En el presente trabajo se distinguen dos partes claramente diferenciadas, a saber, una primera parte en la que se estudian diferentes sistemas pigmentantes y una segunda parte en la que se estudia la influencia del praseodimio en circonas estabilizadas con calcio, itrio y magnesio.Los sistemas pigmentantes estudiados son el amarillo de Pr-ZrSiO4, el sistema Pr-ZrO2 y el sistema Pr-(Ca-ZrO2). El pigmento amarillo de Pr-ZrSiO4 se estudia el mecanismo de síntesis de dicho pigmento mediante la utilización de métodos de síntesis no convencionales, haciendo énfasis en los procedimientos sol-gel.En el sistema Pr-ZrO2 y Pr-(Ca-ZrO2) se pretende optimizar el pigmento amarillo con dicha red huésped en función de los precursores, métodos y polimorfo de circona estabilizado.El praseodimio no estabiliza a temperatura ambiente la circona cúbica/tetragonal. La circona cúbica estabilizada con óxido de calcio y dopada con praseodimio presenta una coloración amarilla, en la que el praseodimio sustituyendo a un ion estructural: formación de una disolución sólida.En la segunda parte de la tesis se estudia el efecto del praseodimio sobre la estabilización, reactividad y sinterizabilidad de circonas tetragonales y cúbicas estabilizadas en función del método de síntesis: cerámica, coloide, resina de citratos y gel polimérico.En el sistema Pr-(Ca-ZrO2) se siguen dos tratamientos: estabilización-sinterización simultánea y estabilización-sinterización sucesiva. Los resultados indican que para obtener buenos densificados y un adecuado control composicional los mejores polvos son los del tipo citrato o coloide tratados por el procedimiento de estabilización ­sinterización simultánea.En función de lo comentado anteriormente se compararon diferentes sistemas estabilizantes (Ca, Y, Mg) cuando son tratados por el procedimiento simultáneo.Por último, dichos materiales son caracterizados desde el punto de vista mecánico, microestructural y de propiedades eléctricas.

In this work two different solution based methods have been used for synthesis ofoxide-wires and homogeneous heterometallic oxides of transparent conductingmaterials. The first method used is an aqueous chemical growth (ACG) method for synthesis ofmicrorods and nanowires of zinc oxide and tin dioxide useful for detection of toxicgases. No desired films have been obtained but some new interesting structures withnew surfaces at the a,b-plane, especially for zinc oxide where a jagged surface hasbeen observed. For low metal-concentrations of zinc, a band-like structure with 120 °angles has been observed to grow along the a- and b-axis instead of the preferredc-axis. The rod- and wire films have been characterized by SEM and XRD. The other solution-based method used is an inorganic sol-gel type where aheterometallic oxide of 80 mol% zinc and 20 mol% tin manufactured for CIGS solarcells acts as an absorption layer. The alkoxide was prepared by first synthesizing a zincmethoxy-ethoxide solution from diethylzinc and methoxy-ethanol and then mixing itwith tin tert-butoxide to get a heterometallic alkoxide solution. Films and powderhave been prepared either in humidified argon atmosphere or in air and characterizedby SEM, TGA and XRD. The XRD pattern just show the two expected phases of zincoxide and the heterometallic zin-tin oxide which improves the homogeneity of theheterometallic oxide. But the TGA show that some carbonating species formed. This method seems promising for large scale manufacturing of absorption layer toCIGS solar cell for commercially use due to low-cost materials, low temperatures andcheap equipment.

