Re-entrant phase behaviour of network fluids: A patchy particle model with temperature-dependent valence

We study a model consisting of particles with dissimilar bonding sites ("patches"), which exhibits self-assembly into chains connected by Y-junctions, and investigate its phase behaviour by both simulations and theory. We show that, as the energy cost epsilon(j) of forming Y-junctions increases, the extent of the liquid-vapour coexistence region at lower temperatures and densities is reduced. The phase diagram thus acquires a characteristic "pinched" shape in which the liquid branch density decreases as the temperature is lowered. To our knowledge, this is the first model in which the predicted topological phase transition between a fluid composed of short chains and a fluid rich in Y-junctions is actually observed. Above a certain threshold for epsilon(j), condensation ceases to exist because the entropy gain of forming Y-junctions can no longer offset their energy cost. We also show that the properties of these phase diagrams can be understood in terms of a temperature-dependent effective valence of the patchy particles. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3605703]

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.

Helical Twisting of Electrospun Liquid Crystalline Cellulose Micro- and Nanofibers

Helically twisted fibers can be produced by electrospinning liquid-crystalline cellulose solutions. Fiber topographies are studied by atomic force microscopy, scanning electron microscopy (see figure) and polarized optical microscopy. The fibers have a nearly universal pitch-to-diameter ratio and comprise both right- and left-handed helices.

Transport mechanism in ionic liquid membranes and the study of thiomersal biodegradation

The initial goal of this work was the development of a supported liquid membrane (SLM) bioreactor for the remediation of vaccine production effluents contaminated with a highly toxic organomercurial – thiomersal. Therefore, two main aspects were focused on: 1) the development of a stable supported liquid membrane – using room temperature ionic liquids (RTILs) – for the selective transport of thiomersal from the wastewater to a biological compartment, 2) study of the biodegradation kinetics of thiomersal to metallic mercury by a Pseudomonas putida strain. The first part of the work focused on the evaluation of the physicochemical properties of ionic liquids and on the SLMs’ operational stability. The results obtained showed that, although it is possible to obtain a SLM with a high stability, water possesses nonnegligible solubility in the RTILs studied. The formation of water clusters inside the hydrophobic ionic liquid was identified and found to regulate the transport of water and small ions. In practical terms, this meant that, although it was possible to transport thiomersal from the vaccine effluent to the biological compartment, complete isolation of the microbial culture could not be guaranteed and the membrane might ultimately be permeable to other species present in the aqueous vaccine wastewater. It was therefore decided not to operate the initially targeted integrated system but, instead, the biological system by itself. Additionally, attention was given to the development of a thorough understanding of the transport mechanisms involved in the solubilisation and transport of water through supported liquid membranes with RTILs as well as to the evaluation of the effect of water uptake by the SLM in the transport mechanisms of water-soluble solutes and its effect on SLM performance. The results obtained highlighted the determinant role played by water – solubilised inside the ionic liquids – on the transport mechanism. It became clear that the transport mechanism of water and water-soluble solutes through SLMs with [CnMIM][PF6] RTILs was regulated by the dynamics of water clusters inside the RTIL, rather than by molecular diffusion through the bulk of the ionic liquid. Although the stability tests vi performed showed that there were no significant losses of organic phase from the membrane pores, the formation of water clusters inside the ionic liquid, which constitute new, non-selective environments for solute transport, leads to a clear deterioration of SLM performance and selectivity. Nevertheless, electrical impedance spectroscopy characterisation of the SLMs showed that the formation of water clusters did not seem to have a detrimental effect on the SLMs’ electrical characteristics and highlighted the potential of using this type of membranes in electrochemical applications with low resistance requirements. The second part of the work studied the kinetics of thiomersal degradation by a pure culture of P. putida spi3 strain, in batch culture and using a synthe tic wastewater. A continuous ly stirred tank reactor fed with the synthetic wastewater was also operated and the bioreactor’s performance and robustness, when exposed to thiomersal shock loads, were evaluated. Finally, a bioreactor for the biological treatment of a real va ccine production effluent was set up and operated at different dilution rates. Thus it was possible to treat a real thiomersal-contaminated effluent, lowering the outlet mercury concentration to values below the European limit for mercury effluent discharges.

Fractional dynamics in liquid manipulation

This paper presents a fractional calculus perspective in the study of signals captured during the movement of a mechanical manipulator carrying a liquid container. In order to study the signals an experimental setup is implemented. The system acquires data from the sensors, in real time, and, in a second phase, processes them through an analysis package. The analysis package runs off-line and handles the recorded data. The results show that the Fourier spectrum of several signals presents a fractional behavior. The experimental study provides useful information that can assist in the design of a control system and the trajectory planning to be used in reducing or eliminating the effect of vibrations.

