Flexoelectricity in liquid crystals is thought to be due to a coupling between dielectric properties and shape anisotropy of the molecules and described by the fiexoelectric coefficients el and e3. Two experiments are needed to measure el and e3 and it is usual to measure the difference (el - e3) and the sum (el + e3) and then calculate el and e3· The first experiment to measure the difference (el - e3) uses a TN structure with an in-plane applied electric field. Due to the dielectric coupling, the director aligns with the electric field and due to the fiexoelectric effect, the director tilts out of plane. This tilt is measured optically using two laser beams at oblique incidence, e.g. 45°. Using a theoretical model the experimental data is fitted and the difference (el - e3) extracted. The second experiment to measure the sum (el + e3) uses a Pi cell. Applying an ac voltage the transmission through the device is a repeating oscillating signal which contains 1st and 2nd harmonics. The 1st harmonic corresponds to the fiexoelectric effect and the 2nd harmonic to the dielectric effect. Using a lock-in amplifier, the harmonics were measured and the sum (el + e3) extracted using a theoretical model to fit the experimental data. Unfortunately, the data proved the experiment to be unreliable and another method was developed, which uses a BAN cell. The third experiment uses simple pulses in a BAN cell and also measures the sum (el + e3). The big disadvantage of the BAN cell is an internal voltage, which is created by the homeotropic alignment layer and the fiexoelectric polarisation. The internal voltage has the same effect on the director profile as the fiexoelectric effect, which is a big problem in measuring fiexoelectricity. Using a material, which is non ionic and has no fiexoelectricity, the internal bias could be measured and taken into account. Applying short de pulses of opposite sign, the fiexoelectric effect can be observed by the optical response and can be measured. Using these experiments, a number of investigation are being carried out such as the correlation between fiexoelectricity and the molecular structure, ions, elastic properties, molecular orientation, dielectric anisotropy 6E, and order parameter S. The results showed that fiexoelectricity only depends on ions and dielectric properties which was very interesting and surprising at the same time.

>Magister Scientiae - MSc / Photovoltaic (PV) devices based on inorganic-organic hybrid active layers have been extensively studied for over a decade now. However, photoactive hybrid layers of material combinations such as rr-P3HT and SiNWs still require further exploration as candidates for solar cell (SC) fabrication, due to favourable optical absorption and charge carrier mobility associated with them respectively. The ultimate goal of the study is to fabricate ITO/PEDOT:PSS/rr-P3HT:SiNWs/Al SCs with different SiNWs content and investigate the different parameters or factors influencing the performance of these cells. The vertically aligned SiNW arrays on a Si wafer were synthesised via metal assisted chemical etching (MACE) and a method of chemically detaching these wires was developed. The average length and the diameter of the SiNWs obtained were 4.5 μm and 0.2 μm, respectively. Different weight ratios of as-synthesised SiNWs were then incorporated within rr-P3HT to form different hybrid solutions, i.e. rr-P3HT: 0.3 wt% SiNWs, rr-P3HT: 0.7 wt% SiNWs and rr-P3HT: 1.3 wt% SiNWs. In addition, a pure rr- P3HT solution was made for reference purposes. SEM characterisation shows that the SiNWs are randomly distributed across the active area, and that the film becomes progressively inhomogeneous upon addition of SiNWs, whereas the TEM characterisation revealed that there is no chemical interaction between the rr-P3HT and SiNWs. The UV-Vis and PL spectra suggest that there are changes in absorption and emission characteristics upon SiNW incorporation into the rr-P3HT matrix, which may have impacted the charge transfer .The electrical properties of the different hybrid films were probed using Hall Effect measurements, which revealed that the conductivity increases with the increase in the concentration of nanowires (NWs). The increase in conductivity upon the addition of SiNWs in the rr-P3HT matrix was related to an increase of the mobility (μ) of charge carriers in the hybrid films.