Sol-gel (solution-gelation) method was used to prepare Ni-Ti and Ni-Ti-Al catalysts for reforming of methane with carbon dioxide. This method, after optimizing the parameters such as hydrolysis and acid/alkoxide ratio, is able to make a Ni-Ti catalyst with a surface area as high as 426m2/g when calcined at 473K; but calcination at higher temperature lead to dramatic decrease in surface area. XRD, XPS, TEM and SEM were used to understand this change. Using a packed bed reactor, the catalysts were evaluated with the reforming reaction. It was found that the activity of the Ni-Ti catalyst increases with the Ni loading in the range of 1-10wt%. The reduction temperature has strong effect on activity of the reduced catalyst. Up to 973K, the activity increases with the reduction temperature; but after 973K, the activity decreases and become 0 when the temperature is over 1023K. The Ni-Ti catalyst also deactivated as 15% after 4h of time on stream. The XRD analysis shows that Ti3O5 formed in the catalyst after higher-temperature reduction as well as after the reaction for a period of time. The formation of Ti3O5 may render the catalyst to loss its activity. However, further study is expected to understand the mechanism. TG/DTA analysis shows that both Ni-Ti and Ni-Ti-Al catalysts had carbon deposition; but the latter maintained higher activity in a longer period of time.

A series of sol-gel based photopolymerizable silica glass for holographic storage have been synthesized via a facile chemical design in an effort to overcome the cracking problem incurred during the irradiation stage. The holographic composite material includes a low molecular weight polydimethylsiloxane (PDMS) with end-capped hydroxyl groups, an epoxide-containing coupling agent, a photopolymerizable acrylate monomer, and the sol-gel-derived silica matrix. Inclusion of PDMS provides improved compression stress and strain and toughness over the original unmodified samples, without deterioration on the diffraction efficiency (£b). A plateau value of £b ~ 40 % can be found under a beam power of 5.02 mW. Correlation between the molecular weight of acrylate polymer and £b of the holographic composite material is described and the discrepancies analyzed. The premature saturation of polymerization in the holographic system is attributed to the retarded free radical polymerization within the silica matrix. Minor variation of £b with photoinitiator concentration is observed, indicating that only moderate molecular weight is required for a reasonably high £b. The crack-free mechanism is based on the chemical and physical interactions within the material system. We also investigated the pore size and volume effect for optical properties, especially in studies of diffraction efficiency. With mixing rubber additives, the pore characteristics change via measurement of BET technique. The results indicated that moderate pore size made high diffraction efficiency for porous matrix and some characterizations also were presented. On the other hand, the optical application of this recording medium was described via 3D projected fringes profilometry (PFP) measurement. We recorded coded pattern on medium by employing fiber devices as light source. Using endoscope as image-derived tool, we get double-projected fringe images on tiny object. By PFP technique, a performed retrieved image can be achieved.

A series of photopolymerizable silica for optical storage has been prepared using sol-gel process in this study. The inorganic-organic hybrid materials were based on methacroloxy-propyl-trimethoxysilane (MPTS) and tetraethylorthosilicate (TEOS). Thin films of the hybrids were prepared using spin coating, knife coating, and the closed-mold methods, while the knife coating showing better film flatness and controlled film thickness. Results indicate crack-free polymerizable silica can be obtained using a recipe with 1 wt% photoinitiator. Samples after irradiation shows increased transmittance, suggesting that photopolymerization did take place with the aid of photoinitiators. Spectroscopic study from FTIR indicates C=C conversion in the acrylic part of MPTS reaches 57.51%. The grating period is observed by the optical microscopy. The maximum diffraction efficiency is 48.21%, as obtained from the sample of pure MPTS. From BET measurements, the pore size of the polymerizable silica increases with the increasing amount of MPTS, consistent with the results from measurements of apparent density. Factors affecting the diffraction efficiency are analyzed; these include sample flatness, sample thickness, the conversion of monomer, and concentration of the photoinitiator. Formation mechanism of the periodic grating is proposed based on this study. Addition of MPTS can greatly alleviate problem of phase separation; yet, movement acrylic segment in MPTS is severely limited. On the other hand, samples with more TEOS tend to be densified more with decreased diffraction efficiency

