Micro – and nanofibers and liquid crystals for ligth-scattering shutters: Simulation of electrp-optical properties

This work demonstrates the feasibility of using polymeric micro- and nanofiber-composed films and liquid crystals as electrically switchable scattering light shutters. We present a concept of electro-optic device based on an innovative combination of two mature technologies: optics of nematic liquid crystals and electrospinning of nanofibers. These devices have electric and optical characteristics far superior to other comparable methods. The simulation presented shows results that are highly consistent with those of experiments and that explain the working mechanism of the devices.

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.

Invariant integrals applied to nematic liquid crystals with small Ericksen number and topological defects

Invariant integrals are derived for nematic liquid crystals and applied to materials with small Ericksen number and topological defects. The nematic material is confined between two infinite plates located at y = -h and y = h (h is an element of R+) with a semi-infinite plate at y = 0 and x < 0. Planar and homeotropic strong anchoring boundary conditions to the director field are assumed at these two infinite and semi-infinite plates, respectively. Thus, a line disclination appears in the system which coincides with the z-axis. Analytical solutions to the director field in the neighbourhood of the singularity are obtained. However, these solutions depend on an arbitrary parameter. The nematic elastic force is thus evaluated from an invariant integral of the energy-momentum tensor around a closed surface which does not contain the singularity. This allows one to determine this parameter which is a function of the nematic cell thickness and the strength of the disclination. Analytical solutions are also deduced for the director field in the whole region using the conformal mapping method. (C) 2013 Elsevier Ltd. All rights reserved.

Reconstructing the architectural evolution of volcanic islands from combined K/AR, morphologic, tectonic, and magnetic data. The Faial Island exemple (Azores)

The morpho-structural evolution of oceanic islands results from competition between volcano growth and partial destruction by mass-wasting processes. We present here a multi-disciplinary study of the successive stages of development of Faial (Azores) during the last 1 Myr. Using high-resolution digital elevation model (DEM), and new K/Ar, tectonic, and magnetic data, we reconstruct the rapidly evolving topography at successive stages, in response to complex interactions between volcanic construction and mass wasting, including the development of a graben. We show that: (1) sub-aerial evolution of the island first involved the rapid growth of a large elongated volcano at ca. 0.85 Ma, followed by its partial destruction over half a million years; (2) beginning about 360 ka a new small edifice grew on the NE of the island, and was subsequently cut by normal faults responsible for initiation of the graben; (3) after an apparent pause of ca. 250 kyr, the large Central Volcano (CV) developed on the western side of the island at ca 120 ka, accumulating a thick pile of lava flows in less than 20 kyr, which were partly channelized within the graben; (4) the period between 120 ka and 40 ka is marked by widespread deformation at the island scale, including westward propagation of faulting and associated erosion of the graben walls, which produced sedimentary deposits; subsequent growth of the CV at 40 ka was then constrained within the graben, with lava flowing onto the sediments up to the eastern shore; (5) the island evolution during the Holocene involves basaltic volcanic activity along the main southern faults and pyroclastic eruptions associated with the formation of a caldera volcano-tectonic depression. We conclude that the whole evolution of Faial Island has been characterized by successive short volcanic pulses probably controlled by brief episodes of regional deformation. Each pulse has been separated by considerable periods of volcanic inactivity during which the Faial graben gradually developed. We propose that the volume loss associated with sudden magma extraction from a shallow reservoir in different episodes triggered incremental downward graben movement, as observed historically, when immediate vertical collapse of up to 2 m was observed along the western segments of the graben at the end of the Capelinhos eruptive crises (1957-58).

Evidences for direct magnetic patterning via diffusive transformations using femtosecond laser interferometry

The application of femtosecond laser interferometry to direct patterning of thin-film magnetic alloys is demonstrated. The formation of stripe gratings with submicron periodicities is achieved in Fe1-xVx (x=18-34wt. %) layers, with a difference in magnetic moments up to Delta mu/mu similar to 20 between adjacent stripes but without any significant development of the topographical relief (<1% of the film thickness). The produced gratings exhibit a robust effect of their anisotropy shape on magnetization curves in the film plane. The obtained data witness ultrafast diffusive transformations associated with the process of spinodal decomposition and demonstrate an opportunity for producing magnetic nanostructures with engineered properties upon this basis.

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.

Post-processing Techniques in Free Boundary Flows during Liquid Composite Moulding Processes

Post-processing a finite element solution is a well-known technique, which consists in a recalculation of the originally obtained quantities such that the rate of convergence increases without the need for expensive remeshing techniques. Postprocessing is especially effective in problems where better accuracy is required for derivatives of nodal variables in regions where Dirichlet essential boundary condition is imposed strongly. Consequently such an approach can be exceptionally good in modelling of resin infiltration under quasi steady-state assumption by remeshing techniques and with explicit time integration, because only the free-front normal velocities are necessary to advance the resin front to the next position. The new contribution is the post-processing analysis and implementation of the freeboundary velocities of mesolevel infiltration analysis. Such implementation ensures better accuracy on even coarser meshes, which in consequence reduces the computational time also by the possibility of employing larger time steps.

Numerical Method to Predict Void Formation during The Liquid Composite Molding Process

Void formation during the injection phase of the liquid composite molding process can be explained as a consequence of the non-uniformity of the flow front progression. This is due to the dual porosity within the fiber perform (spacing between the fiber tows is much larger than between the fibers within in a tow) and therefore the best explanation can be provided by a mesolevel analysis, where the characteristic dimension is given by the fiber tow diameter of the order of millimeters. In mesolevel analysis, liquid impregnation along two different scales; inside fiber tows and within the open spaces between the fiber tows must be considered and the coupling between the flow regimes must be addressed. In such cases, it is extremely important to account correctly for the surface tension effects, which can be modeled as capillary pressure applied at the flow front. Numerical implementation of such boundary conditions leads to illposing 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. A numerical procedure was formulated and is implemented in an existing Free Boundary Program to reduce this error significantly.

