arXiv subjects

P. S. Clegg

Publications and source records attributed to P. S. Clegg.

14 recordsLinked to original sources

arXiv2013

Colloidal templating at a cholesteric - oil interface: Assembly guided by an array of disclination lines

We simulate colloids (radius $R \sim 1μ$m) trapped at the interface between a cholesteric liquid crystal and an immiscible oil, at which the helical order (pitch p) in the bulk conflicts with the orientation induced at the interface, stabilizing an ordered array of disclinations. For weak anchoring strength W of the director field at the colloidal surface, this creates a template, favoring particle positions eitheron top of or midway between defect lines, depending on $α= R/p$. For small $α$, optical microscopy experiments confirm this picture, but for larger $α$ no templating is seen. This may stem from the emergence at moderate W of a rugged energy landscape associated with defect reconnections.

cond-mat.soft↗

arXiv2008

Influence of particle composition and thermal cycling on bijel formation

Colloidal particles with appropriate wetting properties can become very strongly trapped at an interface between two immiscible fluids. We have harnessed this phenomenon to create a new class of soft materials with intriguing and potentially useful characteristics. The material is known as a bijel: bicontinuous interfacially-jammed emulsion gel. It is a colloid-stabilized emulsion with fluid-bicontinuous domains. The potential to create these gels was first predicted using computer simulations. Experimentally we use mixtures of water and 2,6-lutidine at the composition for which the system undergoes a critical demixing transition on warming. Colloidal silica, with appropriate surface chemistry, is dispersed while the system is in the single-fluid phase; the composite sample is then slowly warmed well beyond the critical temperature. The liquids phase separate via spinodal decomposition and the particles become swept up on the newly created interfaces. As the domains coarsen the interfacial area decreases and the particles eventually become jammed together. The resulting structures have a significant yield stress and are stable for many months. Here we begin to explore the complex wetting properties of fluorescently-tagged silica surfaces in water-lutidine mixtures, showing how they can be tuned to allow bijel creation. Additionally we demonstrate how the particle properties change with time while they are immersed in the solvents.

cond-mat.soft↗

arXiv2008

Dynamics of a colloid-stabilized cream

We use x-ray photon correlation spectroscopy to investigate the dynamics of a high volume fraction emulsion creaming under gravity. The dodecane-in-water emulsion has interfaces stabilized solely by colloidal particles (silica). The samples were observed soon after mixing: as the emulsion becomes compact we discern two regimes of ageing with a cross-over between them. The young emulsion has faster dynamics associated with creaming in a crowded environment accompanied by local rearrangements. The dynamics slow down for the older emulsion although our studies show that motion is associated with large intermittent events. The relaxation rate, as seen from the intensity autocorrelation function, depends linearly on the wave vector at all times; however, the exponent associated with the line shape changes from 1.5 for young samples to less than 1 as the emulsion ages. The combination of ballisticlike dynamics, an exponent that drops below 1 and large intermittent fluctuations has not been reported before.

cond-mat.soft↗

arXiv2008

Fluid-bicontinuous gels stabilized by interfacial colloids: low and high molecular weight fluids

Carefully tuned composite materials can have properties wholly unlike their separate constituents. We review the development of one example: colloid-stabilized emulsions with bicontinuous liquid domains. These non-equilibrium structures resemble the sponge mesophase of surfactants; however, in the colloid-stabilized case the interface separating the liquid domains is itself semi-solid. The arrangement of domains is created by arresting liquid-liquid phase separation via spinodal decomposition. Dispersed colloids exhibiting partial wettability become trapped on the newly created interface and jam together as the domains coarsen. Similar structures have been created in polymer blends stabilized using either interfacial nanoparticles or clay platelets. Here it has been possible to create the domain arrangement either by phase separation or by direct mixing of the melt. The low molecular-weight liquid and polymer based structures have been developed independently and much can be learnt by comparing the two.

cond-mat.soft↗

arXiv2007

Bicontinuous emulsions stabilized solely by colloidal particles

Recent large-scale computer simulations suggest that it may be possible to create a new class of soft solids, called `bijels', by stabilizing and arresting the bicontinuous interface in a binary liquid demixing via spinodal decomposition using particles that are neutrally wetted by both liquids. The interfacial layer of particles is expected to be semi-permeable, hence, if realised, these new materials would have many potential applications, e.g. as microreaction media. However, the creation of bijels in the laboratory faces serious obstacles. In general, fast quench rates are necessary to bypass nucleation, so that only samples with limited thickness can be produced, which destroys the three-dimensionality of the putative bicontinuous network. Moreover, even a small degree of unequal wettability of the particles by the two liquids can lead to ill-characterised, `lumpy' interfacial layers and therefore irreproducible material properties. Here we report a reproducible protocol for creating three-dimensional samples of bijel in which the interfaces are stabilized by essentially a single layer of particles. We demonstrate how to tune the mean interfacial separation in these bijels, and show that mechanically, they indeed behave as soft solids.

