Liquid crystal necklaces: cholesteric drops threaded by thin cellulose fibres

Liquid crystals in confined geometries exhibit numerous complex structures often including topological defects that are controlled by the nematic elasticity, chirality and surface anchoring. In this work, we study the structures of cholesteric droplets pierced by cellulose fibres with planar anchoring at droplet and fibre surfaces. By varying the temperature we demonstrate the role of twisting power and droplet diameter on the equilibrium structures. The observed structures are complemented by detailed numerical simulations of possible director fields decorated by defects. Three distinct structures, a bipolar and two ring configurations, are identified experimentally and numerically. Designing cholesteric liquid crystal microdroplets on thin long threads opens new routes to produce fibre waveguides decorated with complex microresonators.

Microscopic Theory of Anchoring Transitions at the Surfaces of Pure Liquid-Crystals and their Mixtures .1. The Fowler Approximation

We have generalized earlier work on anchoring of nematic liquid crystals by Sullivan, and Sluckin and Poniewierski, in order to study transitions which may occur in binary mixtures of nematic liquid crystals as a function of composition. Microscopic expressions have been obtained for the anchoring energy of (i) a liquid crystal in contact with a solid aligning surface; (ii) a liquid crystal in contact with an immiscible isotropic medium; (iii) a liquid crystal mixture in contact with a solid aligning surface. For (iii), possible phase diagrams of anchoring angle versus dopant concentration have been calculated using a simple liquid crystal model. These exhibit some interesting features including re-entrant conical anchoring, for what are believed to be realistic values of the molecular parameters. A way of relaxing the most drastic approximation implicit in the above approach is also briefly discussed.

How foam-like is the shear-induced lamellar phase of an ionic liquid crystal?

Philosophical Magazine Letters Volume 88, Issue 9-10, 2008 Special Issue: Solid and Liquid Foams. In commemoration of Manuel Amaral Fortes

Neural-network approach to modeling liquid crystals in complex confinement

Finding the structure of a confined liquid crystal is a difficult task since both the density and order parameter profiles are nonuniform. Starting from a microscopic model and density-functional theory, one has to either (i) solve a nonlinear, integral Euler-Lagrange equation, or (ii) perform a direct multidimensional free energy minimization. The traditional implementations of both approaches are computationally expensive and plagued with convergence problems. Here, as an alternative, we introduce an unsupervised variant of the multilayer perceptron (MLP) artificial neural network for minimizing the free energy of a fluid of hard nonspherical particles confined between planar substrates of variable penetrability. We then test our algorithm by comparing its results for the structure (density-orientation profiles) and equilibrium free energy with those obtained by standard iterative solution of the Euler-Lagrange equations and with Monte Carlo simulation results. Very good agreement is found and the MLP method proves competitively fast, flexible, and refinable. Furthermore, it can be readily generalized to the richer experimental patterned-substrate geometries that are now experimentally realizable but very problematic to conventional theoretical treatments.

Neural-network approach to modeling liquid crystals in complex confinement

Finding the structure of a confined liquid crystal is a difficult task since both the density and order parameter profiles are nonuniform. Starting from a microscopic model and density-functional theory, one has to either (i) solve a nonlinear, integral Euler-Lagrange equation, or (ii) perform a direct multidimensional free energy minimization. The traditional implementations of both approaches are computationally expensive and plagued with convergence problems. Here, as an alternative, we introduce an unsupervised variant of the multilayer perceptron (MLP) artificial neural network for minimizing the free energy of a fluid of hard nonspherical particles confined between planar substrates of variable penetrability. We then test our algorithm by comparing its results for the structure (density-orientation profiles) and equilibrium free energy with those obtained by standard iterative solution of the Euler-Lagrange equations and with Monte Carlo simulation results. Very good agreement is found and the MLP method proves competitively fast, flexible, and refinable. Furthermore, it can be readily generalized to the richer experimental patterned-substrate geometries that are now experimentally realizable but very problematic to conventional theoretical treatments.

What is the shape of an air bubble on a liquid surface?

We have calculated the equilibrium shape of the axially symmetric meniscus along which a spherical bubble contacts a flat liquid surface by analytically integrating the Young-Laplace equation in the presence of gravity, in the limit of large Bond numbers. This method has the advantage that it provides semianalytical expressions for key geometrical properties of the bubble in terms of the Bond number. Results are in good overall agreement with experimental data and are consistent with fully numerical (Surface Evolver) calculations. In particular, we are able to describe how the bubble shape changes from hemispherical, with a flat, shallow bottom, to lenticular, with a deeper, curved bottom, as the Bond number is decreased.

