High dielectric constant materials are of technological importance as they lead to the miniaturization of the electronic devices. In this context, the observation of anomalously high dielectric constant (>104) in the body-centered cubic perovskite-related (Space group Im3) material Calcium Copper Titanate ((CaCu3Ti4O12)(CCTO)) over wide frequency (100 Hz – 1MHz at RT) and temperature (100 – 600 K at 1 kHz ) ranges has attracted a great deal of attention. However, high dielectric constant in CCTO is not well understood yet, though internal barrier layer capacitor (IBLC) mechanism is widely been accepted. Therefore, the present work has been focused on the preparation and characterization of CCTO ceramic and to have an insight into the origin of high dielectric constant. Influence of calcination temperature, processing conditions, microstructure (and hence grain size), composition, doping etc on the electrical characteristics of CCTO ceramics were investigated. Electrical properties were found to be strongly dependent on these parameters. The dielectric constant in CCTO was observed to be reduced considerably on substituting La+3 on Ca+2 site. The formation temperature of CCTO was lowered substantially (when compared to conventional solid-state reaction route) by adopting molten-salt synthesis. The dielectric loss in CCTO was reduced by incorporating glassy phases at the grain boundary. Potential candidates for the practical applications such as charge storage devices, capacitors etc, with dielectric constant as high as 700 at 300 K was accomplished in a three-phase percolative composite fabricated by incorporating Aluminium particle into CCTO-epoxy composite. Polycrystalline CCTO thin films with dielectric constant as high as ~ 5000 (1 kHz and 400 K) were fabricated on Pt(111)/Ti/SiO2/Si substrates using radio frequency magnetron sputtering. Effect of sintering conditions on the microstructural, ferroelectric and varistor properties of CCTO and LCTO ceramics belonging to the high and low dielectric constant members of ACu3M4O12 family of oxides were investigated in detail and are compared. Ferroelectric-like hysteresis loop (P vs E) and weak pyroelectricity were observed in CCTO and plausible mechanisms for this unusual phenomenon have been proposed.

This report details the discovery of a method for rhodium catalyzed asymmetric conjugate additions of heteroaryl nucleophiles to α,β-unsaturated carbonyl compounds. This work has successfully employed heteraryl titanates in enantioselective conjugate addition to α,β-unsaturated carbonyl compounds for the first time. Moreover, the utility of benzofuranyl, benzothiophenyl, and pyrrolo zinc reagents has been exemplified in enantioselective conjugate additions. We have found that the precatalyst [Rh(COD)acac]/OMeBIPHEP is broadly effective for enantioselective conjugate additions. Each heterocycle tested exhibited unique reactivity with respect to both conversion and enantioselectivity; reactivities of heteroaryl zinc reagents and heteroaryl titanates in enantioselective conjugate additions to α,β-unsaturated carbonyl compounds are sometimes complementary. Efforts directed towards the development of a method for rhodium-free enantioselective conjugate addition of furan to α,β-unsaturated carbonyl compounds are also described. / text

Thesis (M.S.)--Massachusetts Institute of Technology, Dept. of Materials Science and Engineering, 1982. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND SCIENCE. / Includes bibliographical references. / by Mark V. Parish. / M.S.

