O objetivo deste trabalho foi implementar um sistema para a determinação do coeficiente piroelétrico em materiais poliméricos. O método consiste em variar a temperatura da amostra de forma senoidal e medir a corrente em função do tempo. Através do sinal da corrente elétrica e da sua diferença de fase com a temperatura, separa-se a corrente elétrica de origem piroelétrica, a partir da qual se determina o coeficiente piroelétrico. Apresenta-se a caracterização do sistema abrangendo aspectos como o intervalo de temperatura das medidas e amplitude e freqüência da oscilação da temperatura. O método foi empregado para realizar medidas exploratórias com o polímero ferroelétrico poli(fluoreto de vinilideno), PVDF, polarizado pela aplicação de uma rampa de tensão, e com o polímero poli(metacrilato de metila), PMMA, com corante polar, polarizado com o triodo de corona. Nas medidas foram variados os parâmetros do processo de polarização elétrica tais como o campo elétrico máximo e a temperatura / An experimental setup to measure the pyroelectric coefficient of polymers was implemented. The method is based on the measurement of the electric current generated by the sample when its temperature was set to oscillate sinusoidally. Using the measured current and its phase difference related with the temperature thepyroelectric current was obtained, from that the pyroelectric coefficient was determined. It is shown the characterization of the experimental system such as the temperature amplitude and frequency interval of operation. The method was applied in exploratory measurements employing the ferroelectric polymer poly(vynilidene fIuoride), PVDF, poled by a ramp voltage, and the poly(methyl metacrylate), PMMA, having a polar dye, poled with the carona triode. Measurements were performed far different poling conditions such as the maximum applied field and temperature

The crystal structure of caesium permanganate has been determined. CsMn0₄ crystallises in the orthorhombic space group Pnma. There are four molecules per unit cell with a = 10.0692 Å, b = 5.8080 Å, c = 7.9470 Å. The structure was determined by Fourier syntheses on the (010) and (001) projections and refined by two-dimensional difference syntheses. The structure is similar to that of KMn0₄. The manganese is surrounded by four oxygen atoms at an average distance of 1.629 Å arranged in a slightly distorted tetrahedron. The caesium is surrounded by eight manganese atoms at an average distance of 4.381 Å.

O objetivo deste trabalho foi implementar um sistema para a determinação do coeficiente piroelétrico em materiais poliméricos. O método consiste em variar a temperatura da amostra de forma senoidal e medir a corrente em função do tempo. Através do sinal da corrente elétrica e da sua diferença de fase com a temperatura, separa-se a corrente elétrica de origem piroelétrica, a partir da qual se determina o coeficiente piroelétrico. Apresenta-se a caracterização do sistema abrangendo aspectos como o intervalo de temperatura das medidas e amplitude e freqüência da oscilação da temperatura. O método foi empregado para realizar medidas exploratórias com o polímero ferroelétrico poli(fluoreto de vinilideno), PVDF, polarizado pela aplicação de uma rampa de tensão, e com o polímero poli(metacrilato de metila), PMMA, com corante polar, polarizado com o triodo de corona. Nas medidas foram variados os parâmetros do processo de polarização elétrica tais como o campo elétrico máximo e a temperatura / An experimental setup to measure the pyroelectric coefficient of polymers was implemented. The method is based on the measurement of the electric current generated by the sample when its temperature was set to oscillate sinusoidally. Using the measured current and its phase difference related with the temperature thepyroelectric current was obtained, from that the pyroelectric coefficient was determined. It is shown the characterization of the experimental system such as the temperature amplitude and frequency interval of operation. The method was applied in exploratory measurements employing the ferroelectric polymer poly(vynilidene fIuoride), PVDF, poled by a ramp voltage, and the poly(methyl metacrylate), PMMA, having a polar dye, poled with the carona triode. Measurements were performed far different poling conditions such as the maximum applied field and temperature

