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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
241

Membrane technologies for hydrogen and carbon monoxide recovery from residual gas streams. Tecnologías de membranas para la recuperación de hidrógeno y monóxido de carbono de gases residuales

David, Oana Cristina 19 July 2012 (has links)
This PhD thesis work is aimed to the separation and recovery of valuable gases from industrial residual gas streams by means of membrane technology. In this thesis, a case of study is defined as the tail gas generated in the manufacturing of carbon black. It is envisaged that membrane technology will allow to obtain H2 enriched permeate stream when polymeric membranes are used and CO can be obtained as permeate gas stream when facilitated transport - supported liquid membranes are used. Chapter I of this thesis gives a brief introduction over different gas separation methods and shows the industrial sources and importance of H2 and CO. Chapter II and III of this thesis deal with the study of polymeric membrane based separation of hydrogen from mixed gas streams composed of H2, CO, N2 and CO2 at different operation conditions, using dense and hollow fiber membranes prepared with a commercial glassy polymer, Matrimid. In chapter IV a comprehensive look at the reaction mechanism and the equilibrium parameters obtained from the experimental characterization of the physical and chemical solubility of carbon monoxide 1-Hexyl-3-methylimidazolium chlorocuprate ionic liquid is presented. Finally, in Chapter V overall conclusions of the entire work are made. Also prospects for further research are included. / Esta tesis doctoral está enfocada hacia la separación y recuperación de hidrogeno y monóxido de carbono de efluentes gaseosos residuales procedentes de procesos industriales de combustión mediante la tecnología de membranas. Se ha definido como caso de estudio la corriente de gases generada en la fabricación de negro de carbono. Se espera que el uso de tecnologías de separación con membranas permita obtener en el lado del permeado de la membrana una corriente enriquecida en hidrógeno al emplear una membrana polimérica y una corriente enriquecida en monóxido de carbono mediante el transporte facilitado a través de una membrana líquida soportada. El Capítulo I de la tesis contiene una introducción sobre los distintos métodos de separación de gases y presenta las fuentes e importancia industrial de H2 y CO. Los capítulos II y III de la tesis abarcan el estudio de la separación selectiva de hidrógeno a partir de corrientes gaseosas compuestas por mezclas de H2, CO, N2 y CO2 utilizando membranas: (I) planas y densas y (II) asimetrics de fibra hueca, preparadas a partir de un polímero comercial de tipo vítreo, denominado Matrimid. El capítulo IV está enfocado en un análisis exhaustivo sobre el mecanismo de reacción y los parámetros de equilibrio obtenidos mediante la caracterización experimental de la solubilidad física y química del monóxido de carbono en el líquido iónico puro 1-Hexil-3-metilimidazolio cloruro en 1-Hexil-3-metilimidazolio clorocuprato Finalmente, el capítulo V presenta las conclusiones globales del trabajo de tesis doctoral. Además, se incluyen perspectivas para la investigación futura.
242

Effect of alkaline conditions on near-field processes of a spent nuclear fuel geological repository