Magnetic flux density distribution in the air gap of a ferromagnetic core with superconducting blocks: three-dimensional analysis and experimental NMR results

The design of magnetic cores can be carried out by taking into account the optimization of different parameters in accordance with the application requirements. Considering the specifications of the fast field cycling nuclear magnetic resonance (FFC-NMR) technique, the magnetic flux density distribution, at the sample insertion volume, is one of the core parameters that needs to be evaluated. Recently, it has been shown that the FFC-NMR magnets can be built on the basis of solenoid coils with ferromagnetic cores. Since this type of apparatus requires magnets with high magnetic flux density uniformity, a new type of magnet using a ferromagnetic core, copper coils, and superconducting blocks was designed with improved magnetic flux density distribution. In this paper, the designing aspects of the magnet are described and discussed with emphasis on the improvement of the magnetic flux density homogeneity (Delta B/B-0) in the air gap. The magnetic flux density distribution is analyzed based on 3-D simulations and NMR experimental results.

Transcranial magnetic resonance guided focused ultrasound: neurosurgery applications

Mestrado em Radiações Aplicadas às Tecnologias da Saúde

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.

A cellulosic liquid crystal pool for cellulose nanocrystals: structure and molecular dynamics at high shear rates

Cellulose and its derivatives, such as hydroxypropylcellulose (HPC) have been studied for a long time but they are still not well understood particularly in liquid crystalline solutions. These systems can be at the origin of networks with properties similar to liquid crystalline (LC) elastomers. The films produced from LC solutions can be manipulated by the action of moisture allowing for instance the development of a soft motor (Geng et al., 2013) driven by humidity. Cellulose nanocrystals (CNC), which combine cellulose properties with the specific characteristics of nanoscale materials, have been mainly studied for their potential as a reinforcing agent. Suspensions of CNC can also self-order originating a liquid-crystalline chiral nematic phases. Considering the liquid crystalline features that both LC-HPC and CNC can acquire, we prepared LC-HPC/CNC solutions with different CNC contents (1,2 and 5 wt.%). The effect of the CNC into the LC-HPC matrix was determined by coupling rheology and NMR spectroscopy - Rheo-NMR a technique tailored to analyse orientational order in sheared systems. (C) 2015 Elsevier Ltd. All rights reserved.

Influence of the substrate on structure and magnetic properties of Co-N thin films

Cubic cobalt nitride films were grown onto different single crystalline substrates Al2O3 (0 0 0 1) and (1 1 View the MathML source 0), MgO (1 0 0) and (1 1 0) and TiO2 (1 0 0) and (1 1 0). The films display low atomic densities compared with the bulk material, are ferromagnetic and have metallic electrical conductivity. X-ray diffraction and X-ray absorption fine structure confirm the cubic structure of the films and with RBS results indicate that samples are not homogeneous at the microscopic scale, coexisting Co4+xN nitride with nitrogen rich regions. The magnetization of the films decreases with increase of the nitrogen content, variation that is shown to be due to the decrease of the cobalt density, and not to a decrease of the magnetic moment per cobalt ion. The films are crystalline with a nitrogen deficient stoichiometry and epitaxial with orientation determined by the substrate.

Antibacterial activity of Ionic Liquids based on ampicillin against resistant bacteria

Antibacterial activity of novel Active Pharmaceutical Ingredient Ionic Liquids (API-ILs) based on ampicillin anion [Amp] have been evaluated. They showed growth inhibition and bactericidal properties on some sensitive bacteria and especially some Gram-negative resistant bacteria when compared to the [Na][Amp] and the initial bromide and chloride salts. For these studies were analysed the minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBIC) against sensitive Gram-negative bacteria Escherichia coli ATCC 25922 and Klebsiella pneumonia (clinically isolated), as well as sensitive Gram positive S. Aureus ATCC 25923, Staphylococcus epidermidis and Enterococcus faecalis and completed using clinically isolated resistent strains: E. coli TEM CTX M9, E. coli CTX M2 and E. coli AmpC Mox. From the obtained MIC values of studied APIs-ILs and standard [Na][Amp] were derived RDIC values (relative decrease of inhibitory concentration). High RDIC values of [C16Pyr][Amp] especially against two resistant Gram-negative strains E. coli TEM CTX M9 (RDIC>1000) and E. coli CTX M2 (RDIC>100) point clearly to a potential promising role of APIs-ILs as antimicrobial drugs especially against resistant bacterial strains.

Low temperature structural transitions in dipolar hard spheres: the influence on magnetic properties

We investigate the structural chain-to-ring transition at low temperature in a gas of dipolar hard spheres (DRS). Due to the weakening of entropic contribution, ring formation becomes noticeable when the effective dipole-dipole magnetic interaction increases, It results in the redistribution of particles from usually observed flexible chains into flexible rings. The concentration (rho) of DI-IS plays a crucial part in this transition: at a very low rho only chains and rings are observed, whereas even a slight increase of the volume fraction leads to the formation of branched or defect structures. As a result, the fraction of DHS aggregated in defect-free rings turns out to be a non-monotonic function of rho. The average ring size is found to be a slower increasing function of rho when compared Lo that of chains. Both theory and computer simulations confirm the dramatic influence of the ring formation on the rho-dependence of the initial magnetic susceptibility (chi) when the temperature decreases. The rings clue to their zero total dipole moment are irresponsive to a weak magnetic field and drive to the strong decrease of the initial magnetic susceptibility. (C) 2014 Elsevier B.V. All rights reserved.