cond-mat.soft↗

arXiv2006

Fluid-bicontinuous emulsions stabilized by colloidal particles

Using controlled spinodal decomposition, we have created a fluid-bicontinuous structure stabilized by colloidal particles. We present confocal microscopy studies of these structures and their variation with kinetic pathway. Our studies reveal a rigid multilayer of colloidal particles jammed at the interface which prevents the liquids demixing for many hours. The arrangement of two-fluid domains, interpenetrating on the meso-scale, could be useful as a microreaction medium.

cond-mat.soft↗

arXiv2006

Neutron Scattering and magnetization studies of Ba$_2$Cu$_{2.95}$Co$_{0.05}$O$_4$Cl$_2$: A decorated two-dimensional antiferromagnet

Ba$_2$Cu$_3$O$_4$Cl$_2$ has two inter-penetrating square Cu sublattices, one with square root 2 times the in-plane spacing of the other. Isotropic magnetic interactions between the two sublattices are completely frustrated. Quantum fluctuations resolve the intrinsic degeneracy in the ordering direction of the more weakly coupled sublattice in favor of collinear ordering. We present neutron scattering and magnetization studies of the magnetic structure when the Cu ions are substituted with Co. The Co spins create new magnetic interactions between the two sublattices. The ordering behavior of both Cu sublattices is retained largely unmodified. Between the phase transitions of the two sublattices spin-glass behavior is observed. Magnetization results show a strong enhancement to the ferromagnetic aspect of the magnetic structure. The combination of glassy behavior and large moments strongly suggest that the Co moments induce the formation of local canted states.

cond-mat.str-el↗

arXiv2005

Calorimetric study of the nematic to smectic-\textit{A} and smectic-\textit{A} to smectic-\textit{C} phase transitions in liquid-crystal+aerosil dispersions

A high-resolution calorimetric study has been carried out on nano-colloidal dispersions of aerosils in the liquid crystal 4-\textit{n}-pentylphenylthiol-4'-\textit{n}-octyloxybenzoate ($\bar{8}$S5) as a function of aerosil concentration and temperature spanning the smectic-\textit{C} to nematic phases. Over this temperature range, this liquid crystal possesses two continuous XY phase transitions: a fluctuation dominated nematic to smectic-\textit{A} transition with $α\approx α_{XY} = -0.013$ and a mean-field smectic-\textit{A} to smectic-\textit{C} transition. The effective critical character of the \textit{N}-Sm\textit{A} transition remains unchanged over the entire range of introduced quenched random disorder while the peak height and enthalpy can be well described by considering a cut-off length scale to the quasi-critical fluctuations. The robust nature of the \textit{N}-Sm\textit{A} transition in this system contrasts with cyanobiphenyl-aerosil systems and may be due to the mesogens being non-polar and having a long nematic range. The character of the Sm\textit{A}-Sm\textit{C} transition changes gradually with increasing disorder but remains mean-field-like. The heat capacity maximum at the Sm\textit{A}-Sm\textit{C} transition scales as $ρ_S^{-0.5}$ with an apparent evolution from tricritical to a simple mean-field step behavior. These results may be generally understood as a stiffening of the liquid crystal (both the nematic elasticity as well as the smectic layer compression modulus $B$) with silica density.

cond-mat.soft↗

arXiv2005

Colloid-stabilized emulsions: behaviour as the interfacial tension is reduced

We present confocal microscopy studies of novel particle-stabilized emulsions. The novelty arises because the immiscible fluids have an accessible upper critical solution temperature. The emulsions have been created by beginning with particles dispersed in the single-fluid phase. On cooling, regions of the minority phase nucleate. While coarsening these nuclei become coated with particles due to the associated reduction in interfacial energy. The resulting emulsion is arrested, and the particle-coated interfaces have intriguing properties. Having made use of the binary-fluid phase diagram to create the emulsion we then make use of it to study the properties of the interfaces. As the emulsion is re-heated toward the single-fluid phase the interfacial tension falls and the volume of the dispersed phase drops. Crumpling, fracture or coalescence can follow. The results show that the elasticity of the interfaces has a controlling influence over the emulsion behaviour.