Compósitos cerâmicos planares de titanato zirconato de bário, BaTi1-xZrxO3, foram produzidos e os efeitos da quantidade de Zr4+ em suas propriedades funcionais foram estudados. As amostras foram fabricadas pelo método convencional de processamento cerâmico e pela técnica de deposição de fitas cerâmicas a partir de BaTi1-xZrxO3 com x=0, 0,05, 0,1, 0,15 e 0,2 sintetizados pelo método hidrotermal e pelo método dos precursores poliméricos. Foram realizadas caracterizações estrutural (difração de Raios X pelo método do pó e espectroscopia Raman), composicional (espectroscopia por dispersão de energia), microestrutural (microscopia eletrônica de varredura, ensaios de dilatometria) e funcional (permissividade elétrica, coeficiente piezoelétrico d33, coeficiente piroelétrico e histerese ferroelétrica). Além disso, a regra da mistura de fase foi utilizada para prever a permissividade elétrica dos compósitos e as tensões mecânicas internas e seus efeitos na permissividade elétrica e na temperatura de Curie de policristais de BaTiO3 foram simulados. As análises dos dados e as discussões foram realizadas considerando o modelo fenomenológico de Devonshire, a modificação de Forsbergh deste modelo para incluir efeitos de tensões mecânicas bidimensionais e o modelo de policristal tetragonal de BaTiO3 sugerido por Buessem. Os resultados mostram a existência de tensões residuais bidimensionais que surgem após o resfriamento dos compósitos devido às diferenças nos coeficientes de expansão térmica das fases constituintes. Os métodos de obtenção das amostras afetaram o tamanho final dos grãos e as espessuras das interfaces dos compósitos, sendo que, em geral, eles são menores e mais finos nas fitas cerâmicas homogêneas do que nas correspondentes cerâmicas homogêneas. Os compósitos apresentaram deslocamento da Tc para maiores temperaturas e aumento do grau de difusividade da transição. A presença das tensões mecânicas residuais e as características microestruturais, juntamente com os modelos utilizados, explicam qualitativamente a permissividade elétrica obtida. Concluí-se que a quantidade de Zr4+ modifica o comportamento das camadas durante a sinterização e altera o coeficiente de dilatação. Estas mudanças geram tensões mecânicas residuais que afetam a microestrutura e as propriedades funcionais dos compósitos. Portanto, a produção de compósitos cerâmicos ferroelétricos deve considerar a correlação existente entre microestrutura e tensões residuais para que suas propriedades sejam otimizadas. / Planar BaTi1-xZrxO3 ceramic composites had their functional properties investigated. These composites were obtained by the conventional ceramic processing technique and by tape casting technique. Furthermore, BaTi1-xZrxO3 x=0, 0.05, 0.1, 0.15 and 0.2 were synthesized by the polymeric precursors method and by the hydrothermal synthesis to study the synthesis influences and to study the effect of Zr4+ on the functional properties of the composites. Structural characterization (X-Ray powder diffraction and Raman spectroscopy), compositional analysis (energy dispersive X-Ray spectroscopy), microestrutural evaluation (scanning electron microscopy, dilatometry measurements) and functional properties characterization (electrical permittivity, piezoelectric coefficient d33, pyroelectric coefficient and ferroelectric hysteresis) were performed. Furthermore, the composites electrical permittivity was predicted by the simple mixture and the internal mechanical stress distribution and it´s effects on both, electrical permittivity and Curie´s temperature (Tc) of BaTiO3 polycrystals, were simulated. The analyses and discussions were supported by 1- Devonshire´s phenomenological theory, 2- Forsbergh´s modification to Devonshire´s theory to include the two-dimensional stress effects on Tc and 3- Buessem´s BaTiO3 tetragonal polycrystal model. The results show that the sintered composites present two-dimensional residual stresses after cooling due to the constrained sintering of the layers and their thermal expansion coefficient mismatch. The methods of sample preparation led to differences in grain size and interface thickness, with the homogeneous ceramic tapes presenting smaller grain sizes and thinner thickness than the conventional homogeneous ceramics. On the other hand, the composites showed a Tc shift to higher temperatures, a more diffuse phase transition and residual mechanical stresses. Concluding, the Zr4+ substitution of Ti4+ modifies the layer´s sintering behavior and their thermal expansion coefficient. These changes lead to microstructure modifications that affect the functional properties of planar BaTi1-xZrxO3 composites. Thus, the design of ferroelectric composites should take into consideration the correlations between microstructure and residual stresses in order to optimize their functional properties.

No description available.

