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[pt] Partículas que apresentam dois lados com propriedades químicas distintas são chamadas de Janus, como uma referência ao deus de duas faces da mitologia Romana. A combinação de propriedades diferentes em um mesmo sistema vem se demonstrando interessante para inúmeras aplicações. Neste trabalho, nanopartículas de ouro anfifílicas foram sintetizadas através do recobrimento seletivo dos hemisférios do núcleo metálico, por dois polímeros, sendo um hidrofóbico e outro hidrofílico. Em seguida, foi realizado o crescimento preferencial de dióxido de titânio apenas na face com recobrimento hidrofílico. Os resultados obtidos pela caracterização estrutural e físico-química confirmaram a formação de nanopartículas de ouro com um hemisfério recoberto por dióxido de titânio de baixa cristalinidade e alta porosidade, provando seu caráter Janus. As nanopartículas Janus obtidas foram testadas como fotocatalisadores para produção de gás hidrogênio a partir da água. Os resultados mostraram sua atividade superior em relação a nanopartículas formadas apenas por titânia. Portanto, este estudo descreve uma nova estratégia para obtenção de nanopartículas Janus, que podem ser utilizadas para diferentes aplicações, e ainda demonstra sua importância nas áreas de catálise e de produção de gás hidrogênio como combustível renovável. / [en] Particles possessing two sides with different chemical properties are named Janus, as a reference to the double-faced god of Roman mythology. The combination of two different properties in the same system has been showing interesting for numerous applications. In this work, amphiphilic gold nanoparticles were synthesized by selectively coating the metallic nucleus hemispheres with two polymers, one hydrophobic and one hydrophilic. Then, a preferential growth of titanium dioxide over the hydrophilic face was performed. The results obtained by structural and physicochemical characterization confirmed the formation of gold nanoparticles with one hemisphere coated by titanium dioxide with low crystallinity and high porosity, proving the Janus character. The obtained Janus nanoparticles were tested as photocatalysts for hydrogen production from water. Results showed the superior activity in comparison to nanoparticles comprised only by titania. Thus, this study describes a new strategy to obtain Janus nanoparticles, which can be used for different applications and also demonstrates their importance in the fields of catalysis and production of hydrogen gas as renewable fuel.

The atomic layer deposition (ALD) growth of titania thin films was studied for the infiltration of silica photonic crystals. Titania thin films were grown in a custom-built ALD reactor by the alternating pulsing and purging of TiCl4 and water vapor. The conformal nature of ALD growth makes it an ideal candidate for the infiltration of the complex opal structure. Titania is a high refractive index material, which makes it a popular material for use in photonic crystal (PC) applications. Photonic crystals are periodic dielectric structures that forbid the propagation of light in a certain wavelength range. This forbidden range is known as the photonic band gap (PBG). A refractive index contrast of at least 2.8 is required for a complete PBG in an inverted opal structure. Therefore, the rutile structure of titania is more desirable for use in PCs due to its higher index of refraction than the anatase or brookite structure. The growth mechanisms and film properties of the TiO2 thin films were studied. Investigation of the growth mechanisms revealed saturated growth rate conditions for multiple temperature regions. Film characterization techniques included XRD, SEM/EDS, XPS, AFM, reflectivity, and index of refraction measurements. Post growth heat treatment was performed to study the conversion from the as-deposited crystal structure to the rutile structure. After optimization of the deposition process, the infiltration of silica opals for PC applications was attempted. The filling fraction was optimized by increasing the pulse and purge lengths at a deposition temperature of 100oC. Although the silica opals were successfully infiltrated using ALD of TiO2, the long range order of the PC was destroyed after the heat treatment step required to achieve the high index rutile structure.

