C films, that have been reported recently. The colloids favor parallel alignment of the liquid crystal molecules at their surfaces and, for sufficiently strong anchoring, will generate a pair of defects at the poles of the colloidal particles. The elastic free energy of the liquid crystal matrix will, in turn, affect the shape of the colloids. In this study we will focus on elliptical soft colloids and determine how their equilibrium shapes depend on the elastic constants of the liquid crystal, the anchoring strength, the surface tension, and the size of the colloids. A shape diagram is obtained analytically, by minimizing the Frank elastic free energy, in the limit of small eccentricities. The analytical results are verified, and generalized to arbitrary eccentricities, by numerical minimization of an appropriate Landau free energy. The latter is required for an adequate description of the topological defects when the liquid crystal correlation length is comparable to the size of the colloidal particles.