Leang Po Shan = 利用飛行時間散射反衝符號測量譜儀研究LiTaO3(001)單晶之表面電荷動態特性 / 梁寶珊. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2003. / Includes bibliographical references (leaves 50-51). / Text in English; abstracts in English and Chinese. / Leang Po Shan = Li yong fei xing shi jian san she fan chong fu hao ce liang pu yi yan jiu LiTaO3(001) dan jing zhi biao mian dian he dong tai te xing / Liang Baoshan. / Chapter 1 --- Introduction --- p.1 / Chapter 1.1 --- Ferroelectricity and pyroelectricity of LiTαO3 --- p.1 / Chapter 1.2 --- Surface Studies of Ferroelectrics --- p.5 / Chapter 1.2.1 --- Size Effect and Importantce of Surface Properties --- p.5 / Chapter 1.2.2 --- General Difficulties in Surface Studies of Ferroelectrics --- p.5 / Chapter 1.2.3 --- Applicability of TOF-SARS in the Analysis of Ferro- electrics --- p.6 / Chapter 1.3 --- Surface Charge Dynamics on Ferroelectrics --- p.7 / Chapter 1.3.1 --- Surface Charge Screening of Spontaneous Polarization --- p.7 / Chapter 1.3.2 --- Discharge of Excessive Surface Charge --- p.7 / Chapter 1.4 --- Objectives of the Thesis Work: TOF-SARS Study of Surface Charge Dynamics of LiTαO3 --- p.11 / Chapter 2 --- Ion-Surface Interaction --- p.13 / Chapter 3 --- Time-of-Flight (TOF) Ion Scattering and Recoiling Spectrom- eter --- p.17 / Chapter 3.1 --- TOF Ion Scattering and Recoiling Spectrometer --- p.18 / Chapter 3.2 --- Ion Column --- p.19 / Chapter 3.2.1 --- Ion Source --- p.19 / Chapter 3.2.2 --- Pulsing System --- p.19 / Chapter 3.2.3 --- ExB Wien Filter Mass Analyzer --- p.20 / Chapter 3.2.4 --- Einzel Lens --- p.20 / Chapter 3.2.5 --- Neutral Beam Trap --- p.20 / Chapter 3.2.6 --- Vacuum Chamber and Manipulator --- p.20 / Chapter 3.3 --- Variable Angle Detector --- p.23 / Chapter 3.3.1 --- Setup --- p.23 / Chapter 3.3.2 --- Beam Alignment --- p.24 / Chapter 4 --- Results and Analysis --- p.25 / Chapter 5 --- Study of Charge Relaxation Process --- p.35 / Chapter 5.1 --- Derivation of Surface Electric Potential --- p.35 / Chapter 5.2 --- Data Analysis --- p.40 / Chapter 6 --- Conclusion --- p.49 / Bibliography --- p.50

The performance of a novel micro-thermodielectric power generation device (MTDPG) was investigated in order to determine if thermodielectric power generation can compete with current portable power generation technologies. Thermodielectric power generation is a direct energy conversion technology that converts heat directly into high voltage direct current. It requires dielectric (i.e., capacitive) materials whose charge storing capabilities are a function of temperature. This property is exploited by heating these materials after they are charged; as their temperature increases, their charge storage capability decreases, forcing them to eject a portion of their surface charge to an appropriate electronic storage device. Previously, predicting the performance of a thermodielectric power generator was hindered by a poor understanding of the materials thermodynamic properties and the affect unsteady heat transfer losses have on system performance. In order to improve predictive capabilities in this study, a thermodielectric equation of state was developed that describes the relationship between the applied electric field, the surface charge stored by the thermodielectric material, and its temperature. This state equation was then used to derive expressions for the material's thermodynamic states (internal energy, entropy), which were subsequently used to determine the optimum material properties for power generation. Next, a numerical simulation code was developed to determine the heat transfer capabilities of a micro-scale parallel plate heat recuperator (MPPHR), a device designed specifically to a) provide the unsteady heating and cooling necessary for thermodielectric power generation and b) minimize the unsteady heat transfer losses of the system. The previously derived thermodynamic equations were then incorporated into the numerical simulation code, creating a tool capable of determining the thermodynamic performance of an MTDPG, in terms of the thermal efficiency, percent Carnot efficiency, and energy/power density, when the material properties and the operating regime of the MPPHR were varied. The performance of the MTDPG was optimized for an operating temperature range of 300 500 K. The optimization predicted that the MTDPG could provide a thermal efficiency of 29.7 percent. This corresponds to 74.2 percent of the Carnot efficiency. The power density of this MTDPG depends on the operating frequency and can exceed 1,000,000 W/m3.