A fabricação e a caracterização de eletrólitos compósitos Nafion - TiO2, e seu uso em células PEM (Proton Exchange Membrane) operando em temperaturas elevadas (~ 130 ºC) foram estudados. A operação em altas temperaturas da célula PEM traz benefícios, como o aumento da cinética das reações eletródicas, o aumento da cinética de transporte difusional nos eletrodos e o aumento da tolerância da célula ao contaminante monóxido de carbono. O Nafion ®, eletrólito polimérico comumente empregado em células PEM, possui condutividade elétrica dependente da quantidade de água contida em sua estrutura. Desta forma, o aumento da temperatura de operação da célula acima de 100 ºC causa a desidratação do polímero diminuindo acentuadamente sua condutividade elétrica. Para aumentar o desempenho dos eletrólitos operando em altas temperaturas, eletrólitos compósitos (Nafion-TiO2) foram preparados pelo método de conformação por evaporação em molde. A adição de partículas higroscópicas de titânia (TiO2) na matriz polimérica visa melhorar as condições de umidificação do eletrólito em temperaturas elevadas. Três tipos de partículas de titânia com diferentes áreas de superfície específica e formas distintas foram investigados. Compósitos à base de Nafion com adição de 2,5 a 15% em massa de partículas de titânia com forma aproximadamente esférica e com área de superfície específica de até ~115 m2g-1 apresentaram maiores valores da temperatura de transição vítrea do que o polímero. Este aumento melhora a estabilidade do eletrólito durante a operação de células a combustível PEM em 130 ºC. Os compósitos formados a partir da adição de nanotubos derivados de titânia apresentaram pronunciado ganho de desempenho e maior estabilidade térmica em operação de células acima de 100 ºC. Neste caso, a elevada área superficial e a forma dos nanotubos de titânia contribuíram significativamente para o aumento da absorção e da retenção de água do compósito. Por outro lado, as curvas de polarização mostraram um aumento na polarização por queda ôhmica com o aumento da concentração das partículas cerâmicas adicionadas. A morfologia do polímero não foi alterada com a adição de partículas inorgânicas, portanto, o desempenho dos compósitos reflete uma competição entre a adição de uma fase isolante, que diminui a condutividade elétrica, e o aumento da estabilidade térmica ou da retenção de água do compósito. Os eletrólitos compósitos testados provaram serem promissores na aplicação em células PEM em temperaturas acima de 100 ºC. / The fabrication and characterization of Nafion - TiO2 composites, and the use of such electrolytes in PEM (Proton Exchange Membrane) fuel cell operating at high temperature (130 °C) were studied. The operation of a PEM fuel cell at such high temperature is considered as an effective way to promote fast electrode reaction kinetics, high diffusional transport, and high tolerance to the carbon monoxide fuel contaminant. The polymer Nafion® is the most used electrolyte in PEM fuel cells due to its high proton conductivity. However, the proton transport in Nafion is dependent on the water content in the polymeric membrane. The need of absorbed water in the polymer structure limits the operation of the fuel cell to temperatures close to 100 °C, above which Nafion exhibits a fast decrease of the ionic conductivity. In order to increase the performance of the electrolyte operating at high temperatures, Nafion-TiO2 composites have been prepared by casting. The addition of titania hygroscopic particles to the polymeric matrix aims at the enhancement of the humidification of the electrolyte at temperatures above 100 °C. Three types of titania particles with different specific surface area and morphology have been investigated. Nafion-based composites with the addition of titania nanoparticles, in the 2.5-15 wt.% range, with nearly spherical shape and specific surface area up to ~115 m2g-1 were found to have higher glass transition temperature than the polymer. Such an increase improves the stability of the electrolyte during the fuel cell operation at high temperatures. The addition of titania-derived nanotubes results in a pronounced increase of the performance of PEM fuel cell operating at 130 °C. In this composite, the high specific surface area and the tubular shape of the inorganic phase are responsible for the measured increase of both the absorption and retention of water of the composite electrolyte. Nonetheless, the polarization curves of fuel cell using the composite electrolytes exhibited an increase of the ohmic polarization associated with the addition of the insulating titania particles. As the chemical structure of Nafion was observed to be insensitive to the addition of the inorganic particles, the high performance of the composite electrolytes is a result of competing effects: the decrease of the electrical conductivity and a higher thermal stability or water absorption/retention capacity. The experimental results suggest that the Nafion-TiO2 composites are promising electrolytes for PEM fuel cells operating at temperatures above ~100 °C.

In this work we have explored the possibility of using surfactant/polyelectrolyte complexes as templates to synthesize inorganic mesostructured materials mainly with a film morphology. Inorganic species deposit in those regions of the films which are filled with a polymer hydrogel, surrounding the arrays of ordered surfactant micelles. This method produced thick robust films where the inorganic regions are reinforced and functionalized by the polymer, thus these materials are expected to have potential applications in separation, absorption, catalysis and chemical sensing. Initial work involved mixing silicate precursors directly into CTAB/PEI solutions to form highly ordered 2D hexagonal silica films at the air/water interface. Time resolved synchrotron SAXS allowed investigation of processes occurring in solution during the reaction, from which a film growth mechanism was proposed. Films had good thermal properties and after post-synthesis TMOS vapour treatment, retained structure upon template removal. Silica gel monoliths with various mesostructures were also rapidly fabricated in one minute with surfactant/LPEI complexes. Cat-ionic surfactant mixtures with polymers were also employed to template silica films with different cubic mesostructures at the air/water interface. The mesophases of the interfacial films were enriched due to more complicated interactions between the polymers and two surfactants. Polymer molecular weight, total composite concentration, chemical nature of the polymer as well as the cationic-anionic surfactant molar ratio was used to systematically control the silica film mesophase. Robust titania films were also prepared with cat-anionic surfactant mixtures and polymers at the air/water interface. Although the film mesostructure was lost after calcination, the in-situ and dry free-standing films display ordered cubic mesostructures and the films are stable to calcination after post-synthesis treatment. Ordered lamellar iron oxide films templated by SDS/LPEI complexes were also prepared at the air/water interface.