Orientador: Augusto Batagin Neto / Coorientador: Francisco Carlos Lavarda / Banca: José Humberto Dias da Silva / Banca: Giovani Fornereto Gozzi / Resumo: O uso de materiais orgânicos em dispositivos optoeletrônicos tornou-se atraente devido a vários fatores, como o baixo custo de obtenção do produto final, bem como a leveza e a flexibilidade dos dispositivos produzidos. Dentre estes dispositivos incluem-se as células eletroquímicas poliméricas emissoras de luz (PLECs). Tais dispositivos eletrônicos emissores de luz orgânicos são compostos de uma blenda entre um polímero semicondutor e um eletrólito contendo um sal e um condutor iônico polimérico. No entanto, alguns dos mecanismos básicos envolvidos na operação destes dispositivos ainda não são completamente compreendidos. De fato, é bem conhecido que interações específicas envolvendo o polímero semicondutor e o sal iônico desempenham um papel importante de transporte de carga, mesmo sem a plena compreensão dos detalhes associados a essas interações. Neste contexto, aqui relatamos uma abordagem teórica que visa desvendar aspectos básicos sobre o assunto. Para tanto, as propriedades estruturais e de reatividade do polímero semicondutor poli [(9,9-dioctilfluorenil-2,7-diil)-co-(1,4-vinilenofenileno)] e do sal triflato de lítio foram avaliados através de cálculos de estrutura eletrônica empregando o Método Paramétrico 3 (PM3) (abordagem semi-empírica) e a Teoria do Funcional da Densidade (usando o funcional de correlação e troca B3LYP e o conjunto de base 6-31G). Para identificar os locais onde as interações polímero-sal ocorrem preferencialmente, cálculos de reatividade local for... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The use of organic materials in optoelectronic devices has become attractive due to several factors, such as the low cost of the final products, as well as the lightness and flexibility of the resulting devices. These devices include polymer light emitting electrochemical cells (PLECs). Such organic light-emitting devices are based on a blend that includes a semiconductor polymer, a salt and an ionic conductor. However, some of the basic mechanisms involved in the operation of these devices are still not completely understood. Indeed, it is well known that specific interactions involving the semiconducting polymer and the ionic salts play an important role in the charge transport, even without the full understanding of the associated details of these interactions. In this context, we report a theoretical approach that aims to uncover basic aspects about the subject. Therefore, the structural and reactivity properties of the semiconductor polymer poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(1,4-vinylenephenylene)] and lithium triflate salt were evaluated via electronic structure calculations employing Parametric Method 3 (PM3) semi-empirical approach and Density Functional Theory (using B3LYP exchange-correlation functional and 6-31G basis set). To identify the sites where polymer-salt interactions occur, local reactivity calculations were performed employing Condensed-to-atoms Fukui Indexes. The obtained results suggest that the presence the salt ions induces significant changes ... (Complete abstract click electronic access below) / Mestre

Based on rst principles calculations the structural, mechanical stability and electronic properties of molybdenum chalcogenides 2H-MoX2 (X = S, Se, Te) have been studied using density functional theory (DFT). The generalized gradient approximation (GGA) proposed by Perdew, Burke and Ernzerhof (PBE) was employed together with the projector augmented plane wave (PAW) method. The van der Waals interactions in the Grimme (DFT-D2) and Lundqvist and Langreth (vdW-DF) approximations have been added on top of PBE or revised PBE in order to take into account the weak interactions between layers of 2H-MoX2 (X = S, Se, Te). The structural properties include the equilibrium lattice parameters, the cohesive energy and the formation energy. Besides we have studied the mechanical stability of these compounds by examining the elastic constants using the PBE, vdW-DF, and DFT-D2 approximations. Other quantities related to the mechanical properties such as the Young's modulus, the Poisson's ratio and the bulk modulus were also calculated. Electronic properties of bulk 2H-MoX2 (X = S, Se, Te) have been investigated using density functional theory (via band structure and projected density of state), and a partially self-consistent GW (GW0) approximation. We have investigated electronic properties ( band structure) for monolayers 1H-MoX2 (X = S, Se, Te) using a single shot GW (G0W0) approximation. Optical properties for monolayer 1H-MoX2 (X = S, Se, Te) were studied using the Bethe-Salpeter equation (BSE).

A dissertation submitted to the Faculty of Engineering and the Built Environment, University of the Witwatersrand, in fulfilment of the requirements for the degree of Master of Science in Engineering 25 May 2017 / Two of the main contributors to high voltage insulation failure are thermal and electrical stresses. The failures may be mitigated by using nanodielectrics. The enhanced effect of nanoparticles in nanodielectrics is attributed to an interaction zone/interphase around each individual nanoparticle between the nanoparticle and host polymer. However, particle clumping or agglomerates are a major challenge in nanodielectric technology. In this work mitigation of the clumping challenges was explored through Rheology in determining optimal particle loading levels. The nanodielectrics studies were Boron Nitride and Carbon Nanospheres in Araldite Epoxy. The rheology results indicated an optimal loading level of 1.09 vol % to 1.35 vol% for Boron Nitride in Epoxy and 0.33 vol% for Carbon Nanospheres in Epoxy. Microscopy, dielectric spectroscopy, electrical tree characterisation, thermal expansion and laser flash analysis were used to validate the efficacy of the rheology results. The results indicated improved properties of the resultant dielectric such as; increased mechanical stiffness, increased electrical resistance and the percolation threshold, partial discharge suppression and increased thermal conductivity at the glass transition temperature. This study has established a rheology-based technique incorporated in the manufacturing process to determine the optimal filler loading of C/Epoxy and BN/Epoxy nanodielectrics. Future work is recommended as investigating either new particle types such as Sulphur hexafluoride in Carbon Nanospheres or mixtures of Carbon Nanospheres and Boron Nitiride. / MT 2017

