Discrete thinning of free-standing smectic films in the de Gennes “pre-smectic liquid” model

It is shown that the successive discrete thinning of free-standing smectic films (FSSFs), which is observed when the films are heated above the temperature of the smectic A-nematic bulk phase transition, has a natural explanation in terms of the de Gennes “pre-smectic liquid” model, provided that a sufficiently large external compressive force is applied to the free surfaces of the FSSF. In a real situation this force stems from the curvature of the surrounding miniscus, which plays the role of a volume reservoir. In this model a superheated FSSF is stabilized by balancing the external compressive and elastic forces. When heating takes place the bulk modulus of the pre-smectic lattice decreases, and when the superheating reaches a critical value, the FSSF is subject to a long-wavelength instability in thickness beause the external compressive and elastic forces can no longer be balanced for a fixed number of smectic layers. If a superheated FSSF possesses adequate stability against disruption, the balance of forces, which was disrupted, and hence the stability of the FSSF can be restored as a result of spontaneous thinning of the film to a thickness corresponding to a smaller number of smectic layers. In general, heating of a superheated FSSF is accompanied by a series of such thinning transitions. Near the critical points where the balance of the forces breaks down, the dislocation mechanism of spontaneous thinning, which could be responsible for the stratified nature of the progressive discrete thinning of real FSSFs, can become dangerous. Zh. éksp. Teor. Fiz. 115, 61–69 (January 1999)     

Steps on the smectic a liquid crystal surface and their interaction with an edge dislocation

The step on the smectic A surface is modelled using a part of an edge dislocation solution. Then a step-edge dislocation interaction in a finite smectic A sample is calculated and discussed.     

Solid-state morphology of aromatic-aliphatic polyester crystallized from smectic liquid crystal

The solid-state morphology of poly(hexamethylene p,p'-bi-benzoate) (BB-6) and its dependence on the texture of the smectic liquid crystal state from which it crystallized were studied using electron microscopy, polarizing optical microscopy, and small-angle x-ray diffractometry. Thin films of BB-6 suitable for the microscopy were prepared by casting a hot solution of the polymer in tetrabromoethane onto mica at 150°C. The as-cast film of BB-6 was first heated to 260°C, maintained in the smectic range (210°C), and then cooled gradually to room temperature. A number of types of defect structures—such as Dupan cyclides, edge dislocation, tilt walls, and disclinations — were observed in the solid BB-6 formed from the smectic melt. On the basis of the electron microscopy and small-angle x-ray diffractometry, it is suggested that folded-chain crystals are formed during the crystallization from the smectic melt. Electron microscopic observations of the solid BB-6 and its orientation behavior under shear can be reasonably explained by assuming the presence of a precursory chain-folded layer structure in the smectic liquid crystal of BB-6.     

A model of crack based on dislocations in smectic A liquid crystals

A plastic crack model for smectic A liquid crystals under longitudinal shear is suggested. The solution of the screw dislocation in smectic A is the key to the correct result that we obtained by overcoming a longstanding puzzle. We further use the dislocation pile-up principle and the singular integral equation method to construct the solution of the crack in the phase. From the solution, we can determine the size of the plastic zone at the crack tip and the crack tip opening （tearing） displacement, which are the parameters relevant to the local stability/instability of materials. Our results may be useful for developing soft-matter mechanics.     

Meniscus-Induced Thinning of Smectic Nanofilms

JETP Letters - A new mechanism of thinning of smectic nanofilms is discovered, differing from that previously described in experimental and theoretical works. The size and shape of a meniscus...     

Topology and Geometry of Smectic Order on Compact Curved Substrates

Smectic order on arbitrary curved substrate can be described by a differential form of rank one (1-form), whose geometric meaning is the differential of the local phase field of the density modulation. The exterior derivative of 1-form is the local dislocation density. Elastic deformations are described by superposition of exact differential forms. We use the formalism of differential forms to systematically classify and characterize all low energy smectic states on torus as well as on sphere. A two dimensional smectic order confined on either manifold exhibits many topologically distinct low energy states. Different states are not accessible from each other by local fluctuations. The total number of low energy states scales as the square root of the system area. We also address the energetics of 2D smectic on a curved substrate and calculate the mean field phase diagram of smectic on a thin torus. Finally, we discuss the motion of disclinations for spherical smectics as low energy excitations, and illustrate the interesting connection between spherical smectic and the theory of elliptic functions.     

Light-induced layer by layer thickening in photosensitive liquid crystal membranes

Photosensitive smectic membranes of pure liquid crystal (LC) were studied under white light illumination. A thickness increase is observed in the illuminated film area. Appropriate light and thermal conditions lead to a thickening layer by layer process. This unusual phenomenon is opposite to the well-known step-by-step thinning transitions under heating. We give a phenomenological interpretation for thickening based on layer transport of LC matter towards the illuminated area.     