This thesis describes the study of the thermal response of the pyroelectric material named lithium tantalate or LT (LiTaO3) in aid of this material's possible use for temperature measurement. The temperature range studied was between 5-99oC. The sensor was excited using a silicon rubber heater. The lithium tantalate sensor and the rubber heater were enclosed such that the temperature would reach steady state faster. The enclosure was a small insulated box in order to reduce any extraneous effects on the sensor. The output signal of the lithium tantalate sensor was then amplified by using four different amplifying circuits and the voltage output was studied. The amplifying circuits included Current Mode, double Current Mode, Voltage Mode, and a modified Wien Oscillator. Results demonstrated linear dependencies of the voltage output as a function of temperature for the Voltage Mode and the modified Wien Oscillator. Using the modified Wien Oscillator amplifying circuit the slope of the line a 2.1mV/oC and for the Voltage Mode the slope was 1mV/oC. For both cases it was found that the range for the standard deviation of the measurements was 0.5< The data showed that the lithium tantalate sensor could be used as a temperature measuring device for the range mentioned above. The resolution of the data is high enough to be able to be detected with modern measuring devices and the standard deviation is low enough to allow for such measurements. Moreover, the linear dependence of the data allows for accurate measurements at each temperature within the range.

The structural origin of the temperature-dependent ferroelectricity in Si-doped HfO₂ thin films is systematically examined. From temperature-dependent polarization-electric field measurements, it is shown that remanent polarization increases with decreasing temperature. Concurrently, grazing incidence X-ray diffraction shows an increase in the orthorhombic phase fraction with decreasing temperature. The temperature-dependent evolution of structural and ferroelectric properties is believed to be highly promising for the electrocaloric cooling application. Magnetization measurements do not provide any indication for a change of magnetization within the temperature range for the strong crystalline phase transition, suggesting that magnetic and structural properties are comparatively decoupled. The results are believed to provide the first direct proof of the strongly coupled evolution of structural and electrical properties with varying temperature in fluorite oxide ferroelectrics.

Field-induced ferroelectricity in (doped) hafnia and zirconia has attracted increasing interest in energy-related applications, including energy harvesting and solid-state cooling. It shows a larger isothermal entropy change in a much wider temperature range compared with those of other promising candidates. The field-induced phase transition occurs in an extremely wide temperature range, which contributes to the giant electrocaloric effect. This article examines the possible origins of a large isothermal entropy change, which can be related to the extremely broad phase transitions in fluorite-structured ferroelectrics. While the materials possess a high entropy change associated with the polar–nonpolar phase transition, which can contribute to the high energy performance, the higher breakdown field compared with perovskites practically determines the available temperature range.

