Submitted by Johnny Rodrigues (johnnyrodrigues@ufcg.edu.br) on 2018-03-23T19:48:20Z No. of bitstreams: 1 JOCIELYS JOVELINO RODRIGUES - TESE PPGEQ 2015..pdf: 2539318 bytes, checksum: 88878182929175962ca411ac34f42556 (MD5) / Made available in DSpace on 2018-03-23T19:48:20Z (GMT). No. of bitstreams: 1 JOCIELYS JOVELINO RODRIGUES - TESE PPGEQ 2015..pdf: 2539318 bytes, checksum: 88878182929175962ca411ac34f42556 (MD5) Previous issue date: 2015 / Capes / Este trabalho teve como objetivo, desenvolver peneiras moleculares utilizando fontes de sílica convencional (TEOS) e alternativa (cinza da casca de arroz), utilizá-las como suportes para catalisadores de Cobalto destinados à síntese de FischerTropsch, e também, investigar o efeito da introdução de rutênio como promotor na reação acima mencionada. Preparou-se a SBA-15 a partir de um gel com composição molar: 1.0 FONTE DE SÍLICA: 0.017 P123: 5.7 HCl: 193 H2O. Os catalisadores foram preparados pelo processo de impregnação úmida utilizando solução de 0,1 M de (Co(NO3)2.6H2O). Na sequência, foi incorporado o promotor rutênio usando solução aquosa de 0,1M de Cloreto de Rutênio (RuCl3xH2O). As amostras foram caracterizadas por DRX, EDX, TG/ATD, MEV, MET, RTP e adsorção física de N2. A reação de Fischer-Tropsch foi conduzida em reator leito de lama durante 6 horas de reação a 240oC e pressão de 20 bar, utilizando uma relação molar H2/CO = 1. A obtenção da SBA-15 utilizando fontes de sílica convencional e alternativa pôde ser confirmada pelos difratogramas, com destaque para a SBA-15 obtida com a fonte alternativa cinzas da casca de arroz, resíduo agrícola produzido em longa escala e que praticamente não tem aplicação comercial. Os difratogramas dos catalisadores na faixa angular de 0-8º mostraram que após a impregnação dos metais e calcinação, não ocorreram modificações na estrutura hexagonal dos materiais mesoporosos, observando-se os picos principais da fase do SBA-15. As análises de adsorção física de N2 das peneiras moleculares SBA-15 (CCA) e SBA15 (TEOS), mostram isotermas com perfil do tipo IV e histerese H1, características de materiais mesoporosos. As análises térmicas das peneiras moleculares SBA-15 (TEOS) e SBA-15 (CCA) indicaram a eliminação do direcionador (Pluronic) no processo de calcinação. As áreas superficiais específicas dos catalisadores diminuem e o volume de poro varia, devido ao bloqueio parcial dos poros pelo cobalto e pelo promotor rutênio, mas a estrutura da peneira molecular SBA-15 não é alterada. Os perfis de RTP dos catalisadores das séries Co/SBA-15 e Ru/Co/SBA-15 permitiram verificar a presença de picos distintos que pode ser causado pela redução dos óxidos de cobalto. A MET mostrou espécies de cobalto na forma esférica com tamanho de 20 nm, e após a co-impregnação com rutênio, houve uma melhor dispersão dessas espécies de cobalto resultando em partículas menores com tamanho médio de 10 nm. Os resultados obtidos a partir da síntese de FischerTropsch pelos catalisadores, apresentaram altas seletividades a hidrocarbonetos C5+ de alto valor agregado, bem como, verificou-se que a co-impregnação do promotor rutênio no catalisador Co/SBA-15, favoreceu o aumento da seletividade para hidrocarbonetos C5+ e diminuiu a seletividade para metano, com destaque para o desempenho do catalisador 20%Co/0,5%Ru/SBA-15 preparado com as cinzas da casca de arroz. / The aim of this work was to prepare the mesoporous molecular sieve SBA-15 using conventional silica sources (TEOS) and alternative (Ash rice husk) and uses them as support for cobalt catalysts for the Fischer-Tropsch process. And investigate the introduction of ruthenium as a promoter. It was prepared SBA- 15 from a gel of molar composition : 1.0 silica source : 0.017 P123 : 5.7 HCl : 193 H2O. The catalysts were prepared by wet impregnation process using 0.1 M solution (Co(NO3)2.6H2O) (Vetec). Following ruthenium promoter was incorporated using 0.1 M aqueous solution of ruthenium chloride (RuCl3xH2O). The samples were characterized by XRD, EDX , TG/DTA, SEM, TEM, TPR and adsorption of N2. The Fischer-Tropsch reaction is conducted at 240 °C , pressure of 20 bar using a molar ratio H2/CO = 1, on a