Metastable liquid-liquid phase transition in a single-component system with only one crystal phase and no density anomaly

We investigate the phase behavior of a single-component system in three dimensions with spherically-symmetric, pairwise-additive, soft-core interactions with an attractive well at a long distance, a repulsive soft-core shoulder at an intermediate distance, and a hard-core repulsion at a short distance, similar to potentials used to describe liquid systems such as colloids, protein solutions, or liquid metals. We showed [Nature (London) 409, 692 (2001)] that, even with no evidence of the density anomaly, the phase diagram has two first-order fluid-fluid phase transitions, one ending in a gas¿low-density-liquid (LDL) critical point, and the other in a gas¿high-density-liquid (HDL) critical point, with a LDL-HDL phase transition at low temperatures. Here we use integral equation calculations to explore the three-parameter space of the soft-core potential and perform molecular dynamics simulations in the interesting region of parameters. For the equilibrium phase diagram, we analyze the structure of the crystal phase and find that, within the considered range of densities, the structure is independent of the density. Then, we analyze in detail the fluid metastable phases and, by explicit thermodynamic calculation in the supercooled phase, we show the absence of the density anomaly. We suggest that this absence is related to the presence of only one stable crystal structure.

Simultaneous determination of gross alpha, gross beta and Ra-226 in natural water by liquid scintillation counting.

The determination of gross alpha, gross beta and 226Ra activity in natural waters is useful in a wide range of environmental studies. Furthermore, gross alpha and gross beta parameters are included in international legislation on the quality of drinking water [Council Directive 98/83/EC].1 In this work, a low-background liquid scintillation counter (Wallac, Quantulus 1220) was used to simultaneously determine gross alpha, gross beta and 226Ra activity in natural water samples. Sample preparation involved evaporation to remove 222Rn and its short-lived decay daughters. The evaporation process concentrated the sample ten-fold. Afterwards, a sample aliquot of 8 mL was mixed with 12 mL of Ultima Gold AB scintillation cocktail in low-diffusion vials. In this study, a theoretical mathematical model based on secular equilibrium conditions between 226Ra and its short-lived decay daughters is presented. The proposed model makes it possible to determine 226Ra activity from two measurements. These measurements also allow determining gross alpha and gross beta simultaneously. To validate the proposed model, spiked samples with different activity levels for each parameter were analysed. Additionally, to evaluate the model's applicability in natural water, eight natural water samples from different parts of Spain were analysed. The eight natural water samples were also characterised by alpha spectrometry for the naturally occurring isotopes of uranium (234U, 235U and 238U), radium (224Ra and 226Ra), 210Po and 232Th. The results for gross alpha and 226Ra activity were compared with alpha spectrometry characterization, and an acceptable concordance was obtained.

Simultaneous determination of gross alpha, gross beta and Ra-226 in natural water by liquid scintillation counting.

The determination of gross alpha, gross beta and 226Ra activity in natural waters is useful in a wide range of environmental studies. Furthermore, gross alpha and gross beta parameters are included in international legislation on the quality of drinking water [Council Directive 98/83/EC].1 In this work, a low-background liquid scintillation counter (Wallac, Quantulus 1220) was used to simultaneously determine gross alpha, gross beta and 226Ra activity in natural water samples. Sample preparation involved evaporation to remove 222Rn and its short-lived decay daughters. The evaporation process concentrated the sample ten-fold. Afterwards, a sample aliquot of 8 mL was mixed with 12 mL of Ultima Gold AB scintillation cocktail in low-diffusion vials. In this study, a theoretical mathematical model based on secular equilibrium conditions between 226Ra and its short-lived decay daughters is presented. The proposed model makes it possible to determine 226Ra activity from two measurements. These measurements also allow determining gross alpha and gross beta simultaneously. To validate the proposed model, spiked samples with different activity levels for each parameter were analysed. Additionally, to evaluate the model's applicability in natural water, eight natural water samples from different parts of Spain were analysed. The eight natural water samples were also characterised by alpha spectrometry for the naturally occurring isotopes of uranium (234U, 235U and 238U), radium (224Ra and 226Ra), 210Po and 232Th. The results for gross alpha and 226Ra activity were compared with alpha spectrometry characterization, and an acceptable concordance was obtained.