Martínez Torrents, Albert 17 March 2015 (has links)
The contact ofthe spent nuclear fuel (SNF) with water dueto a failure in the canister would be a conservative but still plausible hypothesis in the safety assesment of a deep geologic repository (DGR). Concrete and cementitious materia Is will be part ofthe DGR structure. Water in contactwith those materials will have a very alkaline pH. Once the water gets in contact with the SNF the following 4 stages may take place: Radiolysis, Oxidation, Dissolution and Secondary Phase Formation. The formation of uranyl-peroxide complexes was studied at alkaline media by using UV-Visible spectrophotometry and the STAR cede. Two different com plexes were found ata H202/U(VI) ratio lower than 2. A graphical method was u sed in arder to obtain the formation constants ofsuch complexes and the STAR program was used to refine the formation constants values because ofits capacityto treatmultiwavelength absorbance data and refining equilibrium constants. The values obtained far the two equilibrium constants were: lag ¡3°1, 1,4 = 28.1 ± 0.1 and lag ¡3°1,2,6=36.8 ± 0.2. At hydrogen peroxide concentrations higherthan 10-5 mol dm-3, and in the absence of carbonate, the U02(02)2(0H)24-complex is predominant in solution. Time-resolved laser-induced fluorescence spectroscopy(TRLFS) was used to studythe speciation ofuranium(VI) atvery alkaline pH (11-13), at room temperature and in the absence of C02. Fluorescence lifetimes fer (U02)3(0H)7-, U02(0H)3-and U02(0H)42- were determined far pH between 11and13. Measurements at 1 O K were made, obtaining two different lifetimes in the pH range between 12 and 13.5, indicating the presence oftwo different species: U02(0H)3- and U02(0H)42-. The difference between the Iifetimes allowed the calculation ofthe contribution of each species to the total fluorescence signal intensity. lt was observed that hydrogen peroxide produces a quenching effect to the fluorescence of the uranium species. At pH 12 the quenching is static, which points to the formation of a non-fluorescent complex between U(VI) and hydrogen peroxide. Using the Stern-Volmer equation far static quenching, the equilibrium formation constant of the first species, U0202(0H)22-, was calculated to be logKO = 28.7 ± 0.4. A flow-through experimental reactor has been designed in arder to perform studies at both high pressure, high tem perature conditions and high surface salid to volume leachant ratios.Using this new reactor the evolution of uranium concentrations released from an U02 sample was studied atdifferent conditions. The results show that at hydrogen pres sures between 5 and 7 bars, hydrogen peroxide does not seem to significantlyoxidize the uranium (IV) oxide. Uranium concentrations in those experiments remain between 10-8 mol¿l-1 and 10-9 molof-1. The effects of alpha-radiolysis were determined, on one hand, through the generation of radiolytic products: H2, 02, HCIO and H202, and on the other hand from the dissolution ofboth U and Pu. The studies were focused on the effect produced by different dos e rates, different ionic strength as well as varying the Iocation ofthe alpha-emitters (either into the pellets or dissolved in solution) The experiments were performed at pH 12. Regarding the 02 and H2 production neither the Iocation ofthe alpha-emitters nor the ionic strength had any effect on the gas formation. At high ionic strength onlythe HCIO formation is observed, while at Iow ionic strength onlythe H202 formation is observed. The experimenta 1 data regarding the form ation of 02 and H2 was s ucces s fully fitted us ing the Macks im a-C hem is t software.The sorption of Se(IV) and Se(VI) on uranium peroxide has been studied consídering the sorption kinetics, the sorption isotherms and the effect ofpH. Selenium sorption on studtite is fitted with a pseudosecond arder reaction model; Both selenium(IV) and