Transient hexagonal structures in sheared emulsions of isotropic inclusions on smectic bubbles in microgravity conditions.

We describe the collective behavior of isotropic droplets dispersed over a spherical smectic bubble, observed under microgravity conditions on the International Space Station (ISS). We find that droplets can form two-dimensional hexagonal structures changing with time. Our analysis indicates the possibility of spatial and temporal periodicity of such structures of droplets. Quantitative analysis of the hexagonal structure including the first three coordination circles was performed. A peculiar periodic-in-time ordering of the droplets, related to one-dimensional motion of droplets with non-uniform velocity, was found.

Global influence of mantle temperature and plate thickness on intraplate volcanism.

The thermochemical structure of lithospheric and asthenospheric mantle exert primary controls on surface topography and volcanic activity. Volcanic rock compositions and mantle seismic velocities provide indirect observations of this structure. Here, we compile and analyze a global database of the distribution and composition of Neogene-Quaternary intraplate volcanic rocks. By integrating this database with seismic tomographic models, we show that intraplate volcanism is concentrated in regions characterized by slow upper mantle shear-wave velocities and by thin lithosphere (i.e. <100 km). We observe a negative correlation between shear-wave velocities at depths of 125-175 km and melt fractions inferred from volcanic rock compositions. Furthermore, mantle temperature and lithospheric thickness estimates obtained by geochemical modeling broadly agree with values determined from tomographic models that have been converted into temperature. Intraplate volcanism often occurs in regions where uplifted (but undeformed) marine sedimentary rocks are exposed. Regional elevation of these rocks can be generated by a combination of hotter asthenosphere and lithospheric thinning. Therefore, the distribution and composition of intraplate volcanic rocks through geologic time will help to probe past mantle conditions and surface processes.

Mafic tiers and transient mushes: evidence from Iceland.

It is well established that magmatism is trans-crustal, with melt storage and processing occurring over a range of depths. Development of this conceptual model was based on observations of the products of magmatism at spreading ridges, including Iceland. Petrological barometry and tracking of the solidification process has been used to show that the Icelandic crust is built by crystallization over a range of depths. The available petrological evidence indicates that most of the active rift zones are not underlain by extensive and pervasive crystal mush. Instead, the microanalytical observations from Iceland are consistent with a model where magmatic processing in the lower crust occurs in sills of decimetric vertical thickness. This stacked sills mode of crustal accretion corresponds to that proposed for the oceanic crust on the basis of ophiolite studies. A key feature of these models is that the country rock for the sills is hot but subsolidus. This condition can be met if the porosity in thin crystal mushes at the margins of the sills is occluded by primitive phases, a contention that is consistent with observations from cumulate nodules in Icelandic basalts. The conditions required for the stabilization of trans-crustal mushes may not be present in magmatic systems at spreading ridges. This article is part of the Theo Murphy meeting issue 'Magma reservoir architecture and dynamics'.

Spontaneous liquid crystal and ferromagnetic ordering of colloidal magnetic nanoplates.

Ferrofluids are familiar as colloidal suspensions of ferromagnetic nanoparticles in aqueous or organic solvents. The dispersed particles are randomly oriented but their moments become aligned if a magnetic field is applied, producing a variety of exotic and useful magnetomechanical effects. A longstanding interest and challenge has been to make such suspensions macroscopically ferromagnetic, that is having uniform magnetic alignment in the absence of a field. Here we report a fluid suspension of magnetic nanoplates that spontaneously aligns into an equilibrium nematic liquid crystal phase that is also macroscopically ferromagnetic. Its zero-field magnetization produces distinctive magnetic self-interaction effects, including liquid crystal textures of fluid block domains arranged in closed flux loops, and makes this phase highly sensitive, with it dramatically changing shape even in the Earth's magnetic field.

Melting during late-stage rifting in Afar is hot and deep.

Investigations of a variety of continental rifts and margins worldwide have revealed that a considerable volume of melt can intrude into the crust during continental breakup, modifying its composition and thermal structure. However, it is unclear whether the cause of voluminous melt production at volcanic rifts is primarily increased mantle temperature or plate thinning. Also disputed is the extent to which plate stretching or thinning is uniform or varies with depth with the entire continental lithospheric mantle potentially being removed before plate rupture. Here we show that the extensive magmatism during rifting along the southern Red Sea rift in Afar, a unique region of sub-aerial transition from continental to oceanic rifting, is driven by deep melting of hotter-than-normal asthenosphere. Petrogenetic modelling shows that melts are predominantly generated at depths greater than 80 kilometres, implying the existence of a thick upper thermo-mechanical boundary layer in a rift system approaching the point of plate rupture. Numerical modelling of rift development shows that when breakup occurs at the slow extension rates observed in Afar, the survival of a thick plate is an inevitable consequence of conductive cooling of the lithosphere, even when the underlying asthenosphere is hot. Sustained magmatic activity during rifting in Afar thus requires persistently high mantle temperatures, which would allow melting at high pressure beneath the thick plate. If extensive plate thinning does occur during breakup it must do so abruptly at a late stage, immediately before the formation of the new ocean basin.