"The phase content and grain size of titanium dioxide often have a strong influence on properties for a variety of applications. In many cases it would be desirable to produce the stable rutile phase with an ultra-fine particle size (<10nm), but most low temperature synthesis methods produce predominantly the metastable anatase phase. The anatase-rutile transformation in TiO2 is known to be affected by dopant type and concentration, as well as the titanium precursor used in solution chemical synthesis. Recently, use of cavitation in the synthesis process has been shown to yield smaller grain size for a variety of oxides. However, the relative importance of these synthesis variables on the grain size and phase content of TiO2 is not well understood. In this study, Taguchi analysis was used to determine the relative effects of dopants (Sn), titanium precursor (butoxide, sulfate, chloride), and cavitation power on grain size and phase content. Precursor residuals were also measured by analytical chemistry. Grain size and phase content results were analyzed statistically to determine whether there is a size dependence of the anatase-rutile transformation. Results show that grain size is strongly dependent on the concentration of chlorine. Absent chlorine, a definite grain size-phase content correlation exists; rutile content increases as grain size decreases. An L-4 orthogonal Taguchi analysis shows chlorine content and tin content as the major influences on the final product. With minimum grain size and maximum rutile content being considered optimal, our best result was 100% rutile and an average grain size of 5nm, which was achieved by acoustic synthesis with 3% tin dopant and low residual chlorine. "

Sedimentation is one of many characterization tools used to test materials in nanotechnology. Characterization of settling behavior is complex as there are many variables which can affect sedimentation. In our research, we focused on sedimentation in colloidal systems with the aid of an optical turbidometer. Nanoparticles of CeO2 (Ceria Oxide) and TiO2 (Titanium Dioxide) are embedded onto a polymeric matrix of a thermally responsive microgel of poly(N-isopropylacrylamide) (PNIPAM) and interpenetrating chains of poly(acrylic acid) to create novel composites. The composites are loaded with the inorganic oxide nanoparticles at different weight percent from a low value of 10 weight % to 75 weight %. The loading of the colloidal particles affects the sedimentation rate. In this thesis a turbidomenter is used to characterize the settling rate, which is an important characteristic for application of these new composites. TiO2 is a key constituent in many industrial products; cosmetics, paints, ceramics and used in waste water remediation. It is a potent photocatalyst which breaks down almost any organic compound when exposed to ultraviolet light. By combining nanoparticles of TiO2 with microgels of a polymer, the composites can facilitate use and recovery of the catalyst. Gravity settling of these loaded composites provides an easy separation of TiO2 nanoparticles. In this context, characterization of settling plays an important role. CeO2 composites are used to polish oxide coatings in the semiconductor industry and sedimentation of the composite particles is important as it can affect the efficiency of the planarization process. Therefore, measuring sedimentation of these composites is necessary. In this study, the settling behavior is measured optically for a variety of conditions that differ in loading of inorganic nanoparticles within the microgels, temperature of the solution, and concentration of particles in solution. The overall goal is to understand the sedimentation behavior of these novel composites and facilitate their use in industrial processes.

Biomass-fed cogeneration units and waste incinerators have the advantages of producing efficiently heat and power and of reducing the amount of CO2 emitted per produced energy. However, they produce toxic polychlorinated VOCs (dioxins), CO and NOx. This thesis aims at developing a catalytic system for the total oxidation of chlorinated VOCs that: i) convert efficiently chlorinated VOCs below 250 °C and ii) resist to the exhaust co-pollutants (H2O, CO, NOx). Moreover, this thesis aims at having a complete understanding of the catalytic mechanism. Part I demonstrated that VOx/TiO2 based catalysts are very efficient in the total oxidation of chlorobenzene (taken as a model molecule). In particular, they proved to be highly resistant against deactivation. Moreover, Part I established that the addition of secondary phases producing VOx-WOx/TiO2 or VOx-MoOx/TiO2 induces a synergetic effect that improves the performances. Furthermore, the replacement of a classical TiO2 by a sulfated one improves the catalytic activity. In Part II, the investigation of the co-pollutants influence on the catalysts performances demonstrated their quite good resistance. Indeed, the presence of CO does not induce any deactivation of the catalysts while NOx induces a huge improvement of the catalysts ability to destroy chlorinated VOCs. This beneficial effect is explained by the in situ production of a strong oxidant (NO2) that speeds up the reoxidation of the reduced VOx sites. Nevertheless, H2O vapor can affect negatively the catalyst activity when present in a high concentration. Part III, by revisiting catalytic and characterization results exposed in Part I and II, demonstrated that the catalytic mechanism proceeds in four steps: i) adsorption of chlorinated VOCs on Brønsted sites, ii) VOx redox sites give some of their lattice oxygen atoms to oxidize the aromatic ring producing H2O and COx, iii) reoxidation of the VOx reduced sites thanks to the gas stream oxidant (O2) and iv) retrieving of the chlorine from the surface. The second and third steps compose a Mars and van Krevelen mechanism and the third one is the mechanism rate limiting step. Our work shows that the performances can be improved by tuning the redox properties of the VOx phases: i) improvement of the reducibility and ii) stabilization of the vanadium oxidation level above a limit value, estimated around 4.87.

