The additive effects in matrix dispersed liquid crystals

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

Effect of ionic liquid anion and cation on the physico-chemical properties of poly(vinylidene fluoride)/ionic liquid blends

Poly(vinylidene fluoride), PVDF, has been blended with different ionic liquids (IL) in order to evaluate the effect of the different IL anions and cations on the electroative -phase, thermal, mechanical and electrical properties of the polymer blend. [C2MIM][Cl], [C6MIM][Cl], [C10MIM][Cl], [C2MIM][NTf2], [C6MIM][NTf2], [C10MIM][NTf2] have been selected and were introduced in the polymer at a weight percentage of 40 wt%. It was found that the incorporation of ILs into the PVDF matrix leads to an increase of the -phase content due to the strong electrostatic interactions between the dipolar moments of PVDF and the ILs. Further, the incorporation of ILs into PVDF strongly decreases the elastic modulus and increases the electrical conductivity of the blend with respect to the pure polymer matrix, all these effects being accompanied by a modification of the crystallization kinetics, as indicated by the modified spherulitic microstructure. Thus, novel PVDF/IL blends films with high transparency, excellent antistatic properties, and highly polar crystal form fraction were successfully achieved.

Freezing of 4He and its liquid-solid interface from density functional theory

We show that, at high densities, fully variational solutions of solidlike types can be obtained from a density functional formalism originally designed for liquid 4He . Motivated by this finding, we propose an extension of the method that accurately describes the solid phase and the freezing transition of liquid 4He at zero temperature. The density profile of the interface between liquid and the (0001) surface of the 4He crystal is also investigated, and its surface energy evaluated. The interfacial tension is found to be in semiquantitative agreement with experiments and with other microscopic calculations. This opens the possibility to use unbiased density functional (DF) methods to study highly nonhomogeneous systems, like 4He interacting with strongly attractive impurities and/or substrates, or the nucleation of the solid phase in the metastable liquid.

Lattice-gas model of orientable molecules: Application to liquid crystals

We have analyzed a two-dimensional lattice-gas model of cylindrical molecules which can exhibit four possible orientations. The Hamiltonian of the model contains positional and orientational energy interaction terms. The ground state of the model has been investigated on the basis of Karl¿s theorem. Monte Carlo simulation results have confirmed the predicted ground state. The model is able to reproduce, with appropriate values of the Hamiltonian parameters, both, a smectic-nematic-like transition and a nematic-isotropic-like transition. We have also analyzed the phase diagram of the system by mean-field techniques and Monte Carlo simulations. Mean-field calculations agree well qualitatively with Monte Carlo results but overestimate transition temperatures.

Finite-size scaling investigation of the liquid-liquid critical point in ST2 water and its stability with respect to crystallization.

The liquid-liquid critical point scenario of water hypothesizes the existence of two metastable liq- uid phases low-density liquid (LDL) and high-density liquid (HDL) deep within the supercooled region. The hypothesis originates from computer simulations of the ST2 water model, but the stabil- ity of the LDL phase with respect to the crystal is still being debated. We simulate supercooled ST2 water at constant pressure, constant temperature, and constant number of molecules N for N ≤ 729 and times up to 1 μs. We observe clear differences between the two liquids, both structural and dynamical. Using several methods, including finite-size scaling, we confirm the presence of a liquid-liquid phase transition ending in a critical point. We find that the LDL is stable with respect to the crystal in 98% of our runs (we perform 372 runs for LDL or LDL-like states), and in 100% of our runs for the two largest system sizes (N = 512 and 729, for which we perform 136 runs for LDL or LDL-like states). In all these runs, tiny crystallites grow and then melt within 1 μs. Only for N ≤ 343 we observe six events (over 236 runs for LDL or LDL-like states) of spontaneous crystal- lization after crystallites reach an estimated critical size of about 70 ± 10 molecules.