Liquid crystal beads constrained on thin cellulosic fibers: Electric field induced microrotors and N-I transition

We directly visualize the response of nematic liquid crystal drops of toroidal topology threaded in cellulosic fibers, suspended in air, to an AC electric field and at different temperatures over the N-I transition. This new liquid crystal system can exhibit non-trivial point defects, which can be energetically unstable against expanding into ring defects depending on the fiber constraining geometries. The director anchoring tangentially near the fiber surface and homeotropically at the air interface makes a hybrid shell distribution that in turn causes a ring disclination line around the main axis of the fiber at the center of the droplet. Upon application of an electric field, E, the disclination ring first expands and moves along the fiber main axis, followed by the appearance of a stable "spherical particle" object orbiting around the fiber at the center of the liquid crystal drop. The rotation speed of this particle was found to vary linearly with the applied voltage. This constrained liquid crystal geometry seems to meet the essential requirements in which soliton-like deformations can develop and exhibit stable orbiting in three dimensions upon application of an external electric field. On changing the temperature the system remains stable and allows the study of the defect evolution near the nematic-isotropic transition, showing qualitatively different behaviour on cooling and heating processes. The necklaces of such liquid crystal drops constitute excellent systems for the study of topological defects and their evolution and open new perspectives for application in microelectronics and photonics.

MASS CONSERVATION ENHANCEMENT OF FREE BOUNDARY FLOWS IN COMPOSITES MANUFACTURING

Undesirable void formation during the injection phase of the liquid composite molding process can be understood as a consequence of the non-uniformity of the flow front progression, caused by the dual porosity of the fiber perform. Therefore the best examination of the void formation physics can be provided by a mesolevel analysis, where the characteristic dimension is given by the fiber tow diameter. In mesolevel analysis, liquid impregnation along two different scales; inside fiber tows and within the spaces between them; must be considered and the coupling between these flow regimes must be addressed. In such case, it is extremely important to account correctly for the surface tension effects, which can be modeled as capillary pressure applied at the flow front. When continues Galerkin method is used, exploiting elements with velocity components and pressure as nodal variables, strong numerical implementation of such boundary conditions leads to ill-posing of the problem, in terms of the weak classical as well as stabilized formulation. As a consequence, there is an error in mass conservation accumulated especially along the free flow front. This article presents a numerical procedure, which was formulated and implemented in the existing Free Boundary Program in order to significantly reduce this error.

Enantiomeric fraction evaluation of pharmaceuticals in environmentalmatrices by liquid chromatography-tandem mass spectrometry

The interest for environmental fate assessment of chiral pharmaceuticals is increasing and enantioselective analytical methods are mandatory. This study presents an enantioselective analytical method for the quantification of seven pairs of enantiomers of pharmaceuticals and a pair of a metabolite. The selected chiral pharmaceuticals belong to three different therapeutic classes, namely selective serotonin reuptake inhibitors (venlafaxine, fluoxetine and its metabolite norfluoxetine), beta-blockers (alprenolol, bisoprolol, metoprolol, propranolol) and a beta2-adrenergic agonist (salbutamol). The analytical method was based on solid phase extraction followed by liquid chromatography tandem mass spectrometry with a triple quadrupole analyser. Briefly, Oasis® MCX cartridges were used to preconcentrate 250 mL of water samples and the reconstituted extracts were analysed with a Chirobiotic™ V under reversed mode. The effluent of a laboratory-scale aerobic granular sludge sequencing batch reactor (AGS-SBR) was used to validate the method. Linearity (r2 > 0.99), selectivity and sensitivity were achieved in the range of 20–400 ng L−1 for all enantiomers, except for norfluoxetine enantiomers which range covered 30–400 ng L−1. The method detection limits were between 0.65 and 11.5 ng L−1 and the method quantification limits were between 1.98 and 19.7 ng L−1. The identity of all enantiomers was confirmed using two MS/MS transitions and its ion ratios, according to European Commission Decision 2002/657/EC. This method was successfully applied to evaluate effluents of wastewater treatment plants (WWTP) in Portugal. Venlafaxine and fluoxetine were quantified as non-racemic mixtures (enantiomeric fraction ≠ 0.5). The enantioselective validated method was able to monitor chiral pharmaceuticals in WWTP effluents and has potential to assess the enantioselective biodegradation in bioreactors. Further application in environmental matrices as surface and estuarine waters can be exploited.