slurry reactor for a reaction time of 8 h. Obtaining the SBA -15 silica using conventional sources and alternative could be confirmed by X ray diffraction , with emphasis on the SBA -15 obtained with the alternative source of rice husk ash , a residue of agriculture abundant and cheap that is usually discarded. The XRD patterns of the catalysts in the angular range 0-8º showed that after impregnation and calcination of the metal changes did not occur in the hexagonal structure of mesoporous materials , observing the main peaks of the phase of SBA -15. The physical adsorption of N2 analysis of SBA -15 molecular sieves (CCA) and SBA -15 (TEOS) show with type IV isotherm profile and H1 hysteresis characteristics of mesoporous material. The thermal analysis of SBA -15 molecular sieves (TEOS) and SBA -15 (CCA) indicated the elimination of the template (Pluronic) in the calcination process. The specific surface areas of the catalysts decreases , and the pore volume changes due to partial blockage of the pores by cobalt and ruthenium promoter, but the structure of SBA -15 molecular sieve is not changed. TPR profiles of the catalysts of the series Co /SBA- 15 and Ru /Co /SBA -15 evidenced the presence of distinctive peaks that can be caused by the reduction of cobalt oxides. TEM showed cobalt species on spherical 20 nm in size, and after co- impregnation with ruthenium was a better dispersion of these cobalt species resulting in particles with average size smaller than 10 nm. The results obtained from the Fischer- Tropsch the catalysts showed high selectivity to hydrocarbons C5+ of high value, and it was found that co- impregnation of the ruthenium promoter in the Co catalyst /SBA -15 promoted the increase of selectivity to C5+ hydrocarbons and decreased the selectivity to methane, highlighting the performance of the catalyst 20 % Co/0.5 % Ru/SBA-15 prepared with the ashes of the rice husk .

Multifunctional superparamagnetic iron oxide nanoparticles (SPIONs) coated with silica are a promising research field for lots of biomedical applications. The scope of this work is a preparation of SPIONs and coating them with silica to form core-shell structured nanoparticles for nanomedicine applications. SPIONs were synthesized by two chemical methods – co-precipitation and thermal decomposition of organic iron precursor. Prepared nanoparticles were carefully characterized –average size, size distribution, morphology, crystallinity, colloidal stability and magnetic properties were studied. After comparing SPIONs synthetized by two routes the most suitable method for biomedical applicable nanoparticles preparation is determined. The nanomedicine requires nanoparticles of the highest quality. The next step was coating SPIONs with silica shell. For this purpose inverse microemulsion method was chosen. TEOS was used as a silica precursor. Mean size, size distribution, magnetic properties, structure of silica shell were studied.

Incontinence diapers or disposable absorbent pads provide essential help to people having such a physical difficulty. However, during prolonged used of these products in daily life, the skin inside pad area may get fragile and damaged which are difficult to recover in old ages. Therefore a skin friendly sensor can be added to the inner layer of pad that would monitor the skin condition and signal any abnormalities to the wearer. Smart materials which can change color upon variation of skin pH were incorporated with synthetic nonwoven layers of the pad. Among various incorporation methods of these materials, ‘sol-gel’ coating technique was found to be successfulfor applications on optical sensor and on fewother fabric types. Thus ‘sol-gel’ method with modified recipe for different dye and chemical combinations were experimented in this project.Several developed samples showed color change (e.g. yellow to red) that can be easily detected by wearers’ eyes.Additionally, the methods and materials involved showed no adverse effect on health and environment. Thus this study succeeds to provide with a mean for skin health monitor based on nonwoven textiles by incorporation of color changing materials.