Mineral inventory of continuously erupting basaltic andesites at Arenal volcano, Costa Rica: implications for interpreting monotonous, crystal-rich, mafic arc stratigraphies

Except for the first 2 years since July 29, 1968, Arenal volcano has continuously erupted compositionally monotonous and phenocryst-rich (similar to35%) basaltic andesites composed of plagioclase (plag), orthopyroxene (opx), clinopyroxene (cpx), spinel olivine. Detailed textural and compositional analyses of phenocrysts, mineral inclusions, and microlites reveal comparable complexities in any given sample and identify mineral components that require a minimum of four crystallization environments. We suggest three distinct crystallization environments crystallized low Mg# (<78) silicate phases from andesitic magma but at different physical conditions, such as variable pressure of crystallization and water conditions. The dominant environment, i.e., the one which accounts for the majority of minerals and overprinted all other assemblages near rims of phenocrysts, cocrystallized clinopyroxene (Mg# similar to71-78), orthopyroxene (Mg# similar to71-78), titanomagnetite and plagioclase (An(60) to An(85)). The second environment cocrystallized clinopyroxene (Mg# 71-78), olivine (<Fo(78)), titanomagnetite, and very high An (similar to90) plagioclase, while the third cocrystallized clinopyroxene (Mg# 71-78) with high (>7) Al/Ti and high (>4 wt.%) Al2O3, titanomagnetite with considerable Al2O3 (10-18 wt.%) and possibly olivine but appears to lack plagioclase. A fourth crystallization environment is characterized by clinopyroxene (e.g., Mg#=similar to78-85; Cr2O3=0.15-0.7 wt.%), Al-, Cr-rich spinel olivine (similar toFo(80)), and in some circumstances high-An (>80) plagioclase. This assemblage seems to record mafic inputs into the Arenal system and crystallization at high to low pressures. Single crystals cannot be completely classified as xenocrysts, antecrysts (cognate crystals), or phenocrysts, because they often contain different parts each representing a different crystallization environment and thus belong to different categories. Bulk compositions are mostly too mafic to have crystallized the bulk of ferromagnesian minerals and thus likely do not represent liquid compositions. On the other hand, they are the cumulative products of multiple mixing events assembling melts and minerals from a variety of sources. The driving force for this multistage mixing evolution to generate erupting basaltic andesites is thought to be the ascent of mafic magma from lower crustal levels to subvolcanic depths which at the same time may also go through compositional modification by fractionation and assimilation of country rocks. Thus, mafic magmas become basaltic andesite through mixing, fractionation and assimilation by the time they arrive at subvolcanic depths. We infer new increments of basaltic andesite are supplied nearly continuously to the subvolcanic reservoir concurrently to the current eruption and that these new increments are blended into the residing, subvolcanic magma. Thus, the compositional monotony is mostly the product of repetitious production of very similar basaltic andesite. Furthermore, we propose that this quasi-constant supply of small increments of magma is the fundamental cause for small-scale, decade-long continuous volcanic activity; that is, the current eruption of Arenal is flux-controlled by inputs of mantle magmas. (C) 2004 Elsevier B.V. All rights reserved.

