Shear Alignment and Instability of Smectic Phases

We consider the shear flow of well-aligned one-component smectic phases, such as thermotropic smectics and lamellar diblock copolymers, below the critical region. We show that, as a result of thermal fluctuations of the layers, parallel ($c$) alignment is generically unstable and perpendicular ($a$) alignment is stable against long-wavelength undulations. We also find, surprisingly, that both $a$ and $c$ are stable for a narrow window of values for the anisotropic viscosity.Comment: To appear in PRL. Revtex, 1 figure

Shear instabilities of freely standing thermotropic smectic-A films

In this Letter we discuss theoretically the instabilities of thermotropic freely standing smectic-A films under shear flow\cite{re:wu}. We show that, in Couette geometry, the centrifugal force pushes the liquid crystal toward the outer boundary and induces smectic layer dilation close to the outer boundary. Under strong shear, this effect induces a layer buckling instability. The critical shear rate is proportional to $1/\sqrt{d}$, where $d$ is the thickness of the film.Comment: 12 pages, 2 figure

Simulations of a single membrane between two walls using a Monte Carlo method

Quantitative theory of interbilayer interactions is essential to interpret x-ray scattering data and to elucidate these interactions for biologically relevant systems. For this purpose Monte Carlo simulations have been performed to obtain pressure P and positional fluctuations sigma. A new method, called Fourier Monte-Carlo (FMC), that is based on a Fourier representation of the displacement field, is developed and its superiority over the standard method is demonstrated. The FMC method is applied to simulating a single membrane between two hard walls, which models a stack of lipid bilayer membranes with non-harmonic interactions. Finite size scaling is demonstrated and used to obtain accurate values for P and sigma in the limit of a large continuous membrane. The results are compared with perturbation theory approximations, and numerical differences are found in the non-harmonic case. Therefore, the FMC method, rather than the approximations, should be used for establishing the connection between model potentials and observable quantities, as well as for pure modeling purposes.Comment: 10 pages, 10 figure

Incommensurate Smectic Order at the Free Surface in the Nematic Phase of 4−N−Heptylphenyl−4′−(4"−Nitrobenzoyloxy)Benzoate(DB7NO2)4-N-Heptylphenyl-4'-(4"-Nitrobenzoyloxy)Benzoate (DB7NO_2)

We report x-ray reflectivity measurements on the free surface of $4-n-heptylphenyl-4'-(4"-nitrobenzoyloxy)benzoate (DB7NO_2)$ at the nematic to smectic-A phase transition, $T_{NA}=99.9^{\circ}C$. The free surface in the nematic phase exhibits smecticlike ordering at two q vectors, one which is commensurate with the smectic-A monolayer q vector $q_2$. The other q vector is incommensurate corresponding to ordering at $\sim 0.59q_2$. The commensurate peak constructively interferes with the air-liquid interface while the incommensurate peak destructively interferes. These results are compared with bulk-phase x-ray scattering measurements.Engineering and Applied Science

Oscillatory Shear Flow-Induced Alignment of Lamellar Melts of Hydrogen-Bonded Comb Copolymer Supramolecules

In this work we present the orientational behavior of comb copolymer-like supramolecules P4VP(PDP)1.0, obtained by hydrogen bonding between poly(4-vinylpyridine) and pentadecylphenol, during large-amplitude oscillatory shear flow experiments over a broad range of frequencies (0.001-10 Hz). The alignment diagram, presenting the macroscopic alignment in T/TODT vs ω/ωc, contains three regions of parallel alignment separated by a region of perpendicular alignment. For our material, the order-disorder temperature TODT = 67 °C and ωc, the frequency above which the distortion of the chain conformation dominates the materials’ viscoelasticity, is around 0.1 Hz at 61 °C. For the first time flipping from a pure transverse alignment via biaxial transverse/perpendicular alignment to a perpendicular alignment as a function of the strain amplitude was found.

High-resolution x-ray study of the nematic - smectic-A and smectic-A - smectic-C transitions in 8barS5-aerosil gels

The effects of dispersed aerosil nanoparticles on two of the phase transitions of the thermotropic liquid crystal material 4-n-pentylphenylthiol-4'-n-octyloxybenzoate 8barS5 have been studied using high-resolution x-ray diffraction techniques. The aerosils hydrogen bond together to form a gel which imposes a weak quenched disorder on the liquid crystal. The smectic-A fluctuations are well characterized by a two-component line shape representing thermal and random-field contributions. An elaboration on this line shape is required to describe the fluctuations in the smectic-C phase; specifically the effect of the tilt on the wave-vector dependence of the thermal fluctuations must be explicitly taken into account. Both the magnitude and the temperature dependence of the smectic-C tilt order parameter are observed to be unaffected by the disorder. This may be a consequence of the large bare smectic correlation length in the direction of modulation for this transition. These results show that the understanding developed for the nematic to smectic-A transition for octylcyanobiphenyl (8CB) and octyloxycyanobiphenyl (8OCB) liquid crystals with quenched disorder can be extended to quite different materials and transitions.Comment: 7 pages, 8 figure

Kinetic Arrest in Polyion-Induced Inhomogeneously-Charged Colloidal Particle Aggregation

Polymer chains adsorbed onto oppositely charged spherical colloidal particles can significantly modify the particle-particle interactions. For sufficient amounts of added polymers, the original electrostatic repulsion can even turn into an effective attraction and relatively large kinetically stable aggregates can form which display several unexpected and interesting peculiarities and some intriguing biotechnological implications. The attractive interaction contribution between two oppositely particles arises from the correlated adsorption of polyions at the oppositely charged particle surfaces, resulting in a non-homogeneous surface charge distribution. Here, we investigate the aggregation kinetics of polyion-induced colloidal complexes through Monte Carlo simulation, in which the effect of charge anisotropy is taken into account by a DLVO-like intra-particle potential, as recentely proposed by Velegol and Thwar [D. Velegol and P.K. Thwar, Langmuir, 17, 2001]. The results reveal that in the presence of a charge heterogeneity the aggregation process slows down due to the progressive increase of the potential barrier height upon clustering. Within this framework, the experimentally observed cluster phases in polyelectrolyte-liposomes solutions should be considered as a kinetic arrested state.Comment: 9 pages. 11 figure

Hard Spheres in Vesicles: Curvature-Induced Forces and Particle-Induced Curvature

We explore the interplay of membrane curvature and nonspecific binding due to excluded-volume effects among colloidal particles inside lipid bilayer vesicles. We trapped submicron spheres of two different sizes inside a pear-shaped, multilamellar vesicle and found the larger spheres to be pinned to the vesicle's surface and pushed in the direction of increasing curvature. A simple model predicts that hard spheres can induce shape changes in flexible vesicles. The results demonstrate an important relationship between the shape of a vesicle or pore and the arrangement of particles within it.Comment: LaTeX with epsfig; ps available at http://dept.physics.upenn.edu/~nelson/index.shtml Phys Rev Lett in press (1997