A new but relatively simple processing study was conducted to investigate the microstructure-property relationships of alumina/aluminium titanate (AAT) composites. The objectives of this study were: (a) to develop a process for fabricating AAT and β-spodumene modified AAT composites using a solid-state reaction method and functionally-graded AAT using an infiltration technique, and (b) to evaluate the effects of dispersed aluminium titanate (AT) on the phase relations, microstructure and mechanical properties of alumina-based composites. The study has revealed that the processing procedures played an important rule in the microstructural development of AAT composites. The microstructure and properties of AAT composites have been found to be strongly influenced by the presence of dispersed AT. The phase relations in the AAT system have been characterised by x-ray diffraction (XRD) and neutron diffraction (ND). Rietveld analysis showed that the AT content increased in proportion with the amount of rutile added. The dynamic ND study showed that AT commenced to form at ~1310°C The presence of AT caused a reduction of hardness but an improvement in fracture toughness. In addition, the presence of AT hindered the processes or kinetics of sintering and densification. The use of β-spodumene has been investigated as a liquid-phase-sintering aid for the densification of AAT composites. XRD, ND, differential thermal analysis (DTA), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Vickers indentation were used to characterise the effect of β-spodumene on the phase relations, densification, microstructure and mechanical properties of AAT composites. The presence of β-spodumene was found to have a profound influence on the phase relations, densification, microstructure and properties of AAT composites. / The addition of β-spodumene caused a small reduction of AT content and a commensurate increase of alumina phase. Functionally-graded AAT composites have been successfully synthesised through infiltration of porous alumina preform with a solution containing TiCl4. The infiltration kinetics of liquid into porous alumina preform has also been investigated and modelled. It was found that the infiltration rate equation proposed by Washburn was proven to be suitable for describing the kinetics of infiltration in terms of preform sintering temperature, viscosity, and multiple infiltrations. The influence of applied pressure was consistent with the model proposed by Travitzky and Shlayen, where the applied pressure enhanced the rate of infiltration. Pre-sintering of alumina preform at 900, 1000 and 1100°C for 2 h resulted in different rates of infiltration which may be attributed to a varying degree in tortuosity of the pore channels. The graded composition character of functionally-graded AAT composites has been determined by XRD and grazing incidence synchrotron diffraction (GISRD). Graded compositions from Rietveld refinement analysis showed that the concentration of AT decreased with depth. In contrast, the α-A12O3 content increased with depth. Microstructural examination by SEM showed that the content of AT grains was the most abundant near the surface and decreased gradually with an increase in depth. The hardness results showed that FGM had a soft graded-region (AT rich) but hard non-graded alumina region. / The lower hardness in the graded region can be attributed to the presence of intrinsically soft AT phase. The presence of graded AT caused a considerable improvement in damage tolerance. The isothermal decomposition of AT at 1100°C both in air and vacuum has been studied. Both ex-situ and in-situ studies have been conducted to examine the effect of environment on the decomposition behaviour of AT. The addition of MgO was effective in enhancing the thermal stability of AT against decomposition both in air and in vacuum.

In this thesis, the a-PMT (amorphous lead magnesium titanate) membranes have been prepared by sol-gel technique as H+ ion sensitive layers. The C-V measurements of the a-PMT/SiO2/Si EIS structures prepared by spin-on coating are used for examining the fabrication parameters and sensing properties. There exhibits the quasi-Nerstain response of 55¡V59 mV/pH in the range of pH 2¡V12, fabricated with the Mg-modified content of 4 mole%, the firing temperature of about 400 ¢J and the thickness of about 0.5

The pyroelectric ceramic thin films and detectors based on PbTiO3[abbreviated to PT] that exhibit a low dielectric constant and a high pyroelectric coefficient, which were fabricated by a sol-gel method in this thesis. The (PVDF/PT) pyroelectric bilayer thin films with low leakage current were deposited on PbTiO3/Pt/SiO2/Si substrates by the spin coating. 1,3 propanediol was used as solvent to minimize the number of cycles of the spin coating and drying processes to obtain the desired thickness of PbTiO3 thin film. By changing the concentrations of PVDF solutions (0.6M~1.0M) and thickness of PVDF thin films (50nm~580nm), the effects of various processing parameters on the bilayer thin films growth and the response of pyroelectric infrared detector device are studied. Experimental results reveal that the thickness of PVDF thin films will influence strongly on dielectricity, ferroelectricity, leakage current and pyroelectricity of (PVDF/PT) bilayer thin films. With the increase of the thickness of PVDF thin films, the relative dielectric constant of (PVDF/PT) bilayer thin films decrease from 63 to 20. The tan£_ increases from 0.00152 to 0.0024, leakage current decreases from 1.54x10-6 A/cm2 to 3.86x10-7 A/cm2, Ec decreases from 70.7 KV/cm to 35 KV/cm, Pr decreases from 6.29 £gC/cm2 to 1.14 £gC/cm2, and £^ decreases from 22.5x10-9 C/cm2K to 6.8 x10-9 C/cm2K with an increase of the thickness of PVDF thin film. In addition, the results also show that the largest figure of merit Fv is 1.31x10-10 Ccm/J as the thickness of PVDF thin film is 80nm. With the increase of the thickness of PVDF thin film, the figure of merit Fm decreases from 2.26x10-8 Ccm/J to 1.07x10-8 Ccm/J. The voltage responsivities (Rv) measured at 20 Hz decrease from 1383 V/W to 804 V/W and the specific detectivities (D*) measured at 100Hz decrease from 2.72x107 cmHz1/2/W to 1.71x107 cmHz1/2/W. From the result of D*/J, the result shows the device possesses the best property as the thickness of the PVDF thin film is 165nm. Therefore, the (PVDF/PT) bilayer thin film with the thickness 165nm of PVDF thin film is the most suitable for the applications of pyroelectric thin film IR detectors.