A dual inclusion strategy for textile polymers has been investigated to increase elastic energy storage capacity of fibers used in high velocity impact applications. Commercial fibers such as Spectra and Dyneema are made from ultra high molecular weight polyethylene (UHMWPE). Dynamic elastic energy of these fibers is still low therefore limiting their wholesale application without a secondary metallic or ceramic component. The idea in this investigation is to develop methodologies so that the elastic energy of polyethylene based fibers can be increased by several folds. This would allow manufacturing of an all-fabric system for high impact applications. The dual inclusion consists of a polymer phase and a nanoscale inorganic phase to polyethylene. The polymer phase was nylon-6 and the inorganic phase was carbon nanotubes (CNTs). Nylon-6 was blended as a minor phase into UHMWPE and was chosen because of its large fracture strain - almost one order higher than that of UHMWPE. On the other hand, CNTs with their very high strength, modulus, and aspect ratio, contributed to sharing of load and sliding of polymer interfaces as they aligned during extrusion and strain hardening processes. A solution spinning process was developed to produce UHMWPE filaments reinforced with CNTs and nylon-6. The procedure involved dispersing of CNTs into paraffin oil through sonication followed by dissolving polymers into paraffin-CNT solution using a homogenizer. The admixture was fed into a single screw extruder for melt mixing and extrusion through an orifice. The extrudate was rinsed via a hexane bath, stabilized through a heater, and then drawn into a filament winder with controlled stretching. In the next step, the as produced filaments were strain-hardened through repeated loading unloading cycles under tension. / Neat and reinforced filaments were characterized through DSC (Differential Scanning Calorimetry), XRD (X-ray Diffraction), Raman Spectroscopy, SEM (Scanning Electron Microscope), and mechanical tests. Phenomenal improvement in properties was found; modulus, strength, fracture strain, and elastic energy increased by 219%, 100%, 107% and 88%, respectively before strain hardening. Once strain hardened the strength, modulus and elastic energy increased by almost one order of magnitude. Source of these improvements were traced to increase in crystallinity and rate of crystallization, formation of microdroplets as a minor phase, sliding between minor and major phases, coating of nanotubes with polymer and alignment of nanotubes. / by Mujibur Rahman Khan. / Thesis (Ph.D.)--Florida Atlantic University, 2010. / Includes bibliography. / Electronic reproduction. Boca Raton, Fla., 2010. Mode of access: World Wide Web.

O objetivo deste trabalho é o de caracterizar o processo de condução do EPDM e de formulações deste material quando nele se incorpora diferentes concentrações de trihidróxido de alumínio (alumina trihidratada). Dois procedimentos experimentais foram utilizados para se obter os resultados: o primeiro utilizando medidas de corrente no estado estacionário variando-se a espessura das amostras, o potencial, o material do eletrodo e a temperatura e o segundo através de medidas da distribuição de cargas elétricas no interior do material empregando o método de propagação de um pulso de pressão. Na análise dos resultados experimentais encontrou-se presença de polarização elétrica e de condução, a qual apresenta dependência linear do logaritmo da condutividade com a raiz do campo, na região de altos campos elétricos. Estudo comparativo de alguns modelos foi realizado sem que nenhum deles explicasse os nossos resultados. Propusemos tentativamente a combinação de efeitos de superfície e de volume. Para o material com crescente concentração de alumina também se encontrou dependência da condutividade com a raiz do campo, mas a interpretação dos resultados ficou mais incerta. Além disto, um efeito quadrático com a concentração de alumina foi encontrado para a polarização e para a condução um efeito linear / This work attempts to characterize the processes of electric conduction in the EPDM copolymer and its composites with several contents of alumina trihydrate filler. Two different experimental procedures were employed: (i) measurements of the steady state electric current for several sample thicknesses, applied voltages, temperatures, and different types of electrode (ii) charge distribution measurements using the pressure wave propagation method. The results showed that there is an electric polarization superimposed to an electric conduction. For high electric fields a linear dependence of the log of the conductivity versus the square root of the electric field was found. Several theoretical models were employed aimed at explaining the experimental results but none gave satisfactory results. It seems that the most adequate model is one in which both surface and bulk processes are considered. When the content of alumina trihydrate filler was increased, a linear dependence between the logs of conductivity against the square root of the electric field was again observed, though the results could not be readily interpreted. It was also found that the electric polarization and the electric conductivity show a quadratic and a linear dependence on the alumina trihydrate content, respectively