In this thesis, the physical properties of certain multi-functional organic crystals were studied in detail. This study involves the growth of single crystals of Glucuronic acidγ-lactone (GAL), Imidazoliumtartarate (IMLT), (Bis)imidazoliumtartarate (BIMLT), and Diisopropylammonium iodide (DPI) and investigations of their optical, dielectric, piezoelectric, pyroelectric, and ferroelectric properties as a function of temperature and dependence on crystal structure in these organic crystals. Piezoelectric resonance was observed at certain frequencies when dielectric constant was monitored along the b-plate of GAL crystals. The electro-mechanical coupling coefficient estimated at the resonance near 1 MHz frequency revealed an exceptionally large value in GAL similar to that in inorganic lead titanate. The dependence of the piezoelectric resonance frequency on temperature was studied in detail. These crystals showed excellent second- and third-order nonlinear optical properties as well as high laser damage threshold. The high values of χ(2) andχ(3), laser damage threshold, and low UV cut-off makes GAL crystals an interesting prospect for NLO and laser applications. Towards this goal, GAL crystals were studied in detail with regard to determination of directions of dielectric axes, optic axes, and collinear phase-matching. Single crystals of another promising NLO organic crystal, IMLT were also grown which showed interesting dielectric, piezoelectric, and NLO properties. The dielectric dispersion with temperature provided an insight to the polarization mechanisms. Like GAL, IMLT also exhibits piezoelectric resonance. The existence of only one easy axis of vibration in IMLT enabled the candidate to identify the first resonance peak as corresponding to the fundamental mode of oscillation in the sample. This also helped to determine many piezoelectric parameters. By angular phase matching, one direction of phase matching in IMLT was identified. The conversion efficiency of IMLT along this direction was determined which was high in comparison to that in a standard KDP crystal. At piezoelectric resonance frequencies, the electro-optic response due to photo-elastic contributions is enhanced. Single crystals of organic ferroelectric BIMLT were grown by mixing two moles of imidazole with one mole of l-tartaric acid. The controversy with regard to the phase transition temperature of BIMLT was clarified by the DSC and structural analysis in this work. Previously, studies on BIMLT were limited to polycrystalline samples and single crystals with inclusions primarily due to the difficulty in growing good quality single crystals from aqueous solution. However, by experimenting the growth process using different solvents, good quality single crystals were achieved without the trapping of mother solution. This remarkable find is a notable result in these crystals for ferroelectric applications. The mechanism of ferroelectricity in BIMLT is mainly attributed to the transfer of protons along N–H---O hydrogen bonds in the direction of b-axis. Interestingly, the values of spontaneous polarization and Curie-temperature in the organic ferroelectric material DPI were significantly high and comparable to several popular inorganic ferroelectrics. The polarization obtained in this material is the highest among reported organic ferroelectrics. In addition to the high Curie temperature and spontaneous polarization, there were unique phase transitions that were revealed in DPI. The mechanism of ferroelectricity is quite complex, mainly being displacive type on account of the change in orientation of dipoles with electric field. Some contribution to ferroelectricity comes from the order-disorder nature of Nitrogen atom.

In recent years bismuth-based, layer-structured perovskites such as SrBi2Nb2O9 (SBN) and SrBi2Ta2O9 (SBT) have been investigated extensively, because of their potential use in ferroelectric random access memories (FeRAMs). In comparison with non-layered perovskite ferroelectrics such as Pb(Zr,Ti)O3 (PZT), these offer several advantages such as fatigue free, lead free, low operating voltages and most importantly their ferroelectric properties are independent of film thickness in the 90 to 500 nm range. For FeRAM device applications, large remnant polarization (Pr), low coercive field (Ec) accompanied by high Curie temperature (Tc) are required for better performance and reliable operation. Much effort has been made to improve the ferroelectric properties of SBN and SBT ceramics by doping on A or B sites. It was known in the literature that partial