Hydrogen ion-sensitive field effect transistor with sol-gel-derived La-modified lead titanate gate Department of Electrical Engineering, National Sun Yat-Sen University *Jen-Fu Su **Ying-Chung Chen Abstract In this thesis the amorphous lead lanthanum titanate (Pb1-xLaxTi1-x/4O3, PLT) membrane has been prepared by sol-gel method as a novel pH-sensitive layer. The lead lanthanum titanate membrane was directly deposited on the SiO2(1000Å)/p-Si substrate by spin-on coating to form the PLT/SiO2/Si EIS structure. The C-V measurement was used for examining the fabrication parameters and sensing properties. Moreover, the PLT membrane was grown onto the SiO2 gate ISFET as the PLT/SiO2 gate ISFET. The electrical properties with the different parameter conditions can be obtained by the I-V measurement. Experimental results show that the fabrication parameters and characteristics of the PLT membrane are determined at the La-modified content about 3 mol% and the firing temperature of 400¢J via the EIS structure. There exhibits the pH response of about 44-52 mV/pH in the range of pH 2-12. Furthermore, the nonideal factors, such as drift of 0.1-0.3 mV/h, hysteresis of 2-13 mV and lifetime decay of about 72 mV/pH-day, can be also obtained via the I-V properties of the ISFET. Finally, the hardware architecture of pH measuring system has been built up. The system makes use of constant current and voltage bias technique to ensure that the variations of the output voltage can give directly the variations of pH value. For the purpose of achieving the function of data calibration and driving the liquid crystal display (LCD), the 8051 microprocessor is employed. Keywords: ISFET, Sol-gel, Lead lanthanum titanate, Drift, Hysteresis, pH meter * Student ** Advisor

The processes of development of nuclear weapons resulted in accumulation of thousands of curies of high-level radioactive waste. Liquid waste produced in the US has been stored in carbon steel tanks in highly alkaline (1-3 M NaOH, 6 M sodium salts) media for fifty years and leakage has occurred. One of the approaches to the solution of the problem of radioactive waste is to adsorb the nuclides on highly selective ion-exchange material, solidify in a glass matrix and dispose in a geological formation. The use of the ion-exchange technology is limited by the time of the sorbent-solution contact required to reduce the activity of the streams to acceptable levels. Inorganic ion-exchangers are promising materials due to their high radiation stability, extreme selectivity, and compatibility with the glass matrix. The contact time can be reduced by improving selectivities, kinetics, and capacities of the materials towards the target ions. This can be accomplished in part through understanding of the origin of ion-exchange selectivity. Crystalline zeotypes with minerals sitinakite (ideal formula Na2Ti2O3SiO4??2H2O) and pharmacosiderite (HM3(TO)4(GeO4)x(SiO4)3-x M = Cs+, Na+, K+, T=Nb5+, Ge4+, Ti4+) structures are excellent candidates for selectivity studies because of their ion-exchange properties tunable by alterations of synthetic procedures, and isomorphous framework substitution. The Nb-substitution in titanium sites reduces the framework charge, whereas Ge substitution decreases the unit cell size if in titanium sites and increases if it in silicon sites. The compounds were hydrothermally synthesized in Ti/Si, Ti/Nb/Si, Ti/Ge/Si forms and characterized by structural and ion-exchange studies. The 25% Nb substitution in titanosilicate sitinakite resulted in enhanced selectivity for cesium and additional bond formation of cesium within the channel. The selectivity for cesium in germanium substituted pharmacosiderite also was correlated with the coordination environment within the channel. In the advanced stages of this study semi-crystalline (sodium nonatitanate) and amorphous (monosodium titanate) materials also were considered because of their remarkable strontium selectivity. In situ X-ray diffraction techniques revealed that the sodium nonatitanate precedes the formation of the TS phase in hydrothermal synthesis. This knowledge allowed us to design and synthesize material for combined cesium and strontium removal.