Athermal photofluidization of glasses.

Azobenzene and its derivatives are among the most important organic photonic materials, with their photo-induced trans-cis isomerization leading to applications ranging from holographic data storage and photoalignment to photoactuation and nanorobotics. A key element and enduring mystery in the photophysics of azobenzenes, central to all such applications, is athermal photofluidization: illumination that produces only a sub-Kelvin increase in average temperature can reduce, by many orders of magnitude, the viscosity of an organic glassy host at temperatures more than 100 K below its thermal glass transition. Here we analyse the relaxation dynamics of a dense monolayer glass of azobenzene-based molecules to obtain a measurement of the transient local effective temperature at which a photo-isomerizing molecule attacks its orientationally confining barriers. This high temperature (T(loc)~800 K) leads directly to photofluidization, as each absorbed photon generates an event in which a local glass transition temperature is exceeded, enabling collective confining barriers to be attacked with near 100% quantum efficiency.

Orientational order parameters of a de Vries-type ferroelectric liquid crystal obtained by polarized Raman spectroscopy and x-ray diffraction.

The orientational order parameters (P{2}) and (P{4}) of the ferroelectric, de Vries-type liquid crystal 9HL have been determined in the SmA and SmC phases by means of polarized Raman spectroscopy, and in the SmA phase using x-ray diffraction. Quantum density functional theory predicts Raman spectra for 9HL that are in good agreement with the observations and indicates that the strong Raman band probed in the experiment corresponds to the uniaxial, coupled vibration of the three phenyl rings along the molecular long axis. The magnitudes of the orientational order parameters obtained in the Raman and x-ray experiments differ dramatically from each other, a discrepancy that is resolved by considering that the two techniques probe the orientational distributions of different molecular axes. We have developed a systematic procedure in which we calculate the angle between these axes and rescale the orientational order parameters obtained from x-ray scattering with results that are then in good agreement with the Raman data. At least in the case of 9HL, the results obtained by both techniques support a "sugar loaf" orientational distribution in the SmA phase with no qualitative difference to conventional smectics A. The role of individual molecular fragments in promoting de Vries-type behavior is considered.

Two-dimensional microrheology of freely suspended liquid crystal films.

Smectic liquid crystals form freely-suspended, fluid films of highly uniform structure and thickness, making them ideal systems for studies of hydrodynamics in two dimensions. We have measured particle mobility and shear viscosity by direct observation of the gravitational drift of silica spheres and smectic islands included in these fluid membranes. In thick films, we observe a hydrodynamic regime dominated by lateral confinement effects, with the mobility of the inclusion determined predominantly by coupling of the fluid flow to the fixed boundaries of the film. In thin films, the mobility of inclusions is governed primarily by coupling of the fluid to the surrounding air, as predicted by Saffman-Delbrück theory.

Modeling dipolar and quadrupolar defect structures generated by chiral islands in freely suspended liquid crystal films.

We report a detailed theoretical analysis of quadrupolar interactions observed between islands, which are disklike inclusions of extra layers, floating in thin, freely suspended smectic- C liquid crystal films. Strong tangential anchoring at the island boundaries results in a strength +1 chiral defect in each island and a companion -1 defect in the film--these forming a topological dipole. While islands of the same handedness form linear chains with the topological dipoles pointing in the same direction, as reported in the literature, islands with different handedness form compact quadrupolar structures with the associated dipoles pointing in opposite directions. The interaction between such heterochiral-island-defect pairs is complex, with the defects moving to minimize the director field distortion as the distance between the islands changes. The details of the interisland potential and the trajectories of the -1 defects depend strongly on the elastic anisotropy of the liquid crystal, which can be modified in the experiments by varying the material chirality of the liquid crystal. A Landau model that describes the energetics of freely mobile defects is solved numerically to find equilibrium configurations for a wide range of parameters.

Chiral isotropic liquids from achiral molecules.

A variety of simple bent-core molecules exhibit smectic liquid crystal phases of planar fluid layers that are spontaneously both polar and chiral in the absence of crystalline order. We found that because of intralayer structural mismatch, such layers are also only marginally stable against spontaneous saddle splay deformation, which is incompatible with long-range order. This results in macroscopically isotropic fluids that possess only short-range orientational and positional order, in which the only macroscopically broken symmetry is chirality--even though the phases are formed from achiral molecules. Their conglomerate domains exhibit optical rotatory powers comparable to the highest ever found for isotropic fluids of chiral molecules.

V -shaped switching ferroelectric liquid crystal structure stabilized by dielectric surface layers.

The " V -shaped switching" mode in high polarization ferroelectric liquid crystals was studied with the aim of stabilizing the monostable bookshelf structure with the spontaneous polarization parallel to the glass plates. The director field in such cells was confirmed to be sensitive to both the liquid crystal properties and the cell parameters. In cells with only polyimide alignment layers, hysteresis free switching was never obtained, with bistable and asymmetric monostable structures compromising the zero-field dark state and preventing an ideal, hysteresis-free analog response. By incorporating a SiO(2) layer between the ITO electrode and the polyimide, the undesired states were suppressed and essentially hysteresis-free switching was obtained for driving frequencies in the range 0.2-200 Hz . Cells rubbed only on one side give more uniform alignment than cells rubbed on both sides but their inherent asymmetry shifts the long-term dark state away from 0 V and causes the response to gray level voltage modulation to be slightly asymmetric. The formation of different types of states as a function of the values of the surface parameters, and the observed stabilization of the V -shaped switching structure by the dielectric surface layers, are in good agreement with an earlier analysis by Copic [Phys. Rev. E 65, 021701 (2002)].