cond-mat.soft↗

arXiv2005

X-ray studies of the phases and phase transitions of liquid crystals

This is a short review of recent x-ray diffraction studies of the phases and phase transitions of thermotropic liquid crystals. The areas covered are twist-grain-boundary phases, antiferroelectric phases studied with resonant x-ray diffraction, and smectic phases within gel structures. In all areas x-ray diffraction has played a key role. Nonetheless open questions remain: the nature of the smectic-C variant of the twist-grain-boundary phase, the origin of antiferroelectric phases, and whether novel Bragg glass states exist for smectic-A gel samples.

cond-mat.soft↗

arXiv2004

From incommensurate to dispersive spin-fluctuations: The high-energy inelastic spectrum in superconducting YBa2Cu3O6.5

We have investigated the spin fluctuations at energy transfers up to ~110 meV, well above the resonance energy (33 meV) in the YBa2Cu3O6.5 ortho-II superconductor using neutron time-of-flight and triple-axis techniques. The spectrum at high energies differs from the low-energy incommensurate modulations previously reported where the incommensurate wave vector is largely independent of energy. Well above the resonance the peak of the spin response lies at wave vectors that increase with energy. Within error the excitations at all energies above the resonance are best described by a ring around the (pi, pi) position. The isotropic wave-vector pattern differs from a recently reported square pattern in different but related systems. The spin spectral weight at high-energies is similar to that in the insulator but the characteristic velocity is ~40% lower. We introduce a method of extracting the acoustic and optic weights at all energies from time-of-flight data. We find that the optic spectral weight extends to surprisingly low-energies of ~25 meV, and infer that the bilayer spin correlations weaken with increase in hole doping. When the low-energy optic excitations are taken into account we measure the total integrated weight around (pi, pi), for energies below 120 meV, to agree with that expected from the insulator. As a qualitative guide, we compare spin-wave calculations for an ordered and a disordered stripe model and describe the inadequacy of this and other stripe models for the high-energy fluctuations.

cond-mat.supr-con↗

arXiv2003

First order isotropic - smectic-A transition in liquid crystal-aerosil gels

The short-range order which remains when the isotropic to smectic-A transition is perturbed by a gel of silica nanoparticles (aerosils) has been studied using high-resolution synchrotron x-ray diffraction. The gels have been created \textit{in situ} in decylcyanobiphenyl (10CB), which has a strongly first-order isotropic to smectic-A transition. The effects are determined by detailed analysis of the temperature and gel density dependence of the smectic structure factor. In previous studies of the continuous nematic to smectic-A transition in a variety of thermotropic liquid crystals the aerosil gel appeared to pin, at random, the phase of the smectic density modulation. For the isotropic to smectic-A transition the same gel perturbation yields different results. The smectic correlation length decreases more slowly with increasing random field variance in good quantitative agreement with the effect of a random pinning field at a transition from a uniform phase directly to a phase with one-dimensional translational order. We thus compare the influence of random fields on a \textit{freezing} transition with and without an intervening orientationally ordered phase.

cond-mat.soft↗

arXiv2003

Evolution of the isotropic to nematic phase transition in octyloxycyanobiphenyl+aerosil dispersions

High-resolution ac-calorimetry has been carried out on dispersions of aerosils in the liquid crystal octyloxycyanobiphenyl (8OCB) as a function of aerosil concentration and temperature spanning the crystal to isotropic phases. The liquid-crystal 8OCB is elastically stiffer than the previously well studied octylcyanobiphenyl (8CB)+aerosil system and so, general quenched random disorder effects and liquid-crystal specific effects can be distinguished. A double heat capacity feature is observed at the isotropic to nematic phase transition with an aerosil independent overlap of the heat capacity wings far from the transition and having a non-monotonic variation of the transition temperature. A crossover between low and high aerosil density behavior is observed for 8OCB+aerosil. These features are generally consistent with those on the 8CB+aerosil system. Differences between these two systems in the magnitude of the transition temperature shifts, heat capacity suppression, and crossover aerosil density between the two regimes of behavior indicate a liquid crystal specific effect. The low aerosil density regime is apparently more orientationally disordered than the high aerosil density regime, which is more translationally disordered. An interpretation of these results based on a temperature dependent disorder strength is discussed. Finally, a detailed thermal hysteresis study has found that crystallization of a well homogenized sample perturbs and increases the disorder for low aerosil density samples but does not influence high density samples.

cond-mat.soft↗

arXiv2003

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.

cond-mat.soft↗