Das Ziel der Arbeit „The Technological improvement of Portuguese pinewood by chemical modification” bestand darin, die Charakteristiken des Holzes der See-Kiefer (Pinus pinaster Ait.) und den Einfluss der chemischen Modifizierung hinsichtlich des Widerstandes gegen Meeresorganismen, sowie ihrer physikalischen und mechanischen Eigenschaften zu untersuchen. Vier Modifizierungstypen wurden getestet: 1,3-Dimethylol-4,5-dihydroxyethylen-Harnstoff (DMDHEU), N-Methylol-Melamine (MMF), Tetra-alkoxysilane (TEOS) und Wachs. Diese Arbeit besteht aus zwei Teilen: eine vorläufige und eine Haupt-Studie. In ersterer wurde eine Vielzahl von Materialeigenschaften untersucht - physikalische und mechanische Eigenschaften und ihre Wechselwirkungen. Besonderes Augenmerk wurde auf die Resistenz gegenüber Meeresorganismen gelegt, wobei die Rolle der Härte, der Form der Proben sowie der Toxizität der Chemikalien untersucht wurde. Im zweiten Teil der Arbeit wurde eine ausführliche Studie zum Thema Kriechen durchgeführt. Art und Grad der Modifizierung wurden in Abhängigkeit von der Belastung, von verschiedenen Umgebungsbedingungen und vom mechano-sorptiven Effekt evaluiert. Obwohl die Steifigkeit nicht signifikant verschieden war, traten Unterschiede in den anderen Eigenschaften auf. Einerseits waren die Anti-Quellungs-Effizienz und Steifigkeit-Stabilisierung erhöht. Andererseits waren die Bruchschlagarbeit und die Gleichgewichtsfeuchte signifikant durch Zellwand-Modifizierung (DMDHEU und MMF-Harz) reduziert, wobei eine enge Wechselbeziehung zwischen letzteren Variablen beobachtet wurde. Unter hohem Belastungsgrad oder unter dem Einfluss des mechano-sorptiven Effekts war für das modifizierte Holz mit Zellwandreaktion (DMDHEU and MMF) das Ausmaß des Kriechens geringer als das des unmodifiziertem Holzes. Für beide Arten von Harz wurde das relative Kriechen deutlich verringert, trotz unterschiedlicher Veränderungen in der Ausgleichsfeuchte, Steifigkeit Stabilisierung und Festigkeit. Die Anti-Kriech-Effizienz zeigte eine enge Korrelation mit der Abnahme der Gleichgewichtsfeuchte, der Anti-Quell-Effizienz und der Steifigkeits-Stabilisationseffizienz. Die lumen-füllende Modifizierung mit TEOS-Lösung hatte weder einen Einfluss auf den Kriech-Faktor noch auf die Gleichgewichtsfeuchte und die Steifigkeits-Stabilisationseffizienz. Bei den Meerwasseruntersuchungen waren die wichtigsten Schlussfolgerungen, dass die Härte und die Form der Proben keinen Einfluss auf die Resistenz gegenüber einem Befall durch die Meerwasser-Bohrschädlinge (Limnoriden und Terediniden) haben. Lumen-füllende Modifizierungen (TEOS und Wachs) hatten keine Wirkung hinsichtlich der Resistenz gegen Meerwasser-Bohrschädlinge. Hölzer, die mit Kondensationsharzen (DMDHEU und MMF) modifiziert waren, waren von einem Befall mit Limnoriden nicht betroffen. Aber nur DMDHEU mit einem Minimum an Modifizierung war geeignet, um einen Befall durch Terediniden über eine Expositionsdauer von 3 Jahren zu verhindern. Die Verwendung von modifiziertem Holz als Baumaterial für nicht-tragende Bauteile wie Anwendungen in Feuchträumen, Wandfassaden oder Gartenmöbeln ist bekannt. Diese Untersuchung unterstützt die Ausweitung seiner Anwendung für tragende Bauteile, besonders wenn das Design durch die Möglichkeit von Deformation bestimmt wird, die seine Funktionsfähigkeit einschränkt. Deshalb müssen das Versprödungsverhalten, insbesondere bei der Zellwand-Modifizierung mit DMDHEU, und die Designmöglichkeiten für mechanische Verbindungen bestimmt werden, um die Anwendungsmöglichkeiten des modifizierten Holzes als tragende Komponente auszuweiten, bei denen oft der Grenzzustand der Tragfähigkeit das Design der strukturellen Komponenten bestimmt.