Electrorheological characterization of dispersions in silicone oil of encapsulated liquid crystal 4-n-penthyl-4 '-cyanobiphenyl in polyvinyl alcohol and in silica

The electrorheological (ER) effect is known as the change in the apparent viscosity upon the application of an external electric field perpendicular to the flow direction. In this work we present the electrorheological behaviour of suspensions in silicone oil of two different dispersed phases: foams of liquid crystal 4-n-penthyl-4'-cyanobiphenyl (5CB) encapsulated in polyvinyl alcohol (PVA) and nano/microspheres of 5CB encapsulated in silica. We will present the viscosity curves under the application of an electric field ranging between 0 and 3 kV mm(-1). The ER effect was observed for the suspensions of 5CB/PVA but not in the case of 5CB/silica. For the case of the suspensions of 5CB/PVA, the effect of the viscosity of the continuum phase and the concentration of the dispersed phase was analysed, showing that the enhancement of the viscosity of the suspension increases with the concentration, as expected, however the continuum phase viscosity has no significant effect, at least in the investigated viscosity range.

Liquid-vapor interfaces of patchy colloids

We investigate the liquid-vapor interface of a model of patchy colloids. This model consists of hard spheres decorated with short-ranged attractive sites ("patches") of different types on their surfaces. We focus on a one-component fluid with two patches of type A and nine patches of type B (2A9B colloids), which has been found to exhibit reentrant liquid-vapor coexistence curves and very low-density liquid phases. We have used the density-functional theory form of Wertheim's first-order perturbation theory of association, as implemented by Yu and Wu [J. Chem. Phys. 116, 7094 (2002)], to calculate the surface tension, and the density and degree of association profiles, at the liquid-vapor interface of our model. In reentrant systems, where AB bonds dominate, an unusual thickening of the interface is observed at low temperatures. Furthermore, the surface tension versus temperature curve reaches a maximum, in agreement with Bernardino and Telo da Gama's mesoscopic Landau-Safran theory [Phys. Rev. Lett. 109, 116103 (2012)]. If BB attractions are also present, competition between AB and BB bonds gradually restores the monotonic temperature dependence of the surface tension. Lastly, the interface is "hairy," i.e., it contains a region where the average chain length is close to that in the bulk liquid, but where the density is that of the vapor. Sufficiently strong BB attractions remove these features, and the system reverts to the behavior seen in atomic fluids.

Phase behavior of shape-changing spheroids

We introduce a simple model for a biaxial nematic liquid crystal. This consists of hard spheroids that can switch shape between prolate (rodlike) and oblate (platelike) subject to an energy penalty Δε. The spheroids are approximated as hard Gaussian overlap particles and are treated at the level of Onsager's second-virial description. We use both bifurcation analysis and a numerical minimization of the free energy to show that, for additive particle shapes, (i) there is no stable biaxial phase even for Δε=0 (although there is a metastable biaxial phase in the same density range as the stable uniaxial phase) and (ii) the isotropic-to-nematic transition is into either one of two degenerate uniaxial phases, rod rich or plate rich. We confirm that even a small amount of shape nonadditivity may stabilize the biaxial nematic phase.

Viscosity measurements of compressed liquid dipropyl and dibutyl adipates

The paper reports viscosity measurements of compressed liquid dipropyl (DPA) and dibutyl (DBA) adipates obtained with two vibrating wire sensors developed in our group. The vibrating wire instruments were operated in the forced oscillation, or steady-state mode. The viscosity measurements of DPA were carried out in a range of pressures up to 18. MPa and temperatures from (303 to 333). K, and DBA up to 65. MPa and temperature from (303 to 373). K, covering a total range of viscosities from (1.3 to 8.3). mPa. s. The required density data of the liquid samples were obtained in our laboratory using an Anton Paar vibrating tube densimeter and were reported in a previous paper. The viscosity results were correlated with density, using a modified hard-spheres scheme. The root mean square deviation of the data from the correlation is less than (0.21 and 0.32)% and the maximum absolute relative deviations are within (0.43 and 0.81)%, for DPA and DBA respectively. No data for the viscosity of both adipates could be found in the literature. Independent viscosity measurements were also performed, at atmospheric pressure, using an Ubbelohde capillary in order to compare with the vibrating wire results. The expanded uncertainty of these results is estimated as ±1.5% at a 95% confidence level. The two data sets agree within the uncertainty of both methods. © 2015 Published by Elsevier B.V.

Liquid crystal mobility and PDLC memory effects

Dissertation presented at Faculdade de Ciências e Tecnologia of Universidade Nova de Lisboa to obtain the Degree of Master in Chemical and Biochemical Engineering

Dielectric study of triton X100: a glass-forming liquid

Dissertação para obtenção do grau de mestre em Engenharia de Materiais

Advanced instrumentation for superheated liquid detectors in dark matter searches

Dissertação para obtenção do Grau de Doutor em Engenharia Física