Electric-field-induced chirality flipping in smectic liquid crystals: the role of anisotropic viscosity.

We demonstrate the homogeneous and permanent reversal of the chirality of a condensed phase by an applied electric field. Tilted chiral smectic layers exhibit a coupled polarization density and molecular orientation fields which reorient about the layer normal as couple of fixed handedness in response to small applied electric fields. Experiments on some bent-core smectics show that above a threshold field the induced rotation can occur instead about the molecular long axis and that, as a result, the handedness of the phase can be flipped. The effect is quantitatively described by a nonequilibrium dissipative model of chiral smectic dynamics with anisotropic rotational viscosities.

Giant-block twist grain boundary smectic phases.

Study of a diverse set of chiral smectic materials, each of which has twist grain boundary (TGB) phases over a broad temperature range and exhibits grid patterns in the Grandjean textures of the TGB helix, shows that these features arise from a common structure: "giant" smectic blocks of planar layers of thickness l(b) > 200 nm terminated by GBs that are sharp, mediating large angular jumps in layer orientation between blocks (60 degrees < Delta < 90 degrees ), and lubricating the thermal contraction of the smectic layers within the blocks. This phenomenology is well described by basic theoretical models applicable in the limit that the ratio of molecular tilt penetration length-to-layer coherence length is large, and featuring GBs in which smectic ordering is weak, approaching thin, melted (nematic-like) walls. In this limit the energy cost of change of the block size is small, leading to a wide variation of block dimension, depending on preparation conditions. The models also account for the temperature dependence of the TGB helix pitch.

Control of molecular orientation in electrostatically stabilized ferroelectric liquid crystals.

The continuously reorientable (XY-like) ferroelectric polarization density of a chiral smectic liquid crystal is shown experimentally to produce nearly complete screening of the applied electric field in an appropriate cell geometry. This screening, combined with the expulsion of polarization charge for large polarization materials, is shown to produce electrostatic control of the orientation of a uniform optic axis or polarization field.

Polarization-modulated smectic liquid crystal phases.

Any polar-ordered material with a spatially uniform polarization field is internally frustrated: The symmetry-required local preference for polarization is to be nonuniform, i.e., to be locally bouquet-like or "splayed." However, it is impossible to achieve splay of a preferred sign everywhere in space unless appropriate defects are introduced into the field. Typically, in materials like ferroelectric crystals or liquid crystals, such defects are not thermally stable, so that the local preference is globally frustrated and the polarization field remains uniform. Here, we report a class of fluid polar smectic liquid crystals in which local splay prevails in the form of periodic supermolecular-scale polarization modulation stripes coupled to layer undulation waves. The polar domains are locally chiral, and organized into patterns of alternating handedness and polarity. The fluid-layer undulations enable an extraordinary menagerie of filament and planar structures that identify such phases.

Biaxial model of the surface anchoring of bent-core smectic liquid crystals.

In synclinically tilted smectic phases, bent-core liquid crystal molecules aligned with the director in the plane of a cell boundary will, in general, have their molecular (bow) planes parallel to the boundary, normal to it, or at a well-defined intermediate orientation. A model describing the interaction of such bent-core (banana-shaped) molecules with planar surfaces that distinguishes energetically between molecules lying flat on the surface and those oriented edge on is given by a biaxial modification of the uniaxial surface anchoring expression used for chiral smectics of rod-shaped molecules. When combined with a field-induced straightening of the smectic layers, the model provides a mechanism for the transition from an analog to a bistable director response observed electro-optically in the ferroelectric banana-shaped material (R,S)-MHOBOW.

Unusual thickness-dependent thermal behavior and anticlinic coupling in chiral smectic free-standing liquid-crystal films.

We observe, in free-standing films of a chiral smectic liquid crystal, a series of discrete transitions in the relative orientation of the tilt of the interior and surface layers. These transitions include a remarkable reentrant synclinic-anticlinic-synclinic ordering sequence of the film surfaces in the presence of an electric field upon cooling. The profiles of the associated heat-capacity anomalies are found to be strongly thickness dependent and exhibit a novel crossover behavior in reduced dimensions. We measure the anticlinic coupling between tilted surface layers in the smectic- A phase.

Electro-optic behavior of liquid-crystal-filled silica opal photonic crystals: effect of liquid-crystal alignment.

Photonic crystals made of nematic liquid crystal intercalated into the void space of close-packed silica spheres (synthetic porous opal) exhibit significant electric-field-induced shift of the optical Bragg reflection peak when the liquid crystal has the long molecular axis oriented parallel to the sphere surfaces. No such effect is observed for comparable fields when the long-axis orientation is normal to the sphere surfaces.