selenium(VI) are sorbed on studtite through a monolayer coverage. Sorptíon is higher at acidic pH than at alkaline pH. / El contacte del combustible nuclear gastat (CNG) amb l'aigua degut a una fallada en la capsula de protecció és una hipótesis conservadora peró plausible en el informe de seguretat de un magatzem geologic profund (MGP). Formigó i ciment seran presents en la estructura del MGP. L'aigua en contacte amb el CNG pot patir4 processos diferents: Radiólisi, Oxidació, Dissolució i Formació de Fases Secundaries. La formació de complexes uranil-peróxid fou estudiada en medi alcalí utilitzant espectrofotometria UV-\ñsible i el codi STAR. Es van trabar dos complexes diferents en una ratio H202/U(VI) per sota de 2. Es va usar un métode grafic per obtenir informació deis complexes esmentats i el programa STAR s'utililzil pera refinar els valors de les constants de formació degut a la seva capacitat pera tractar dades de absorbancia en múltiples longítuds d'ona y per refinar constants d'equilibri. Els valors obtinguts pera les dues constants de equilibri van ser: log ¡3"1,1,4 = 28.1±0.1 í log 13°1 ,2,6=36.8 ± 0.2. A concentracions de peróxid d'hidrogen més altes de 10-5 mol dm-3, i en abséncia de carbonats, el complex U02(02)2(0H)24- es predominant en solució. La espectroscópia de fluorescencia induida per laser resolta en el temps (TRLFS) s'utilitzà per studiar la especiació del urani (VI) a pHs molt alcalins (11-13), a temperatura ambient i en abséncia de C02. Es van determinar els temps de vida de fluorescéncia dels complexes (U02)3(0H)7-, U02(0H)3- i U02(0H)42- a pHs entre 11 i 13. Es varen fer mesures a 1 O K en un rang de pH entre 12 i 13.5, determinant la presència de dos espécies U02(0H)3- i U02(0H)42-. S'observa com el peróxid de hidrogen produeixun efecte de extinció (quenchíng) de la fluorescencia de les espécies de urani. A pH 12 la extinció era estatica, cosa que va apuntar a la formació de un complex no fluorescent entre el U(\11) í el peróxid de hidrogen. Utilitzant la equació de Stern-Volmer pera la extinció estética es va calcular la constant de equilibri de la espécie U0202(0H)22- (logKO = 28.7 ± 0.4). Es va dissenyar un reactor experimental de fluxper fer estudis a altes pressions, a elevades temperatures i a una relació superficie del salid - volum de líxiviant molt alta. Utilitzant aquest nou reactor es va estudiar la evolució de la concentració de urani alliberatde una mostra de U02, en diferents condicions . Els resultats mostren com a pressions de hidrogen entre 5 i 7 bars, el peróxid de hidrogen no sembla que oxidi significativament el óxid de urani(IV). Les concentracions de urani en aquests experiments es mantingueren entre 10-8 mol.l-1 i 10-9mol-l-1. Es determinaren els efectes de la alfa-radiólisi, d'un cantó a través de la generació de productes radiolítics: H2, 02, HCIO i H202 i de l'altre a partir de la dissolució de U i Pu. Els estudis es centraren en el efecte produït per diferents velocitats de dosi, diferents forces ióniques, així com també modificant la localització deis emissors alfa (dins de la pastilla o dissolts en la solució). Els experiments es realitzaren a pH 12. Pel que fa a la producció de 02 i H2, ni la localització deis emissors alfa ni la força iónica tenen cap efecte en la formació de gas. A elevada força iónica s'observa només formació de HCIO, mentre que a baixa força iónica tan sols es veu formació de H202. Les dades experimentals referents a la formació de 02 i H2, es van ajustar amb éxit utilitzant el software Macksima-Chemist. S'ha estudiat la sorció de Se(IV) i Se(VI) en el peróxid de urani considerant la cinética de sorció, la isoterma de sorció i l'efecte del pH. La sorció de Seleni en Studtita s'ajusta a un model de reacció de pseudo-segon ordre. Ambdós Se(IV) i Se(\11) es sorveixen en la Studtita a través de una cobertura monocapa. La sorció es més alta a pH acid que a pH basic
243