El control dels nivells d'oxigen és una etapa crítica en molts processos industrials.En alguns d'aquests, els nivells d'oxigen han de ser detectats i controlats fins i tot en el rang de les ppm. Encara que ja es coneguin molts mètodes, ja provats per a la detecció d'oxigen, la majoria d'ells són costosos i complexes. Altres mètodes més accessibles com els sensors Lambda i les cel·les electroquímiques també presenten alguns problemes. Els primers requereixen d'elevades concentracions d'oxigen o bé de controls de temperatura força precisos amb la finalitat de treballar sense interferència d'altres gasos. Els segons es poden veure afectats per temps d'exposició massa perllongats a gasos "àcids" com el diòxid de carboni i no es recomana el seu ús en atmosferes amb un contingut de més del 25% d'aquests gas.Són moltes les avantatges dels sensors de gasos: baix cost, mida reduïda i solidesa entre d'altres. Això fa que aquests dispositius despuntin com a solució per a la detecció d'oxigen. Molts autors han fet esment a la detecció d'oxigen a nivells de ppm emprant aquests tipus de sensors. De totes formes, la majoria s'han desenvolupat mitjançant tecnologia de capa fina. En aplicacions industrials, la tecnologia més usada és la de capa gruixuda, ja que aquests sensors són més fàcils de fabricar i de dopar que els de capa fina. En el cas dels sensors de capa gruixuda la detecció de traces d'oxigen és una tasca encara difícil i es necessita treballar a elevades temperatures (> 700 ºC).El mecanisme de detecció d'oxigen en els sensors basats en òxids semiconductors es basa en la interdependència de la conductivitat elèctrica d'aquests òxids i la pressió parcial d'oxigen en l'ambient. El diòxid de titani és l'òxid semiconductor que més s'usa en la detecció d'oxigen. Els sensors basats en òxid de titani (en fase cristal·lina rutil) necessiten d'elevades temperatures per a un correcte funcionament (700 ºC-1000 ºC), ja que la detecció d'oxigen en la fase rutil es deu principalment a la difusió dels ion d'aquests gas en el volum del material. Per a que es produeixi la reacció en el volum o propi cos del material es necessiten elevades temperatures. Això comporta un consum també elevat de potència, que a la llarga serà un problema en determinades aplicacions industrials.Al tenir l'òxid de titani en fase anatasa més electrons lliures, la reacció de l'oxigen amb aquests material es pot associar a una reacció superficial. Aquesta reacció es pot donar a temperatures més baixes, al voltant dels 400 ºC-500 ºC i per tant, mantenir la fase anatasa en l'òxid permet disminuir la temperatura de treball, la qual cosa és desitjable per al disseny del sensor.Tal i com es reflecteix en algunes referències bibliogràfiques, en dopar l'òxid de titani amb ions pentavalents com el Nb5+, aquests ions s'introdueixen en l'estructura cristallina de l'òxid de titani en fase anatasa, creant certa tensió interna que provoca una resistència al canvi de fase anatasa a rutil, inhibint el creixement del gra.Per altra banda, també s'ha posat de manifest en moltes fonts que el dopatge d'òxid de titani amb niobi augmenta la sensibilitat d'aquests material vers l'oxigen. Aquests dopatge fa que l'òxid presenti una impedància menor, per la qual cosa es facilita el disseny de l'electrònica associada al sensor.Tenint en compte aquestes dues premisses, un dels objectius d'aquesta tesi ha estat la síntesi, mitjançant la tècnica del sol-gel, de diferents tipus d'òxid de titani per a la fabricació d'un sensor d'oxigen que operi en una marge de temperatura relativament moderat (300 ºC-600 ºC). Es treballà amb òxids sense dopar i amb òxids dopats amb un 3 % de niobi.Cadascun es calcinà a diferents temperatures: 600 ºC, 700 ºC, 800 ºC i 900 ºC.Amb l'objectiu de correlacionar l'estructura i la sensibilitat i selectivitat dels òxids sintetitzats, aquests es van sotmetre a diferents tècniques de caracterització. En primer lloc l'espectrometria de plasma acoblada inductivament (ICP) s'utilitzà amb el fi de determinarne la composició química i quantificar la proporció de cada component. En segon lloc també es va fer servir la difracció de raigs X (XRD) per a determinar les fases cristallines de l'òxid i la mida dels cristalls. També es va analitzar la porositat i es van fer mesures de l'àrea superficial (BET) dels nanopols . En darrer lloc, la microscopia d'escàner d'electrons (SEM) fou aplicada amb la finalitat d'obtenir detalls de l'estructura de la capa activa i de la grandària dels grans. Per a l'anàlisi quantitatiu i també qualitatiu de les capes s'utilitzà l'espectroscopia de dispersió d'energia per raig X (EDS).Com a substrat, es va desenvolupar un substrat d'alúmina que pot albergar quatre capes actives treballant a una mateixa temperatura, conformant així una matriu de sensors.Treballant amb aquests substrat aparegueren certs inconvenients (relacionats amb l'encapsulat del sensor) operant a temperatures superiors als 450 ºC. Això comportà un retard en l'obtenció de resultats amb aquests substrat i es decidí introduir-ne un de nou, resistent a altes temperatures i adquirit en l'Institut Kurchatov (Moscou, Rússia). Tots els resultats presentats en aquesta tesi es van obtenir amb l'ús d'aquests últim substrat. En l'actualitat s'està treballant amb el primer