Dynamics of layer-by-layer thinning of free-standing smectic films

A dynamic model has been proposed for describing the extrusion of a single layer of a liquid-crystal (LC) material into a meniscus from an N-layer circular free-standing smectic film (FSSF). In the framework of this model, the main mechanism responsible for the process of the thinning (extrusion) of the LC material from the N-layer FSSF is based on the appearance of a spatial pressure gradient directed along the radius of the circular FSSF. This gradient is formed due to the difference in the disjoining pressures on both sides of the front separating the N- and (N–1)-layer domains of the smectic film. The proposed model allows taking into account the influence of the meniscus on dynamic characteristics, such as the time required for the complete extrusion of a single layer from the N-layer FSSF and the velocity of propagation of the front separating the N- and (N–1)-layer domains in the process of the thinning of the smectic film formed by molecules of 5-n-alkyl-2-(4-n-(perfluoroalkyl-methyleneoxy))pentyl.     

Collapse of islands in freely suspended smectic nanofilms

A time-nonlinear stage of the collapse of islands in freely suspended smectic nanofilms is observed and investigated. Islands thicker than a nanofilm are prepared and studied, which are unstable inside the dislocation loops, since they increase the energy of the film. Such instability leads to the decrease in the size of islands and is terminated by their collapse. The time dependence of the size of islands is measured experimentally. It is shown that the found dependence is in agreement with the theory of the dynamics of dislocation loops in smectic films developed earlier with allowance for the dissipation of energy in the film and in the meniscus. A nontrivial dynamic coupling between islands in a film resembling Ostwald ripening is also found, though the nonequilibrium kinetics of unstable islands, at which the hydrodynamic flow through a film leads to the decrease in sizes of one island and the increase in those of the other, rather than of the growth of the nucleation centers in the thermodynamically stable phase from the metastable state of the system (described by the Lifshitz–Slezov theory in films), is studied in our experiments.     

Stability of a free-standing liquid-crystal film: The measurement of the interaction between the film surfaces

The interaction energy of the surfaces of a free-standing liquid-crystal film has been determined. The measurements are performed in a smectic phase below the melting temperature of a bulk sample T _C, in the temperature range of structural instability of thin films at T > T _C, and in a quasi-smectic phase at T > T _C. Two modes of smectic-layer motion in the film are detected: they lead to film thinning at T > T _C and film thickening at a low temperature. The measurement results are discussed in terms of recent theoretical concepts.     

Topology of smectic order on compact substrates

Smectic orders on curved substrates can be described by differential forms of rank one (1-forms), whose geometric meaning is the differential of the local phase field of density modulation. The exterior derivative of the 1-form is the local dislocation density. Elastic deformations are described by superposition of exact differential forms. Applying this formalism to study smectic order on a torus as well as on a sphere, we find that both systems exhibit many topologically distinct low energy states that can be characterized by two integer topological charges. The total number of low energy states scales as the square root of the substrate area. For a smectic on a sphere, we also explore the motion of disclinations as possible low energy excitations, as well as its topological implications.     

Determination of bulk values of twist elasticity coefficient in a chiral smectic C* liquid crystal

A method is described for determination of bulk values of a twist elastic coefficient for smectic c-director in chiral smectic liquid crystals with a helical structure. The method was applied to 4-methylbutyloxy phenyl-4-octyloxy-benzoate (C8) in the chiral smectic C* phase. The measurements were performed using optical detection in a small deformation limit. In contrast to the usual methods, initial deformation of the helix (caused by strong surface interactions) was avoided by using homeotropic aligned thick samples. The critical temperature dependence of the measured coefficient was observed. The relation between the measured parameter and the smectic C order parameter is presented.     

Collective behavior of light-induced droplets in smectic membranes

Collective behavior and organization of droplets in thin smectic membranes were investigated using polarized light microscopy. Droplets were nucleated in membranes by light illumination. We observed the formation of periodic hexagonal and square lattice structures from droplets at large droplet concentration. Nearly linear dependence between period of structure and droplet size was found. We observed that droplets are nucleated on dislocations and periodic chain of droplets may be formed along a dislocation.Received: 29 september 2003, Published online: 5 February 2004PACS: 61.30.Eb Experimental determinations of smectic, nematic, cholesteric, and other structures - 64.70.Md Transitions in liquid crystals - 68.03.Cd Surface tension and related phenomena     

Hydrogen-enhanced local plasticity in aluminum: an ab initio study

Dislocation core properties of Al with and without H impurities are studied using the Peierls-Nabarro model with parameters determined by ab initio calculations. We find that H not only facilitates dislocation emission from the crack tip but also enhances dislocation mobility dramatically, leading to macroscopically softening and thinning of the material ahead of the crack tip. We observe strong binding between H and dislocation cores, with the binding energy depending on dislocation character. This dependence can directly affect the mechanical properties of Al by inhibiting dislocation cross-slip and developing slip planarity.     