Evaluation of the composition and development of Maillard reaction in infant formulas / Avaliação da composição e desenvolvimento da reação de Maillard em fórmulas infantis

Nunes, Lauane 19 February 2018 (has links)
Submitted by Marco Antônio de Ramos Chagas (mchagas@ufv.br) on 2018-03-14T11:20:12Z No. of bitstreams: 1 texto completo.pdf: 1286231 bytes, checksum: 48d3bd9233ab5b2b2cbcc95ccd8223a9 (MD5) / Made available in DSpace on 2018-03-14T11:20:12Z (GMT). No. of bitstreams: 1 texto completo.pdf: 1286231 bytes, checksum: 48d3bd9233ab5b2b2cbcc95ccd8223a9 (MD5) Previous issue date: 2018-02-19 / Conselho Nacional de Desenvolvimento Científico e Tecnológico / A fórmula infantil tem a função de substituir ou complementar o leite materno e sua formulação é baseada no leite de vaca modificado. Devido a uma grande quantidade de tratamentos térmicos, as fórmulas estão sujeitas a uma série de reações que causam redução de qualidade, entre elas a reação de Maillard. Além disso, é importante que estes produtos proporcionem quantidades suficientes de todos os nutrientes, por isso, é necessário uma avaliação constante da composição nutricional dos produtos disponíveis no mercado. Portanto, o objetivo deste trabalho foi avaliar a propagação da reação de Maillard em fórmulas infantis e investigar a composição centesimal de produtos em condições de uso ao longo de 60 dias a 4 e 24 oC. Observou-se uma diminuição no teor de lactose, lisina e pH; aumento da umidade, teor de HMF, atividade da água e diferença de cor. Possivelmente, a lactose se associa a algumas proteínas e aminoácidos, como a lisina, nas fases iniciais da reação de Maillard e com o prolongamento do armazenamento, há produção de intermediários como HMF, ácido fórmico, água, entre outros, de tal maneira que os compostos intermediários polimerizam formando os pigmentos conhecidos como melanoidinas. No entanto, ao diminuir a temperatura de armazenamento, observou-se uma diminuição nas taxas de reação de Maillard e, consequentemente, menores perdas nutricionais. Quanto à composição centesimal, quase todas as fórmulas infantis analisadas estavam dentro dos limites estabelecidos. Além disso, elas não representam riscos para a saúde do lactente em relação ao nível de HMF. Porém, ainda são necessários estudos para esclarecer o efeito da reação de Maillard sobre esse tipo de produto, quais os danos reais para as crianças e avaliar os valores de micronutrientes. / Infant formula has the function of replacing or complementing breast milk and its formulation is based on modified cow milk. Due to a large number of heat treatments, the formulas are subject to a series of reactions that cause a reduction in its quality, among them the Maillard reaction. In addition, it is important that these products provide sufficient quantities of all nutrients, therefore, a constant evaluation of the nutritional composition of products available in the market is necessary. Therefore, the objective of this work was evaluate the propagation of Maillard reaction in infant formulas and to investigate the centesimal composition of products under conditions of use over 60 days at 4 and 24 oC. It was observed a decrease in lactose, lysine content and pH; increase in moisture, HMF content, water activity and color difference. Possibly, lactose is associated with some proteins and amino acids, such as lysine, in the initial phases of Maillard reaction, and with the prolongation of the storage, there is production of intermediates such as HMF, formic acid, water, among others, in such a way that the intermediate compounds polymerize forming the pigments known as melanoidins. However by decreasing the storage temperature, it was observed a decrease in the Maillard reaction rates, and consequently, lower nutritional losses. Regarding the centesimal composition, almost all the infant formulas analyzed were within the limits established. In addition, they does not pose health risks to the infant in relation to the level of HMF. However, studies are still needed to clarify the effect of Maillard reaction on this type of product, what the real harm to the infant and review the micronutrient values.
244

Aspectos cinéticos e moleculares da dispersão de quitosano em meios aquosos contendo ácidos orgânicos monopróticos / Kinetic and molecular aspects of the dispersion of chitosan in aqueous media containing monoprotic organic acids