d'ells.Un cop fabricat els sensors, es provà la sensibilitat d'aquests en un sistema de flux continu. Es provaren tres diferents concentracions: 20 ppm d'O2 amb balanç de N2, 30 ppm d' O2 amb balanç CO2 i 15 ppm d'O2 amb balanç CO2. També es testaren les respostes dels sensors cap a altres gasos interferents (SO2, CH4, H2S i C2H4) per a determinar la selectivitat d'aquests sensor vers l'O2 en presència d'interferents.La millor resposta vers l'oxigen s'aconseguí amb els sensors dopats i calcinats a 700 ºC. Aquesta millora es pot atribuir al dopatge amb niobi. Aquets metall inhibeix el creixement del gra i per tant s'aconsegueixen òxids amb major àrea superficial. Un altre motiu pot ser el retard del pas de la fase rutil a la fase anatasa induït també pel dopatge de Niobi.La sensibilitat denotada pels òxids dopats amb niobi i calcinats a 600 ºC fou molt baixa tot i que en principi aquests òxids presentaven característiques físiques potencialment millors que els calcinats a 700 ºC. Aquests fet es pot explicar degut a la presència d' alguns depòsits de carboni que no es pogueren eliminar durant la calcinació. La presència d'aquests dipòsits fou confirmada per l'anàlisi Raman d'aquests materials. Les estructures de carboni presents en aquests residus cobreixen gran part de la superfície de l'òxid i contribueixen a la desactivació del procés catalític que té lloc en aquesta superfície.Concernint a les mesures realitzades sota atmosfera de CO2, els òxids dopats amb niobi i calcinats a 700 ºC també respongueren a l'oxigen. La resposta en el cas de 15 ppm d'O2 s'invertí del tipus oxidant a tipus reductor. A baixes concentracions d'oxigen els ion CO- provinents de la dissociació del CO2 s'adsorbeixen a la superfície del material actiu.L'oxígen, enlloc de deplexionar-se, interactua amb aquests ions per a formar CO2, alliberant electrons a la capa activa i això fa que la natura de la resposta sigui reductora. Les respostes vers altres gasos contaminants com SO2, CH4, H2S foren tipus reductor com era esperat, la qual cosa indicava que el canvi de resposta no era atribuïble al canvi de l'òxid conductor de tipus n a tipus p, si no més aviat en un canvi en la naturalesa de la reacció.Amb l'objectiu de millorar la sensibilitat de l'òxid dopat es provà d'incrementar la seva àrea superficial i porositat utilitzant un surfactant com a motlle durant el procés de síntesi. El surfactant usat fou la dodecilamina, que forma una estructura miscel·lar que fa de motlle en el procés de nucleació de l'òxid, generant així grans menors amb major àrea superficial i major porositat. De tres diferents temptatives, els millors resultats es varen obtenir quan s'addicionaven 8 ml de dodecilamina a la solució del sol-gel immediatament desprès de la hidròlisi dels alcòxids. Les proves XRD mostraren que l'addició del surfactant retarda encara més la transició de les fases rutil a anatasa i també inhibeix el creixement dels cristalls. Aquests resultats es recolzen sobre les micrografies del SEM i l'anàlisi BET, que revelaren un creixement en la porositat del material i un gra menor. Malgrat aquests resultats prometedors en la determinació estructural, les mesures de l'oxigen amb aquests sensors revelaren una poca sensibilitat dels sensors modificats amb el surfactant. Els espectres RAMAN mostraren alguns pics corresponents a diferents morfologies de carboni.Els dipòsits d'aquests material en la superfície, tal i que com s'ha mencionat anteriorment, inhibeixen la resposta de la capa activa vers l'oxigen. / El control de los niveles de oxígeno es una etapa crítica en muchos procesos industriales. En algunos de estos procesos, los niveles de oxígeno deben ser detectados y controlados incluso en el rango de las ppm. Aunque existen varios métodos ya probados para la detección de oxígeno en estos sistemas de control, la mayoría de ellos son costosos y complejos. Otros métodos de detección más accesible como los sensores Lambda o las celdas electoquímicas también presentan problemas: los primeros requieren de altas concentraciones de oxígeno, o de controles de temperatura bastante precisos para poder trabajar sin interferencias de otros gases Los segundos pueden verse afectados por una prolongada exposición a gases "ácidos" como el dióxido de carbono y no se recomienda para uso continuo en atmósferas con un contenido de mas del 25 % de dicho gas.Debido a muchas ventajas tales como su bajo costo, tamaño reducido y solidez, los sensores basados en semiconductores aparecen como una solución para la detección de oxígeno. Algunos autores han reportado la detección de oxígeno a niveles ppm empleando este tipo de sensores. Sin embargo, la mayoría de ellos han sido desarrollados mediante tecnología de capa fina. En aplicaciones industriales, la tecnología más usada es la de capa gruesa, ya que estos sensores son más fáciles de fabricar y de dopar que los sensores de capa fina. En los sensores de capa gruesa, la detección de trazas de oxígeno es aun una tarea difícil de alcanzar, siendo normalmente necesarias altas temperaturas (> 700 ºC) para lograrlo.El mecanismo de detección de oxígeno en los sensores basados en óxidos semiconductores esta basado en la fuerte dependencia de la conductividad eléctrica de estos materiales a la presión parcial de oxígeno