Mechanical behavior of the smectic phases near the phase transitions

We present experimental data on the apparent layer complex rigidity of the smectic A, C, B phases of 40 P90B versus temperature at a fixed frequency of 50 Hz. Across the nematic → smectic A and smectic A → smectic C second order transitions, the modulus of the rigidity coefficient becomes very weak, and its phase undergoes a rapid variation of π, in a range of about 100 mK. At the first order smectic C → smectic $\text{B}$ transition, a corresponding discontinuity is observed. This behavior is tentatively explained in term of coupling of the nematic director (or defects) with the shear flow associated with the compression, and an associated viscoelastic relaxation.     

Molecular models for ferroelectric liquid crystals with conventional and anomalously weak layer contraction

A molecular theory of the ferroelectric smectic C* phase has been developed using the simple model of a chiral molecule composed of a uniaxial core and a pair of off-center nonparallel dipoles which determine molecular chirality and polarity. The interaction between uniaxial cores is modeled by a rather general effective potential which can be used to describe smectic materials with both conventional and anomalously weak layer contraction in the smectic C* phase. Spontaneous polarization, tilt, and layer spacing are calculated numerically as functions of temperature, and it is shown that the variation of the polarization generally deviates from that of the tilt angle. It is shown that this deviation is more pronounced in smectic materials tilting with low layer contraction which corresponds to existing experimental data. The model has been used to reproduce qualitatively the experimental data for polarization, tilt and layer spacing for two similar mixtures exhibiting conventional and anomalously weak layer contraction. The polarization and the tilt are also calculated in the case when the smectic A-smectic C* transition is characterized by the biaxial primary order parameter.     

Surface triple points and multiple-layer transitions observed by tuning the surface field at smectic liquid-crystal-water interfaces

We present an ellipsometric study of the interface between a smectic liquid crystal and water in the presence of a nonionic surfactant. The surfactant concentration serves as a handle to tune the surface field. For sufficiently large surfactant concentrations, a smectic phase is present at the interface in the temperature range above the smectic-A-isotropic bulk transition; when the bulk transition is approached, the thickness of this surface phase grows via a series of layer-by-layer transitions at which single smectic layers are formed. At lower surfactant concentrations, transitions appear at which the thickness of the surface phase jumps by multiple smectic layers, thereby implying the existence of triple points at which surface phases with different smectic layer numbers coexist. This is the first experimental demonstration of such surface triple points which are predicted by theoretical models.     

Hunting for smectic C in calamitic azobenzene ionic liquid crystals with different cationic head groups

The tilted smectic C phase is a rather uncommon phase in ionic liquid crystals (ILCs), whereas the orthogonal smectic A phase is the most common phase in ILCs. We now present 2 new groups of mesogens with an azobenzene core that exhibit smectic C as well as smectic A phases. Their phase sequences and tilt angles were studied by polarizing microscopy, and their temperature‐dependent layer spacings and orientational order parameters were investigated by X‐ray diffraction. We present 1 new amidinium azobenzene mesogen that forms enantiotropic smectic C and A phases and another amidinium as well as 2 new guanidinium azobenzene mesogens that exhibit monotropic smectic C and enantiotropic smectic A phases. With this study, we show that azobenzene is indeed an SmC‐promoting group in ILCs. Comparing these results with our earlier results on azobenzenes with an N‐methylimidazolium head group (N Kapernaum et al, ChemPhysChem 2016, 17, 4116‐4123), we show that the aromaticity of the imidazolium head group plays an important role in the formation of smectic C phases.     

Low-density dislocation arrays at heteroepitaxial Ge/GaAs-interfaces investigated by high voltage electron microscopy

High-voltage electron microscopy in combination with a large-area thinning technique has been applied to thin epitaxial Ge layers on GaAs substrates. These layers exhibit 60° misfit dislocations along the 〈110〉 directions parallel to the interface. Various dislocation reactions are evaluated from the electron micrographs, e.g. the formation of non-glissile 90° dislocations from two nearly parallel 60° dislocations and the annihilation reaction of two crossing 60° dislocations with identical Burgers vectors. The latter reaction occasionally leads to a dislocation multiplication. The misfit dislocations in very thin layers (～0.5 μm thickness and a linear dislocation density of less than 100 dislocation lines/cm) tend to be arranged in groups rather than being equidistant. Consequences for the interpretation of x-ray topograms are discussed.