[EN] ABSTRACT In this Doctoral Thesis, the author carried out the biological evaluation of new silicon-based hybrid (organic-inorganic) coatings, synthesized by sol-gel route, used as osseointegrator and osteoinductor coatings applied to titanium radicular prosthesis in the dental implantology field. The biological evaluation of the new coatings consisted of a complete study to determine the effect of the coatings in the osteoblastic cell line and the tissular effects after the in vivo implantation in rabbit tibia (foreign-body reaction response and osseointegration), by histological study. The biological characterization was complemented with a physicochemical characterization of the materials, determining their topography, wettability, surface reactivity, as well as their degradation rate and silicon delivery, to explain the biological behaviour that each material induced. The coatings that showed a better cell behaviour were selected as material candidates for the in vivo implantation phase. This part of the work consisted of two experimental phases: (1) Characterization Phase I, from which one formulation prototype was obtained, and (2) Characterization Phase II, where different chemical improvements of the prototype were evaluated and a final coating prototype was selected. The degradable coatings that were obtained released silicon compounds during their hydrolytic degradation, inducing the implant osseointegration by distance osteogenesis. The new coatings offer the possibility to functionalize the titanium surface and serve like delivery vehicle of biomolecules and drugs that could improve and accelerate the titanium osseointegration process. / [ES] RESUMEN En esta Tesis Doctoral se llevó a cabo la evaluación biológica de nuevos recubrimientos híbridos (orgánico-inorgánico), sintetizados vía sol-gel, basados en precursores de silicio, como recubrimientos osteointegradores y osteoinductores aplicados a prótesis radiculares de titanio en el ámbito de la implantología dental. La evaluación biológica de los nuevos recubrimientos constó de un estudio completo para determinar el efecto de los recubrimientos sobre cultivos celulares de linaje osteoblástico y el efecto de los tejidos tras la implantación in vivo en tibia de conejo (respuesta de reacción a cuerpo extraño y osteointegración), mediante estudio histológico. La caracterización biológica se complementó con una caracterización físico-química de los materiales, determinando su topografía, su mojabilidad, la reactividad de su superficie, así como su grado de degradación y la liberación de silicio, para explicar el comportamiento biológico que cada uno de los materiales indujo. Los recubrimientos que presentaron un mejor comportamiento celular fueron seleccionados como materiales candidatos para llevar a la fase de implantación in vivo. Este trabajo constó de dos fases experimentales; (1) la Fase de Caracterización I de la que se extrajo una formulación prototipo, sobre la cual se realizaron mejoras químicas evaluadas en la (2) Fase de Caracterización II, de la cual fue elegido el recubrimiento prototipo final. Se obtuvieron recubrimientos degradables en cuya degradación hidrolítica liberaron compuestos de silicio que indujeron la osteointegración de los implantes recubiertos mediante osteogénesis a distancia, sin interferir en el proceso de osteointegración del titanio. Los nuevos recubrimientos ofrecen la posibilidad de funcionalizar la superficie del titanio y servir de vehículo de liberación de biomoléculas y fármacos que puedan mejorar y acelerar el proceso de osteointegración del titanio. / [CAT] RESUM En aquesta Tesi Doctoral es va dur a terme l'avaluació biològica de nous recobriments híbrids (orgànic-inorgànic), sintetitzats via sol-gel, basats en precursors de silici, com recobriments osteointegradors i osteoinductors aplicats a pròtesis radiculars de titani en l'àmbit de la implantologia dental. L'avaluació biològica dels nous recobriments va constar d'un estudi complet per determinar l'efecte dels recobriments sobre cultius cel¿lulars de llinatge osteoblástic i l'efecte dels teixits després de la implantació in vivo en tèbia de conill (resposta