en el ambiente. El dióxido de titanio es el óxido semiconductor más ampliamente usado en la detección de oxígeno. Los sensores basados en TiO2 (usualmente en la fase cristalina rutilo) necesitan trabajar a elevadas temperaturas (700 ºC - 1000 ºC), ya que la detección de oxígeno en la fase rutile se debe principalmente a la difusión de los iones de oxígeno en el volumen del material. Para que se produzca la reacción en el volumen hacen falta altas temperaturas, lo que conlleva un alto consumo de potencia que puede ser un handicap en determinadas aplicaciones industriales.Por otro lado, el dióxido de titanio en fase anatase posee más electrones libres, así que la detección de oxígeno en este material puede asociarse a una reacción de superficie, la cual tiene lugar a no tan altas temperaturas (400 ºC - 500 ºC).Por lo tanto, puede concluirse que mantener la fase anatase permitiría la detección de oxígeno a temperaturas moderadas, lo cual es deseable para el diseño del sensor.Se ha reportado que cuando el TiO2 es dopado con iones pentavalentes, i.e. Nb5+, tales iones se introducen en la estructura cristalina de dicho óxido en estado anatase, obstruyendo la transformación de dicha fase a rutile, inhibiendo el crecimiento del grano.También se ha reportado que el dopado con niobio aumenta la sensibilidad del dióxido de titanio hacia el oxígeno. El óxido dopado también presenta una impedancia más baja a temperaturas de trabajo menores, por lo que se facilita el diseño de la electrónica asociada al sensor.Basándonos en estos puntos, uno de los objetivos de esta tesis fue la síntesis, mediante un proceso de sol-gel, de diferentes tipos de dióxido de titanio para la fabricación de un sensor de oxígeno que opere en un margen de temperaturas moderado (300 ºC - 600 ºC). Para ello se desarrollaron óxidos dopados con un 3 % de niobio y óxidos sin dopar.Cada uno de ellos fue calcinado a diferentes temperaturas: 600 ºC, 700 ºC, 800 ºC y 900 ºC.Con el objetivo de correlacionar la estructura y la sensibilidad y selectividad de los óxidos sintetizados, estos se sometieron a diferentes técnicas de caracterización. La espectroscopia de Plasma Acoplado Inductivamente (ICP) fue empleada para determinar la composición química de las muestras y cuantificar la porción de cada componente. La Difracción de Rayos-X (XRD) fue usada para establecer las fases presentes en la estructura cristalina del material y para determinar el tamaño el tamaño de los cristales en cada material. Se realizaron medidas de área BET con los nanopolvos para conocer el área superficial y la porosidad de cada material. La Microscopia de Escáner de Electrones (SEM) fue aplicado para obtener detalles de la estructura de la capa y del tamaño de las partículas.Para hacer un análisis cuantitativo y cualitativo de las capas se utilizó la Espectroscopia de Dispersión de Energía por Rayos -X (EDS).Para realizar las medidas, se desarrolló un substrato de alúmina para ser usado en el sensor de oxígeno. Este substrato puede soportar cuatro capas activas trabajando a la misma temperatura formando una matriz de sensores. Sin embargo, debido a algunos problemas relacionados con el encapsulado del substrato cuando las temperaturas de trabajo sobrepasaban los 450 ºC, su empleo para el sensor de oxígeno se retrasó y los resultados obtenidos con el mismo no estaban lo suficientemente completos para ser presentados en este trabajo. Para solventar la necesidad de un substrato que pudiese resistir altas temperaturas para aplicaciones de detección de oxígeno, se introdujo un nuevo substrato adquirido en el Instituto Kurchatov (Moscú - Rusia). Los resultados expuestos en este trabajo se obtuvieron con este último substrato.Una vez fabricados los sensores, las capacidades de sensado de los materiales fueron probadas. La sensibilidad hacia el oxígeno fue medida en tres situaciones diferentes: 20 ppm de O2 en balance de N2, 30 ppm y 15 ppm de O2 en balance de CO2. Las respuestas de los sensores hacia otros gases contaminantes (SO2, CH4, H2S y C2H4) también fueron probadas para observar la influencia de dichos gases en el proceso de detección de oxígeno.La mejor respuesta hacia el oxígeno se consiguió con los sensores basados en materiales dopados calcinados a 700 ºC. Esto puede atribuirse a los iones de niobio que inhiben el crecimiento del grano y por lo tanto producen un aumento del área superficial de dichos materiales, que beneficia al mecanismo de detección, y a su fase cristalina, mayoritariamente anatase, la cual permite la detección a las temperaturas deseadas (300 ºC - 600 ºC). Las especies de niobio también contribuyen al proceso de catálisis.Otro motivo puede ser la fase cristalina, mayoritariamente anatase, la cual permite la detección a las temperaturas deseadas (300 ºC - 600 ºC).Por otro lado, los materiales dopados calcinados a 600 ºC tuvieron una pobre respuesta, a pesar de que estos tienen mejores características físicas que los calcinados a 700 ºC. Este hecho puede explicarse por la presencia de algunos depósitos de carbono, residuales del proceso de síntesis, que no pudieron ser eliminados durante la calcinación. La presencia de estos depósitos fue confirmada mediante los análisis Raman de estos materiales.Ya que estas estructuras de carbono cubren gran parte