substitution of Sr2+ by Bi3+ ions in SBN and SBT would increase the Curie temperature and improve the dielectric properties. The focus of the investigations that were taken up was to improve the electrical, dielectric and ferroelectric characteristics of SrBi2Nb2O9 ceramics. It was reported that the ferroelectric and nonlinear optical properties of LiNbO3 and LiTaO3 could be improved when vanadium, the lightest element in group V of the periodic table is substituted for Nb or Ta along with Li and three oxygens. It is with this background the investigations have been taken up to see whether one can extend the same argument to the Aurivillius family of oxides. Therefore, the central theme of the present investigations aimed at substituting Nb5+ by a smaller cation V5+ in SBN and study its influence on the formation temperature, sinterability, structural and microstructural characteristics apart from its physical properties. Recently the optical properties of this material have been recognized to be important from the optical device point of view. Unfortunately single crystal growth of vanadium doped SBN was hampered because of the bismuth and vanadium loss (high volatility) observed in the process of growth. One of the routes that attracted our attention has been the glass-ceramic. It would be interesting to visualize the behavior of crystallites of nano/micrometer size embedded in a glass matrix as these crystals were known to give rise to exotic properties. One of the crucial steps in the process of fabrication of a glass nanocrystalcomposite system in which crystalline phases have symmetries that would eventually give rise to basic non - centrosymmetric properties such as piezoelectric, pyroelectric and Pockels effects, has been to choose a compatible matrix material associated with easy glass forming capability and the ability to evenly disperse dipolar defects within itself. Recent investigations into strontium borate SrB4O7 (SBO), lithium borate Li2B4O7 (LBO) glasses indicated that LBO by virtue of its favorable structure, thermal and optical properties would form a suitable host glass matrix for dispersing layer structured ferroelectric oxides belonging to the Aurivillius family of oxides. Since lithium borate has wide transmission window, it was worth making an attempt to fabricate optical composite of Li2B4O7 (LBO) and vanadium doped SrBi2Nb2O9 (SBVN) and to study its structural, dielectric, pyroelectric, ferroelectric and optical properties. Therefore the present thesis reports detailed investigations into the effect of vanadium doping on the structural and various physical properties of an n = 2 member of the Aurivillius family of oxides in the polycrystalline form and novel glass composites comprising nano/microcrystallites of this phase. Chapter 1 comprises a brief introduction to the dielectric, pyroelectric, ferroelectric and nonlinear optical properties of materials. In addition to the principles and phenomena, the material aspects of these important branches of physics are discussed. It also forms a preamble to the glasses, criteria for glass formation, glass – ceramics and subsequently ferroelectric and nonlinear optical effects that were observed in glasses and glass - ceramics. Chapter 2 describes the material fabrication techniques adopted to prepare polycrystalline and grain – oriented ceramics, glasses and glass nanocrystalcomposites. The details of various structural, dielectric, pyroelectric, ferroelectric and optical measurement techniques employed to characterize these materials are also included. Chapter 3 discloses the fabrication of strontium bismuth niobate ceramics and their characterization for dielectric and impedance properties. The dielectric properties of strontium bismuth niobate ceramics have been modeled based on Jonscher’s Universal formalism. The coefficients of the Jonscher’s expression, exponent n(T) undergoes a minimum and A(T) exhibits a peak at the Curie temperature, Tc (723K). A strong low frequency dielectric dispersion (LFDD) associated with an impedance relaxation has been found to exist in these ceramics in the temperature range 573 - 823K. The Z′′ of the AC complex impedance showed two distinct slopes in the frequency range 100Hz-1MHz suggesting the existence of two dispersion mechanisms. The exponents m and n were obtained from the curve fitting. The exponent n was found to exhibit a minimum at the Curie temperature, Tc (723K) whereas the m was temperature independent. Chapter 4 deals with the fabrication of vanadium doped SrBi2Nb2O9 ceramics and their characterization for