Oligomers of soft and hard segments of unsaturated polyesters (UPE) were synthesized in two steps of esterification. For the hard segment, isophthalic acid was first reacted with 1,2-propanediol, then maleic anhydride was added for further esterification. For the soft segment, diethylene glycol was used to replace 1,2-propanediol. Oligomers of soft and hard segments were blended in different ratios, and then cured with various amount of styrene. Dynamic mechanical and the stress-strain properties of these cured UPEs were evaluated. The results indicated that both stress and strain were above the criteria of the inhibitors when the amount of hard segment oligomer was 30, 60 or 70 wt% of UPE, and the added styrene was 35 or 45 phr relative to UPE. The formula of 30 wt% hard segment, 70 wt% soft segment, and 45 phr styrene was selected for the following studies. Tetraethyl orthosilicate (TEOS) and poly(dimethyl siloxane) were incorporated into the uncured UPE resins via sol-gel process. Then fillers and 5, 10, 15, 20 or 30 wt% of magnesium hydroxide were blended with UPE resins and cured. Self-extinguished phenomenon was observed in the erosion tests when the amount of magnesium hydroxide was equal or higher than 15 wt% relative to UPE. After 101 days of nitroglycerin migration experiments, the migration rate and amount were significantly reduced for these filled specimens compared with the current formula of inhibitors. In addition, 2.5 or 5 phr of phenyl triethoxysilane (PhTES) relative to UPE was added together with TEOS to study the physical properties of the organic-inorganic hybrid materials. When the amount of PhTES was 2.5 phr, it was found that the miscibility between inorganic and organic components improved, and their stress- strain properties also satisfied the criteria of the inhibitors.

The thesis discusses how to utilize Sol-gel method to prepare nano-sized TiO2 films of photoelectrodes and the their use in Dye-Sensitized Solar Cells. The main goal is the study on the production of TiO2 photoelectrodes. When making nano-sized TiO2 films of photoelectrodes, we have to first produce TiO2 sol via the Sol-gel method optical thin films are then made by spin coating. After its spin coating, we study the crystalline phase and morphology of nano-sized TiO2 films of photoelectrodes in terms of two ways: Supercritical drying and oven drying. Among the Dye-Sensitized Solar Cells that are made with different drying methods, owing to higher porosity and surface area, the nano-sized TiO2 films of photoelectrodes made by supercritical drying adsorb more dye molecules and are thus more efficient.

A processing route for development of hydroxyapatite (Ca10(PO4)6(OH)2 or HAp)-titania (TiO2) hybrid coatings on titanium alloy (Ti6Al4V) has been established. HAp powders of different size and morphology were synthesized by aqueous precipitation techniques using different precursor couples and XRD, SEM and FTIR were performed for complete characterization. Hybrid coatings were then prepared via sol-gel by incorporating presynthesized HAp powders into a titanium-alkoxide dip coating solution. Titania network is formed by hydrolysis and condensation of Ti-isopropoxide (Ti[OCH(CH3)2]4) based sols. The effect of titania sol formulation, specifically the effect of organic solvents on the microstructure of the dip coated films calcined at 500 &ordm / C has been investigated. The coatings exhibit higher tendency for cracking when a high vapor pressure solvent, such as ethanol (C2H5OH) is used causing development of higher macroscopic stresses during evaporation of the sol. Titania sol formulations replacing the solvent with n-propanol (CH3(CH2)2OH) and acetly-acetone (C5H8O) combinations enhanced the microstructural integrity of the coating during evaporation and calcination treatments. Sol-gel processing parameters such as multilayer coating application and withdrawal rate can be employed to change the titania thickness in the range of 0.120 - 1.1 microns and to control the microstructure of HAp-titania hybrid coatings. Slower withdraw rates and multi-layer dip coating lead to coatings more vulnerable to cracking. A high calcination temperature in the range of 400 &ordm / C-600 &ordm / C lead to more cracking due to combined effect of densification originated stresses and thermal stresses upon cooling.