Kinetic modeling of mechanisms of industrially important organic reactions in gas and liquid phase

This dissertation is based on 5 articles which deal with reaction mechanisms of the following selected industrially important organic reactions: 1. dehydrocyclization of n-butylbenzene to produce naphthalene 2. dehydrocyclization of 1-(p-tolyl)-2-methylbutane (MB) to produce 2,6-dimethylnaphthalene 3. esterification of neopentyl glycol (NPG) with different carboxylic acids to produce monoesters 4. skeletal isomerization of 1-pentene to produce 2-methyl-1-butene and 2-methyl-2-butene The results of initial- and integral-rate experiments of n-butylbenzene dehydrocyclization over selfmade chromia/alumina catalyst were applied when investigating reaction 2. Reaction 2 was performed using commercial chromia/alumina of different acidity, platina on silica and vanadium/calcium/alumina as catalysts. On all catalysts used for the dehydrocyclization, major reactions were fragmentation of MB and 1-(p-tolyl)-2-methylbutenes (MBes), dehydrogenation of MB, double bond transfer, hydrogenation and 1,6-cyclization of MBes. Minor reactions were 1,5-cyclization of MBes and methyl group fragmentation of 1,6- cyclization products. Esterification reactions of NPG were performed using three different carboxylic acids: propionic, isobutyric and 2-ethylhexanoic acid. Commercial heterogeneous gellular (Dowex 50WX2), macroreticular (Amberlyst 15) type resins and homogeneous para-toluene sulfonic acid were used as catalysts. At first NPG reacted with carboxylic acids to form corresponding monoester and water. Then monoester esterified with carboxylic acid to form corresponding diester. In disproportionation reaction two monoester molecules formed NPG and corresponding diester. All these three reactions can attain equilibrium. Concerning esterification, water was removed from the reactor in order to prevent backward reaction. Skeletal isomerization experiments of 1-pentene were performed over HZSM-22 catalyst. Isomerization reactions of three different kind were detected: double bond, cis-trans and skeletal isomerization. Minor side reaction were dimerization and fragmentation. Monomolecular and bimolecular reaction mechanisms for skeletal isomerization explained experimental results almost equally well. Pseudohomogeneous kinetic parameters of reactions 1 and 2 were estimated by usual least squares fitting. Concerning reactions 3 and 4 kinetic parameters were estimated by the leastsquares method, but also the possible cross-correlation and identifiability of parameters were determined using Markov chain Monte Carlo (MCMC) method. Finally using MCMC method, the estimation of model parameters and predictions were performed according to the Bayesian paradigm. According to the fitting results suggested reaction mechanisms explained experimental results rather well. When the possible cross-correlation and identifiability of parameters (Reactions 3 and 4) were determined using MCMC method, the parameters identified well, and no pathological cross-correlation could be seen between any parameter pair.

Liquid transportation and distribution during (re)wetting : impact on coated papers in printing

In many industrial applications, such as the printing and coatings industry, wetting of porous materials by liquids includes not only imbibition and permeation into the bulk but also surface spreading and evaporation. By understanding these phenomena, valuable information can be obtained for improved process control, runnability and printability, in which liquid penetration and subsequent drying play important quality and economic roles. Knowledge of the position of the wetting front and the distribution/degree of pore filling within the structure is crucial in describing the transport phenomena involved. Although exemplifying paper as a porous medium in this work, the generalisation to dynamic liquid transfer onto a surface, including permeation and imbibition into porous media, is of importance to many industrial and naturally occurring environmental processes. This thesis explains the phenomena in the field of heatset web offset printing but the content and the analyses are applicable in many other printing methods and also other technologies where water/moisture monitoring is crucial in order to have a stable process and achieve high quality end products. The use of near-infrared technology to study the water and moisture response of porous pigmented structures is presented. The use of sensitive surface chemical and structural analysis, as well as the internal structure investigation of a porous structure, to inspect liquid wetting and distribution, complements the information obtained by spectroscopic techniques. Strong emphasis has been put on the scale of measurement, to filter irrelevant information and to understand the relationship between interactions involved. The near-infrared spectroscopic technique, presented here, samples directly the changes in signal absorbance and its variation in the process at multiple locations in a print production line. The in-line non-contact measurements are facilitated by using several diffuse reflectance probes, giving the absolute water/moisture content from a defined position in the dynamic process in real-time. The nearinfrared measurement data illustrate the changes in moisture content as the paper is passing through the printing nips and dryer, respectively, and the analysis of the mechanisms involved highlight the roles of the contacting surfaces and the relative liquid carrier properties of both non-image and printed image areas. The thesis includes laboratory studies on wetting of porous media in the form of coated paper and compressed pigment tablets by mono-, dual-, and multi-component liquids, and paper water/moisture content analysis in both offline and online conditions, thus also enabling direct sampling of temporal water/moisture profiles from multiple locations. One main focus in this thesis was to establish a measurement system which is able to monitor rapid changes in moisture content of paper. The study suggests that near-infrared diffuse reflectance spectroscopy can be used as a moisture sensitive system and to provide accurate online qualitative indicators, but, also, when accurately calibrated, can provide quantification of water/moisture levels, its distribution and dynamic liquid transfer. Due to the high sensitivity, samples can be measured with excellent reproducibility and good signal to noise ratio. Another focus of this thesis was on the evolution of the moisture content, i.e. changes in moisture content referred to (re)wetting, and liquid distribution during printing of coated paper. The study confirmed different wetting phases together with the factors affecting each phase both for a single droplet and a liquid film applied on a porous substrate. For a single droplet, initial capillary driven imbibition is followed by equilibrium pore filling and liquid retreat by evaporation. In the case of a liquid film applied on paper, the controlling factors defining the transportation were concluded to be the applied liquid volume in relation to surface roughness, capillarity and permeability of the coating giving the liquid uptake capacity. The printing trials confirmed moisture gradients in the printed sheet depending on process parameters such as speed, fountain solution dosage and drying conditions as well as the printed layout itself. Uneven moisture distribution in the printed sheet was identified to be one of the sources for waving appearance and the magnitude of waving was influenced by the drying conditions.