microstructural, dielectric, pyroelectric and ferroelectric properties. The average grain size of the SrBi2Nb2O9 (SBN) ceramic containing V2O5 was found to increase with increase in V2O5 content. The dielectric constant (εr) as well as the dielectric loss (D) increased with increase in grain size (6µm-17µm). The pyroelectric coefficient was found to be positive at 300K and showed an increasing trend with increasing grain size. Interestingly, the SrBi2(Nb0.7V0.3)2O9-δ ceramics consisting of 17µm sized grains showed higher remnant polarization (Pr) and lower coercive field (Ec) than those with grains of 7µm. Chapter 5 deals with the dielectric properties which were studied in detail in the 100Hz to 1MHz frequency range at various temperatures (300 – 823 K) for undoped and vanadium (10 mol%) doped SrBi2Nb2O9 (SBVN10) ferroelectric ceramics. A strong low frequency dielectric dispersion was encountered in these ceramics in the 573 – 823 K temperature range. The dielectric constants measured in the wide frequency and temperature ranges for both the samples were found to fit well to the Jonscher’s dielectric dispersion relations. The dielectric behavior of SBN and SBVN10 ceramics was rationalized using the impedance and modulus data. The electrical conductivity studies of layered SrBi2(Nb1-xVx)2O9-δ ceramics with x lying in the range 0 to 0.3 (30 mol%) were centered in the 573 – 823K temperature range as the Curie temperature lies in this range. The concentration of mobile charge carriers (n), the diffusion constant (D0) and the mean free path (a) were calculated using Rice and Roth formalism. The conductivity parameters such as ion hopping rate (ωp) and the charge carrier concentration (K′) term have been calculated using Almond and West formalism. The afore mentioned microscopic parameters were found to be V2O5 content dependent in SrBi2(Nb1-xVx)2O9-δceramics. Chapter 6 describes the fabrication of partially grain – oriented SrBi2(Nb1-xVx)2O9-δ (0 ≤x≤3.0 in molar ratio) ceramics and characterization for their structural, microstructural, dielectric, pyroelectric and ferroelectric properties. The grain – orientation factor and the microstructural features were studied by XRD and scanning electron microscopy as a fuction of sintering temperature and V2O5 content. The dielectric constant measured along the direction parallel and perpendicular to the pressing axis has shown a significant anisotropy. The pyroelectric and ferroelectric properties were superior in the direction perpendicular to the pressing axis (polar) to that in the parallel direction. The fabrication and characterization details of (100 – x) (Li2B4O7) – x (SrO - Bi2O3 - 0.7 Nb2O5 – 0.3 V2O5) (10 ≤ x ≤ 60, in molar ratio) glasses and glass nanocrystal composites are dealt within Chapter 7. The nanocrystallization of strontium bismuth niobate doped with vanadium (SrBi2(Nb0.7V0.3)2O9-δ(SBVN)) has been demonstrated in Li2B4O7 glasses. The glassy nature of the as – quenched samples was established by differential thermal analyses (DTA). The amorphous nature of the as – quenched glasses and crystallinity of glass nanocrystal composites were confirmed by X – ray powder diffraction studies. High resolution transmission electron microscopy (HRTEM) of the glass nanocrystal composites (heat – treated at 783K/6h) confirm the presence of nano rods of SBVN embedded in Li2B4O7 glass matrix. Chapter 8 presents the physical properties of the glasses and glass nanocrystal composites. Dielectric constant of both the as – quenched and glass nanocrystal composites was found to increase with increase in the composition, whereas the loss was observed to decrease with increasing SBVN composition. Different dielectric mixture formulae were employed to analyze the dielectric properties of the glass nanocrystal composite. The electrical behaviour of the glasses and glass nanocrystal composites was rationalized using impedance spectroscopy. The observed pyroelectric response and ferroelectric hysteresis of these composites confirmed the polar nature. Various optical parameters such as optical band gap (Eopt), Urbach energy (∆E), refractive index (n), optical dielectric constant (ε′∞) and ratio of carrier concentration to the effective mass (N/m*) were determined. The effects of composition of the glasses and glass nanocrystal composites on these parameters were studied. Transparent glasses embedded with nanocrystallites of SBVN exhibited intense second harmonic signals in transmission mode when exposed to IR laser light at λ = 1064 nm. The thesis ends with a summary of the important findings and conclusions.