Doped electrically conductive polymers are one of the critical materials that have allowed the current technological revolution. Essentially all of today's applications of doped conductive polymers involve vinyl-related polymers. While the application of conductive polymers is rapidly increasing, there is need for additional materials with different electrical behaviors. The current focus is on studying condensation polymers that contain a metal atom and the possibility of undergoing entire chain delocalization of electrons. The different series of organometallic condensation polymers were synthesized by employing interfacial polycondensation technique and characterization of these products were carried out using standard techniques like light scattering photometer, fourier transform infrared spectroscopy (FTIR), matrix assisted laser desorption ionization time of flight mass spectroscopy (MALDI TOF MS) and nuclear magnetic resonance spectroscopy (NMR). The electrical measurements were carried out employing Genrad 1650-B impedance spectroscopy. Prior studies conducted in this area have led to the pathway of looking at two aspects; first, surveying 60 metal-containing polymers that can undergo entire chain delocalization studying the effect of different substituents on their electrical properties and secondly, doping selected candidates employing iodine. The products derived from 2-nitro-1,4-phenylenediamine and N-methyl-1,4- pheneylenediamines with titanocene dichloride exhibited about 10 3 to 10 5 fold magnitude increases in the electrical conductivity on doping with iodine, moving it near conductive region. This increase is dependent on the concentration of the iodine and is cyclic. The results support the starting premise that selected metal-containing condensation polymers can be doped to increase their electrical conductivity. / Further investigation is warranted to see if metal-containing condensation polymers can be important materials in the electronic industry. This research sets the stage for studying not only metal-containing polymeric materials but also to investigate the ability to increase the conductivity of other condensation polymers such as nylons and polyesters through doping. / by Amitabh J. Battin. / Thesis (Ph.D.)--Florida Atlantic University, 2009. / Includes bibliography. / Electronic reproduction. Boca Raton, Fla., 2009. Mode of access: World Wide Web.

Stable and metastable phases of Fe and Al and structural anomalies of Zn and Cd have been studied by epitaxial Bain path (EBP) and minimum path (MNP) first-principles procedures, based on finding equilibrium structures from minimizing the Gibbs free energy G with respect to structure at a given hydrostatic pressure p and temperature T . The main accomplishments are as follows. (1) This dissertation illustrates the effectiveness of the MNP procedure for finding stable and metastable phases of an element by studying four Bravais phases of Fe including body-centered tetragonal (bct), body-centered cubic (bcc), face-centered cubic (fcc) and rhombohedral (rh) phases. The determination of absolute stability using MNP is new; MNP finds all the elastic constants cjj of a given state and the eigenvalues of the elastic constants matrix, which determine the absolute stability of the state. / (2) We have extended our search for stable and metastable phases from zero temperature to finite temperature, which requires the calculations of the Debye temperature Od from cjj in the case of no symmetry. The Debye theory is modified by introducing a parameter B2 that gives the fraction of the full Debye zero-point energy possessed by the actual dispersive mode frequencies. The value of the lattice parameter of fcc Al at low temperatures,a(T) , is shown to be accurately determined by the modified Debye theory of lattice vibrations and first-principles total energy band calculations with the MNP procedure. (3) The existence of structural anomalies in hcp Zn and Cd has been shown from first-principles total-energy calculations using WIEN2k with the EBP procedure. / Evaluation of the pressure dependence of various elastic quantities which are much more sensitive to the anomaly shows that the anomalies in hcp Zn and hcp Cd exist over a considerable range of pressure; several abrupt changes in the electron distribution are thereby indicated in that pressure range. (4) Calculations on the zone-center transverse optical phonon frequencies Vto(p) of hcp Zn, which found oscillatory behavior of Vto(p) in the pressure range of the anomalies, support the conclusions made in (3) on the structural anomalies. Based on this dissertation research four papers have been published in refereed journals. / by Florin Apostol. / Thesis (Ph.D.)--Florida Atlantic University, 2008. / Includes bibliography. / Electronic reproduction. Boca Raton, Fla., 2008. Mode of access: World Wide Web.

by Chu Kin Fung. / Thesis (M.Phil.)--Chinese University of Hong Kong, 1994. / Includes bibliographical references (leaves 73-75). / Chapter 1 --- Introduction --- p.1 / Chapter 2 --- Preliminaries --- p.6 / Chapter 2.1 --- Basic Notations --- p.6 / Chapter 2.2 --- Function Spaces --- p.8 / Chapter 3 --- Examples of Exactly Solvable Cases --- p.19 / Chapter 4 --- Existence and Uniqueness of Solutions --- p.29 / Chapter 5 --- Properties of Solutions --- p.41 / Chapter 6 --- Perturbation Expansion --- p.49