Souza, Maurício Palmeira Chaves 27 March 2018 (has links)
Submitted by Marco Antônio de Ramos Chagas (mchagas@ufv.br) on 2018-07-09T13:53:30Z No. of bitstreams: 1 textocompleto.pdf: 2032527 bytes, checksum: ce69328abd2036640887a58922e0c8f8 (MD5) / Made available in DSpace on 2018-07-09T13:53:30Z (GMT). No. of bitstreams: 1 textocompleto.pdf: 2032527 bytes, checksum: ce69328abd2036640887a58922e0c8f8 (MD5) Previous issue date: 2018-03-27 / Conselho Nacional de Desenvolvimento Científico e Tecnológico / Quitosano é um polissacarídeo policatiônico de origem animal que apresenta biocompatibilidade e biodegradabilidade, que não se dispersa em água pura, apenas em meios ácidos, limitando sua aplicação a estes meios. Assim, se torna necessário determinar a dispersibilidade máxima deste biopolímero e compreender a nível molecular o seu comportamento em meios aquosos contendo ácidos que apresentam diferentes estruturas moleculares e aplicações biotecnológicas. Neste estudo caracterizou-se o quitosano quanto a sua massa molar viscosimétrica (Mv) e grau de desacetilação (GD%) e por meio de técnicas espectroscópicas, potenciométricas e condutivimétricas buscou-se compreender as interações intermoleculares deste quando disperso em meios aquosos contendo os ácidos monopróticos: glicólico, acético, propiônico e lático. Realizou-se também a quantificação da dispersibilidade máxima e cinética de dispersão do quitosano por espectrofotometria UV-Vis a 275 nm ajustando-se aos dados um modelo matemático exponencial crescente, para cada ácido que constituiu as dispersões nas concentrações [10,30 e 50 mmol.L -¹ ], bem como foram medidos os potenciais ζ das cadeias de quitosano dispersas em cada um dos ácidos na concentraçãode 10mmol.L -¹ . Utilizando o quitosano de Mv 624 KDa e GD % =77,12%, calculou-se as dispersibilidades máximas do polímero = [(0.6 0.7 e 1.35 g.(100mL) -¹ ] para as respectivas concentrações [10,30 e 50 mmol.L -¹ ] de cada um dos ácidos, utilizando modelo matemático de primeira ordem com dois termos, ajustado (R 2 >0.9) aos dados de cinética .A faixa de pH encontradas para a titulação das suspensões variou de 7 a 2.5 e condutividade de 0 a 2000 μs.cm -¹ , nos espectros de FT-IR destacaram- se bandas de NH 3+ , OH e CO. O potencial ζ das cadeias dispersas nos diferentes ácidos não se mostrou diferentes (p<0.05), apresentando-se positivo na faixa de (57,8 ±0.9 mV). Com a análise conjunta dos dados concluiu-se, que os contra-íons decorrentes da ionização dos ácidos não interagiram de maneira significante com os grupos amino protonados do quitosano, de modo que não afetaram a dispersão deste polímero nestes meios. Também foi observado que o processo de dispersão da quitosana é dinâmico ocorrendo em duas etapas, uma primeira etapa, mais rápida e marcada em grande parte, pela maior extensão de protonação das cadeias do biopolímeiro e a segunda mais lenta, marcada principalmente pela solvatação destas cadeias protonadas. / Chitosan is a polycationic polysaccharide of animal origin that presents biocompatibility and biodegradability, which does not disperse in pure water, only in acidic media, limiting its application to these media. Thus, it is necessary to determine the maximum dispersibility of biopolymer and index at the molecular level, its behavior in aqueous media, with different acids and applications, structural and biotechnological applications. In this study chitosan was characterized for its viscosimetric molar mass (Mv) and degree of deacetylation percentual (GD%) and by means of spectroscopic, potentiometric and conductivimetric techniques it was sought to understand the intermolecular interactions of this when dispersed in aqueous media containing the monoprotic acids: glycolic, acetic, propionic and lactic) by means of spectroscopic, potentiometric and conductivity. Quantification of the maximum and kinetic dispersion of chitosan dispersion by UV-Vis spectrophotometry at 275 nm was also performed by adjusting the exponential mathematical model for each acid that constituted the dispersions at the concentrations [10.30 and 50 mmol.L -¹ ], as well as the pot potentials of the chitosan chains dispersed in each of the acids in the concentration of 10 mmol.L -¹ . Using the chitosan of Mv 624 KDa and GD% = 77.12%, the maximum polymer dispersions = [(0.6 0.7 e 1.35 g.(100mL) -¹ ] were calculated for the respective concentrations [10,30 e 50 mmol.L -¹ ] of each of the acids, using mathematical model of first order with two terms, adjusted (R 2 > 0.9) to kinetic data. The pH range found for the titration of the suspensions ranged from 7 to 2.5 and conductivity from 0 to 2000 μs.cm -¹ , in the Infrared spectroscopy with Fourier transform (FT-IR) spectra the bands of NH 3+ , OH and CO were highlighted. The potential ζ of the chains (p <0.05), presenting positive values in the range of (57,8 ±0.9 mV). With the analysis of the data, it was concluded that the ion-ion counter-ion did not interact with. In a significant manner with the protonated amino groups of chitosan, so that they did not affect the dispersion of this polymer in these media. It was also observed that the chitosan dispersion process is dynamic, occurring in two stages, a first step, faster and marked in large part, by the greater protonation extension of the chains of the biopolymer and the second slower, marked mainly by the solvation of these chains protonated.
245

Preparation and study of ternary metal oxide photocathodes for solar energy conversion