de la superficie del material, y que además son poco catalíticas, el resultado es una desactivación de la catálisis.Concerniente a las medidas realizadas en atmósfera de CO2, los óxidos dopados con niobio y calcinados a 700 ºC también respondieron al oxígeno. Sin embargo, la respuesta hacia 15 ppm de oxígeno presentó una inversión de tipo oxidante a tipo reductora. A bajas concentraciones de oxígeno, los iones de CO-, provenientes de la disociación del CO2, se adsorben en la superficie del material activo. El oxígeno, en lugar de deplexionarse, interactúa con estos iones para formar CO2, liberando electrones a la capa activa, dando lugar así a una respuesta reductora. Por otra parte, las respuestas hacia otros gases contaminantes tales como H2S, SO2 y CH4 fueron de tipo reductora, como era esperado, lo cual indica que el cambio de respuesta no puede atribuirse al cambio del óxido conductor de tipo n a tipo p, sino más bien a un cambio en la naturaleza de la reacción.Para mejorar la sensibilidad de los óxidos dopados, se intentó incrementar su área superficial y porosidad usando un surfactante como plantilla o molde durante el proceso de síntesis. El surfactante empleado fue dodecylamina, la cual forma una estructura micelar que hace de molde durante el proceso de nucleación del óxido, generando así granos menores con mayor área superficial y mayor porosidad. Entre tres diferentes intentos, los mejores resultados se obtuvieron cuando 8ml de dodecylamina fueron agregados a la solución del sol-gel inmediatamente después de la hidrólisis de los alkóxidos. Los análisis de XRD de este material mostraron que la adición de surfactante retarda aun más la transición de fase de anatase a rutile y también evita el crecimiento de los cristalitos. Estos resultados son soportados por las microfotografías de SEM y los análisis BET, los cuales mostraron un retardo en el crecimiento del grano y un incremento del área superficial. El área BET también evidenció un incremento de la porosidad del óxido. Sin embargo, los resultados de las medidas de oxígeno revelaron una pobre respuesta de los sensores basados en el óxido en cuestión. Los espectros Raman de este material mostraron algunos picos correspondientes a carbono con diferentes morfologías. Como fue explicado previamente, estos depósitos de carbono retardan la respuesta de este óxido al oxígeno. / Control of oxygen levels is a critical step in many industrial processes. In some of these processes, levels of oxygen must be detected and controlled even in ppm range.Although there are several probed methods for oxygen detection in these control systems, most of them are expensive and complex. More accessible methods as Lambda sensors or electrochemical cells present also problems: first ones need high concentration of oxygen, or an extremely accurate temperature control, to work without interference from other gases.Second ones may be affected by prolonged exposure to "acid" gases such as carbon dioxide and it is not recommended for continuous use in atmospheres which contain more than 25% of CO2.Due to many advantages as low cost, small size and robustness, semiconductor sensors appear as a good solution for oxygen detection. Some authors had reported detection of oxygen at ppm levels employing this kind of sensors. However, most of them were made through thin film technology. For industrial applications, the most usual technology is thick film, because it is easier to fabricate and to dope than thin film sensors. For thick film sensors, detection of traces of oxygen is still a very difficult goal to reach and usually high temperatures (>700 ºC) are needed.The basic oxygen sensitivity mechanism of oxygen sensors based on semiconductor oxides is their strong dependencies of electrical conductivity on oxygen partial pressures.Titanium dioxide is the semiconductor material most widely used for oxygen detection.Titania (usually rutile crystalline phase) based sensors need to work at high temperatures (700 ºC - 1000 ºC), since oxygen detection in rutile state is mainly due to diffusion of oxygen ions in the bulk of the material. For bulk reaction it is necessary to work at these high temperatures, leading to high power consumption, which is not desirable for electronic applications.On the other hand, anatase state Titania has more free electrons. So, oxygen detection can be associated to surface reactions, which take place at not so high temperatures (400 ºC - 500 ºC). Then, it can be derived that maintaining an anatase structure would allow the detection of oxygen at medium temperatures, which is desirable for sensor design.It had been reported that when Titania is doped with pentavalent impurity ions, i.e. Nb5+, such ions get into the anatase Titania crystalline structure, giving rise to a hindering in the phase transformation to rutile and an inhibition in grain growth. It has been also reported that Nb-doped Titania shows higher sensitivity towards oxygen than pure TiO2. The doped material also shows lower impedance at low operating temperatures and hence, it is easier to design associated electronic circuitry.In this work pure Titania and Niobium doped Titania nanopowders were synthesized by a simplified sol-gel route. Based on the literature, the doping concentration