The microstructural, electrochemical and optical properties of sol-gel derived tungsten oxide electrochromic coatings have been investigated. Coatings were formed by spinning of tungsten metal based aqueous sol on glass with native ITO layer. Three sol formulations / acetylated peroxotungstic acid (APTA), peroxotungstic acid (PTA) and titanium-doped peroxotungstic acid (Ti-PTA) were employed to obtain 200-300 nm thick multi-layered coatings. Material and electrochromic characterization of the coatings have been performed by DSC, XRD, SEM, cyclic voltammetry and UV-Vis spectroscopy. The electrochromic performance of the WO3 coatings was influenced by calcination temperature, by sol chemistry and by the adsorbed water content. For all sol formulations the coatings calcined at 250 &deg / C were amorphous and have shown better performance compared to crystalline counterparts calcined at 400 &deg / C. High calcination temperature also leads to formation of WO3 nanocrystals for APTA and PTA derived coatings, titanium doping retards crystallization. Presence of acetic acid as in APTA sol improved the electrochromic and electrochemical performance. This was related to removal of organics- acetic acid and peroxo ligands- during calcination, which results in an open W-O network providing more ion insertion sites. The water adsorption affected the electrochromic performance in different ways for the coatings calcined at 250 &deg / C and 400 &ordm / C. The amorphous coatings with limited structural water removal and excessive hydroxyl groups tend to crystallize by condensation of W-OH groups upon storage in open atmosphere, therefore exhibiting degrading electrochromic activity with aging. Conversely, hydroxyl groups enhanced Li+ ion insertion for the stable crystalline coatings calcined at 400 &deg / C.

Indium tin oxide (ITO) thin films were formed on glass substrates by sol-gel method. Coating sols were prepared using indium chloride tetrahydrate (InCl3&bull / 4H2O) and tin-chloride pentahydrate (SnCl4&bull / 5H2O) stabilized in organic solvents (acetylacetone and ethanol). First attempt was to synthesize ITO thin films using standard/unmodified coating sols. The effect of calcination treatment in air (300 &ndash / 600 &deg / C) and number of coating layer(s) (1, 4, 7 or 10) on optoelectronic properties (electrical conductivity and optical transparency), crystal structure and microstructure of ITO thin films were investigated. In addition, single-layer ITO thin films with optoelectronic properties comparable to multi-layered films were prepared by employing organically modified coating sols. Oxalic acid dihydrate (OAD) &ndash / a drying/microstructure control agent&ndash / addition to standard sol formulation was achieved. The rationale was to improve the optoelectronic properties of ITO films through enhancement in microstructure and chemical characteristics upon OAD addition. The effects of OAD content in the sol formulation and post-coating calcination treatment on electrical/optical properties of ITO films have been reported. Finally, the effects of post coating drying temperature (100 &ndash / 200 &deg / C) and time (10 &ndash / 60 min) on optoelectronic and microstructural properties of OAD-modified ITO thin films were discussed. Thin films have been characterized by scanning electron microscopy (SEM), x-ray diffraction (XRD),x-ray photoelectron spectroscopy (XPS), ultraviolet-visible (UV-Vis) spectroscopy, fourier transform infrared (FTIR) spectroscopy, atomic force microscopy (AFM) and four-point probe measurement techniques. It was shown that film formation efficiency, surface coverage and homogeneity were all enhanced with OAD addition. OAD modification also leads to a significant improvement in electrical conductivity without affecting the film thickness (45&plusmn / 3 nm). Highly transparent (98 % transmittance in visible region) ITO thin films with a sheet resistance as low as 3.8&plusmn / 0.4 k&Omega / /sqr have been obtained by employing coating sols with optimized OAD amount (0.75 M). The optimum post-coating drying temperature (100 &deg / C) and drying time (10 min) was also determined for 0.75 M OAD-modified ITO thin films.