Comprehensive Study of Crystal Growth from Solution

Crystal growth is an essential phase in crystallization kinetics. The rate of crystal growth provides significant information for the design and control of crystallization processes; nevertheless, obtaining accurate growth rate data is still challenging due to a number of factors that prevail in crystal growth. In industrial crystallization, crystals are generally grown from multi-componentand multi-particle solutions under complicated hydrodynamic conditions; thus, it is crucial to increase the general understanding of the growth kinetics in these systems. The aim of this work is to develop a model of the crystal growth rate from solution. An extensive literature review of crystal growth focuses on themodelling of growth kinetics and thermodynamics, and new measuring techniques that have been introduced in the field of crystallization. The growth of a singlecrystal is investigated in binary and ternary systems. The binary system consists of potassium dihydrogen phosphate (KDP, crystallizing solute) and water (solvent), and the ternary system includes KDP, water and an organic admixture. The studied admixtures, urea, ethanol and 1-propanol, are employed at relatively highconcentrations (of up to 5.0 molal). The influence of the admixtures on the solution thermodynamics is studied using the Pitzer activity coefficient model. Theprediction method of the ternary solubility in the studied systems is introduced and verified. The growth rate of the KDP (101) face in the studied systems aremeasured in the growth cell as a function of supersaturation, the admixture concentration, the solution velocity over a crystal and temperature. In addition, the surface morphology of the KDP (101) face is studied using ex situ atomic force microscopy (AFM). The crystal growth rate in the ternary systems is modelled on the basis of the two-step growth model that contains the Maxwell-Stefan (MS) equations and a surface-reaction model. This model is used together with measuredcrystal growth rate data to develop a new method for the evaluation of the model parameters. The validation of the model is justified with experiments. The crystal growth rate in an imperfectly mixed suspension crystallizer is investigatedusing computational fluid dynamics (CFD). A solid-liquid suspension flow that includes multi-sized particles is described by the multi-fluid model as well as by a standard k-epsilon turbulence model and an interface momentum transfer model. The local crystal growth rate is determined from calculated flow information in a diffusion-controlled crystal growth regime. The calculated results are evaluated experimentally.

Crystal Growth and Characterization of Li0.9Mo6O17

Purple bronze Li0.9Mo6O17 has attracted researchers for its low dimensionality and corresponding properties. Although it has been studied for nearly two decades, there are still some unsolved puzzles with this unique material. Single crystals of Li0.9Mo6O17 were grown using the temperature gradient flux technique in this research. The crystal growth was optimized by experimenting different conditions and good quality crystals were obtained. X-ray diffraction results have confirmed the right phase of the crystals. Resistivity measurements and magnetic susceptibility measurements were carried out, and anomalous electronic behaviors were found. All of the samples showed the metal-insulator transition near 20K, followed by behavior that differs from sample to sample: either superconducting, metallic or insulating behavior was observed below 2K. Li0.9Mo6O17 was considered as a quasi-one-dimensional crystal and also a superconducting crystal, which implies a dimensional crossover may occur at the metal-insulator transition. A two-band scenario of the Luttinger liquid model was used to fit the resistivity data and excellent results were achieved, suggesting that the Luttinger theory is a very good candidate for the explanation of the anomalous behavior of Li0.9Mo6O17. In addition, the susceptibility measurements showed Curie paramagnetism and some temperature independent paramagnetism at low temperature. The absence of any anomalous magnetic feature near 20K where the resistivity upturn takes place, suggests that a charge density wave mechanism, which has been proposed by some researchers, is not responsible for the unique properties of Li0.9Mo6O17.

Use of an open photoacoustic cell for the thermal characterisation of liquid crystals

In this paper, we describe the use of an open cell photoacoustic configuration for the evaluation of the thermal effusivity of liquid crystals. The feasibility, precision and reliability of the method are initially established by measuring the thermal effusivities of water and glycerol, for which the effusivity values are known accurately. In order to demonstrate the use of the present method in the thermal characterization of liquid crystals, we have measured the thermal effusivity values in various mesophases of 4-cyano-4 - octyloxybiphenyl (8OCB) and 4-cyano-4 -heptyloxybiphenyl (7OCB) liquid crystals using a variable temperature open photoacoustic cell. A comparison of the measured values for the two liquid crystals shows that the thermal effusivities of 7OCB in the nematic and isotropic phases are slightly less than those of 8OCB in the corresponding phases

Use of an open photoacoustic cell for the thermal characterisation of liquid crystals