in doped materials was set to Nb/Ti = 3 at%. In order to set the crystalline structure of the active materials, they were calcined at four different temperatures: 600 ºC, 700 ºC, 800 ºC and 900 ºC.The obtained materials were characterized by different techniques. The objective of these characterizations was to obtain information about the material structure that could be related to its detection properties. Inductively Coupled Plasma (ICP) spectroscopy was employed to determine the chemical composition of the samples and quantify the amount of each component. X-ray Diffraction (XRD) was used to establish the phases present in the crystalline structure of the material and to determine the size of the crystallites in each material. Area BET measurements were done to nanopowders to know the surface area and the porosity of each material. Scanning Electron Microscopy (SEM) was used to obtain details on the film structure and the grain size. To make quantitative and qualitative analysis, Energy-Dispersive X-ray Spectroscopy (EDS) was also applied.For the measurements, an alumina substrate was developed to be used in the oxygen sensor. This substrate can support four active layers working at the same temperature forming a sensor array. However, due some problems related with the substrate package at working temperatures above 450 ºC, the use of this substrate for oxygen sensor application was delayed and the results obtained whit it were not complete enough to be presented in this work. In order to resolve the necessity of a substrate that can resist high working temperatures for oxygen sensing applications, it was introduced a new substrate acquired from the Kurchatov Institute (Moscow-Russia). The results exposed in this work were obtained by using this last substrate.Using these substrates, the sensing capabilities of the materials were also tested. The sensitivity toward oxygen was measured under three different conditions: 20 ppm of O2 in N2 balance, 30 ppm and 15 pmm of O2 in CO2 balance. The sensors responses toward other pollutant gases (SO2, CH4, H2S and C2H4) were also tested in order to see the influence of such gases in the oxygen detection process.The best response toward oxygen was achieved in those sensors based on Nb-doped materials calcined at 700 ºC. This may be attributed to the niobium ions which hinder the grain growth and hence give rise to a high surface area that benefits the detection mechanism. The good response may be also attributed to the crystalline phase, mostly anatase, which allows the detection at desire temperatures (300 ºC - 600 ºC).On the other hand, the doped materials calcined at 600 ºC had a poor response, in spite of they have better physical characteristics than doped materials calcined at 700 ºC.This problem was mainly related to some carbon deposits detected in these materials trough Raman analyses. Such carbon deposits may be residual of the synthesis process, which could not be eliminated during the calcination. Since these carbon structures cover a great part of the material surface, and they are also poorly catalytic, the result is a deactivation of the catalysis.Concerning to the measurements carried out under CO2 atmosphere, Nb-doped Titania calcined at 700 ºC also responded to oxygen. However, the response toward 15 ppm of oxygen presented an inversion from oxidative type to reductive type. At low oxygen concentrations, the CO- ions from CO2 disassociation are adsorbed on the active material surface. The oxygen, instead deplexing, interacts with these ions forming CO2, liberating electrons to the active layer giving rise to a reductive type response. On the other hand, the responses toward other pollutant gases such H2S, SO2, C2H4 and CH4 were of reduction type, as they were expected, which support the idea that the change in the response type is not due to the change in the physics of the semiconductor oxide from n type to p type, but to a change in the reaction nature.In order to improve the sensing capabilities of doped materials, it was attempted to increase their surface area and porosity by using a surfactant as a template during the synthesis process. The surfactant employed was dodecylamine, which forms a micellar structure that works as template in the nucleation process of the oxide, generating small grains with higher surface area and porosity. Among three different attempts, the best results were obtained when 8 ml of surfactant were added to the sol-gel solution just after the hydrolysis of the metal alkoxides. XRD analyses of this material showed that the addition of surfactant retards even more the phase transition from anatase to rutile and also hinder the crystallites growth. These results were supported by SEM micrographs and BET analysis, which show a hinder in grain growth and an increase of the surface area. Area BET also evidences an increment of the material porosity. However, the results of the oxygen measurement reveal a poor response of the considered material. The Raman spectroscopy of this oxide shows some peaks that correspond to carbon with different morphologies. As it was explained before, these deposits of carbon retard the response of this material toward oxygen.

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.