Vacuum-induced bubble formation in liquid-tempered chocolate

Bubble inclusion is one of the fastest growing operations practiced in the food industry. A variety of aerated foods is currently available in supermarkets, and newer products are emerging all the time. This paper aims to combine knowledge on chocolate aeration with studies performed on bubble formation and dispersion characteristics. More specifically, we have investigated bubble formation induced by applying vacuum. Experimental methods to determine gas hold-up (volume fraction of air), bubble section distributions along specific planes, and chocolate rheological properties are presented. This study concludes that decreasing pressures elevate gas hold-up values due to an increase in the number of bubble nuclei being formed and release of a greater volume of dissolved gases. Furthermore, bubbles are observed to be larger at lower pressures for a set amount of gas because the internal pressure needs to be in equilibrium with the surrounding pressures. Temperature-induced changes to the properties of the chocolate have less of an effect on bubble formation. On the other hand, when different fats and emulsifiers are added to a standard chocolate recipe, milk fat was found to increase, significantly, the gas hold-up values and the mean bubble-section diameters. It is hypothesized that this behavior is related to the way milk fats, which contain different fatty acids to cocoa butter, crystallize and influence the setting properties of the final product. It is highlighted that apparent viscosity values at low shear rate, as well as setting behavior, play an important role in terms of bubble formation and entrainment.

Memory effects in liquid crystal elastomers

Free-standing monodomain liquid crystal elastomer samples are shown to have a complete memory of the orientational configuration at the time of cross-linking. This memory is demonstrated through samples in which the parent polymer system is first aligned in a magnetic field prior to cross-linking. These films show reversible nematic-isotropic phase transitions and x-ray scattering patterns characteristic of nematic phases. The liquid crystal elastomer films exhibit a remarkable memory effect, in that the sample may be held at temperatures well above the nematic-isotropic transition for extended periods ( > 2 weeks), but on cooling into the liquid crystal phase region, both the original director alignment and the degree of preferred orientation are recovered. It is demonstrated that these novel memory effects are equilibrium in nature. The origins of this phenomena in terms of coupling between the mesogenic side-chains and the polymer network are discussed.

Side-chain liquid crystalline elastomers: the relationship between the orientational ordering of the polymer backbone and the length of the coupling chain

The influence of cross-linking on the phase behaviour of a series of side-chain liquid crystalline elastomers has been studied. For samples cross-linked in the temperature range corresponding to the nematic phase, the phase transition was shifted compared to that observed when an identical sample was cross-linked in the isotropic phase. This shift represented a stabilisation of the nematic phase in the former case, in line with theoretical expectations. By utilising a novel, slow cross-linking method, which allows the polymer backbone to take up an equilibrium conformation prior to network formation, it proved possible to monitor the shifts in phase transition temperature as a function of the length of the methylene chain coupling the mesogenic units to the polymer backbone. The results obtained are related to the backbone anisotropy and indicate that the level of orientational order of the polymer in the nematic phase backbone increases with a reduction in the length of the coupling chain.

Relaxation of surface tension in the liquid-solid interfaces of Lennard-Jones liquids

We have established the surface tension relaxation time in the liquid-solid interfaces of Lennard-Jones (LJ) liquids by means of direct measurements in molecular dynamics (MD) simulations. The main result is that the relaxation time is found to be almost independent of the molecular structures and viscosity of the liquids (at seventy-fold change) used in our study and lies in such a range that in slow hydrodynamic motion the interfaces are expected to be at equilibrium. The implications of our results for the modelling of dynamic wetting processes and interpretation of dynamic contact angle data are discussed.