In this paper, we describe the use of an open cell photoacoustic configuration for the evaluation of the thermal effusivity of liquid crystals. The feasibility, precision and reliability of the method are initially established by measuring the thermal effusivities of water and glycerol, for which the effusivity values are known accurately. In order to demonstrate the use of the present method in the thermal characterization of liquid crystals, we have measured the thermal effusivity values in various mesophases of 4-cyano-4 - octyloxybiphenyl (8OCB) and 4-cyano-4 -heptyloxybiphenyl (7OCB) liquid crystals using a variable temperature open photoacoustic cell. A comparison of the measured values for the two liquid crystals shows that the thermal effusivities of 7OCB in the nematic and isotropic phases are slightly less than those of 8OCB in the corresponding phases

Use of an open photoacoustic cell for the thermal characterisation of liquid crystals

In this paper, we describe the use of an open cell photoacoustic configuration for the evaluation of the thermal effusivity of liquid crystals. The feasibility, precision and reliability of the method are initially established by measuring the thermal effusivities of water and glycerol, for which the effusivity values are known accurately. In order to demonstrate the use of the present method in the thermal characterization of liquid crystals, we have measured the thermal effusivity values in various mesophases of 4-cyano-4 - octyloxybiphenyl (8OCB) and 4-cyano-4 -heptyloxybiphenyl (7OCB) liquid crystals using a variable temperature open photoacoustic cell. A comparison of the measured values for the two liquid crystals shows that the thermal effusivities of 7OCB in the nematic and isotropic phases are slightly less than those of 8OCB in the corresponding phases

Use of mirage effect for the detection of phase transitions in liquid crystals

he phenomenon of single beam mirage effect, otherwise known as photothermal deflection (PTD) effect using a He–Ne laser beam has been employed to detect phase transitions in some liquid crystals. It has been observed that anomalous changes in amplitude occur in the PTD signal level near the transition temperature. The experimental details and the results of measurements made in liquid crystals E8, M21 and M24 are given in this paper.

Laser Induced Photoacoustic Technique for the Detection of Phase Transitions in Liquid Crystals

In this paper we report the use of a laser induced phoroacoustic technique for the detection of multiple phase transitions in heptyl-oxy-cyanobiphenyl (70CB) and octyl-oxy-cyanobiphenyl (80CB) liquid crystals. The observed photoacoustic signal amplitude profile carries clear signatures of two tirst order transitions in 70CB and two tirst order and a second order transitions in 80CB. Analysis of the experimental data using Rosencwaig-Gersho theory shows that the sudden decrease in the photoacoustic (PA) signal amplitude during phase transitions is due to a sharp increase in the heat capacity of the samples near the transition temperatures.

Freezing of 4He and its liquid-solid interface from density functional theory

We show that, at high densities, fully variational solutions of solidlike types can be obtained from a density functional formalism originally designed for liquid 4He . Motivated by this finding, we propose an extension of the method that accurately describes the solid phase and the freezing transition of liquid 4He at zero temperature. The density profile of the interface between liquid and the (0001) surface of the 4He crystal is also investigated, and its surface energy evaluated. The interfacial tension is found to be in semiquantitative agreement with experiments and with other microscopic calculations. This opens the possibility to use unbiased density functional (DF) methods to study highly nonhomogeneous systems, like 4He interacting with strongly attractive impurities and/or substrates, or the nucleation of the solid phase in the metastable liquid.

Detection of polycyclic aromatic hydrocarbons using quartz crystal microbalances

A chemically coated piezoelectric sensor has been developed for the determination of PAHs in the liquid phase. An organic monolayer attached to the surface of a gold electrode of a quartz crystal microbalance (QCM) via a covalent thiol-gold link complete with an ionically bound recognition element has been produced. This study has employed the PAH derivative 9-anthracene carboxylic acid which, once bound to the alkane thiol, functions as the recognition element. Binding of anthracene via pi-pi interaction has been observed as a frequency shift in the QCM with a detectability of the target analyte of 2 ppb and a response range of 0-50 ppb. The relative response of the sensor altered for different PAHs despite pi-pi interaction being the sole communication between recognition element and analyte. It is envisaged that such a sensor could be employed in the identification of key marker compounds and, as such, give an indication of total PAH flux in the environment.