de reacció a cos estrany i osteointegració), mitjançant estudi histològic. La caracterització biològica es va complementar amb una caracterització fisicoquímica dels materials, determinant la seva topografia, la seva mullabilitat, la reactivitat de la seva superfície, així com el seu grau de degradació i l'alliberament de silici, per explicar el comportament biològic que cada un dels materials va induir. Els recobriments que van presentar un millor comportament cel¿lular van ser seleccionats com materials candidats per portar a la fase d'implantació in vivo. Aquest treball va constar de dues fases experimentals; (1) la Fase de Caracterització I de la qual es va extreure una formulació prototip, sobre la qual es van realitzar millores químiques avaluades en la (2) Fase de Caracterització II, de la qual va ser elegit el recobriment prototip final. Es van obtenir recobriments degradables, en la seva degradació hidrolítica van alliberar compostos de silici que van induir l'osteointegració dels implants recoberts mitjançant osteogènesi a distància. Els nous recobriments ofereixen la possibilitat de funcionalitzar la superfície del titani i servir de vehicle d'alliberament de biomolècules i fàrmacs per poder millorar i accelerar el procés d'osteointegració del titani. / Lara Sáez, I. (2015). Evaluación biológica de nuevos recubrimientos osteoinductores sintetizados vía sol-gel para aplicación en implantología dental [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/51463 / TESIS

<p>Impressive examples of the generation of hierarchically-patterned, three-dimensional (3-D) structures for the control of light can be found throughout nature. <i>Morpho rhetenor</i> butterflies, for example, possess scales with periodic parallel ridges, each of which consists of a stack of thin (nanoscale) layers (lamellae). The bright blue color of <i>Morpho</i> butterflies has been attributed to controlled scattering of the incident light by the lamellae of the wing scales. Another stunning example is the frustule (microshell) of the <i>Coscinodiscus wailesii</i> diatom, which is capable of focusing red light without possessing a traditional lens morphology. The photonic structures and the optical behaviors of <i>Morpho</i> butterflies and <i>Coscinodiscus wailesii</i> diatoms have been extensively studied. However, no work has been conducted to shift such light manipulation from the visible to the infrared (IR) range via shape-preserving conversion of such biogenic structures. Controlling IR radiation (i.e., heat) utilizing biogenic or biomimetic structures can be of significant utility for the development of energy-harvesting devices. In order to enhance the optical interaction in the IR range, inorganic replicas of biogenic structures comprised of high-refractive-index materials have been generated in this work. Such replicas of <i>Morpho</i> <i>rhetenor</i> scales were fabricated via a combination of sol-gel solution coating, organic pyrolysis, and gas/solid reaction methods. Diatomimetic structures have also been generated via sol-gel coating, gas/solid reaction, and then patterning of pore arrays using focused ion beam (FIB) milling.</p> Throughout the sol-gel solution coating and chemical conversion steps of the processes developed in this study, attention was paid to preserve the starting shapes of the nanopatterned, microscale biogenic or biomimetic structures. Factors affecting such shape preservation included the thicknesses and uniformities of coatings applied to the biogenic or biomimetic templates, nano/microstructural evolution during thermal treatment, and reaction-induced volume changes. A conformal surface sol-gel (SSG) coating process was developed in this work to generate oxide replicas of <i>Morpho rhetenor</i> butterfly scales with precisely-controlled coating thicknesses. The adsorption kinetics and relevant adsorption isotherm of the SSG process were investigated utilizing a quartz crystal microbalance. Analyses of thermodynamic driving forces, rate-limiting kinetic steps, and volume changes associated with various chemical reactions were used to tailor processing parameters for optimized shape preservation.