Díez García, María Isabel 17 January 2018 (has links)
The future energy demand will require a change in the current energy supply. In this regard, the production of hydrogen by photoelectrochemical solar cells is a promising alternative because the fuel is obtained from water and, importantly, its combustion is free of carbon. Many metal oxides, including those having a complex stoichiometry (i.e. ternary oxides) behave as semiconductors and present good stability in aqueous environments, making them attractive candidates for water splitting devices. This thesis focuses on the preparation and study of ternary metal oxide materials as photoelectrodes for water splitting, with emphasis on photocathodes. These materials must meet the requirements for a practical device: low cost, non-toxicity, made of Earth abundant elements, environmentally friendly, etc. The thesis also aims at the study of strategies to improve their photoelectrochemical response. lt comprises the investigation of the kinetics of hydrogen generation reaction and the characteristics of the electrode solution interface by photoelectrochemical impedance spectroscopy. The main points can be summarized as: (i) the effect of an electrochemical oxidative pretreatment in CuFe2Ü4 photocathodes (ii) the investigation of water splitting mechanisms in CaFe2Ü4 photocathodes, (iii) the effect of metal doping in LaFeO3 photocathodes (iv) the study of the photoelectrochemistry of compact and nanoparticulate YFeO3 photocathodes and (v) the effect of a reductive electrochemical treatment in NiTiO3 photoanodes, and comparison with the effect of the treatment in anatase electrodes.
246

Tailoring of carbon materials for their use as electrodes in electrochemical capacitors

Salinas-Torres, David 02 December 2014 (has links)
No description available.
247

Flavour Tagging developments within the LHCb experiment

Grabalosa Gándara, Marc 15 May 2012 (has links)
Flavour Tagging at the LHCb experiment is a fundamental tool for the measurement of B oscillations and the study of CP violation. This document explains the development of different tagging techniques and the different strategies used to combine them to determine the flavour of the B meson as precisely as possible. The response of the tagging algorithms also needs to be optimized and calibrated. Both procedures are described using the available LHCb datasets corresponding to various integrated luminosities. First results on the tagging performances are shown for different control channels and physics measurements.
248

Clústeres Calcogenuro de Metales del Grupo 6 con Relevancia en Catálisis Asimétrica y Bifásica

Guillamón Torres, Eva María 05 June 2009 (has links)
El trabajo de investigación que se expone en esta Tesis Doctoral presenta la síntesis de una nueva familia de compuestos trinucleares de fórmula general [M3Q4X3(difosfina)3]+ (M = Mo, W; Q = S, Se; X = Cl, Br, H) y son el punto de partida para la preparación de nuevos derivados heterodimetálicos M3M'Q4 (M' = Cu, Pd y Ni). Atendiendo a la naturaleza del ligando difosfina incorporado a la unidad, estos compuestos poseen diferentes propiedades. Concretamente, se han incorporado difosfinas solubles en agua y difosfinas ópticamente activas con el fin de estudiar y evaluar las cualidades de los nuevos derivados en catálisis bifásica (de bajo impacto medioambiental) y en catálisis asimétrica, respectivamente. También se presenta la asociación de los aniones quirales TRISPHAT, BINPHAT y TMT(Ph) con los sistemas racémicos [Mo3S4Cl3(difosfina)3]+ y [Mo3M'S4Cl3(dmpe)3]+ (con difosfina = dmpe, dppe) para su resolución. Finalmente, se detallan todos los estudios teóricos llevados a cabo sobre diferentes sistemas. Concretamente, la epimerización del catión [Mo3S4Cl3(dppe)3]+, la protonación del clúster hidruro [Mo3S4H3((R,R)-Me-BPE)3]+, el equilibrio ácido-base del clúster [Mo3S4Cl3(dhmpe)3]+ y la evaluación de la actividad catalítica de los derivados ópticamente puros Mo3CuQ4 en reacciones de ciclopropanación.
249

Tratamientos de superficie sobre titanio comercialmente puro para la mejora de la osteointegración de los implantes dentales

Aparicio Bádenas, Conrado 15 April 2005 (has links)
El éxito clínico de los implantes dentales, fabricados en titanio comercialmente puro (Ti c.p.), está basado en la consecución de la osteointegración, es decir, la conexión directa estructural y funcional entre el hueso vivo, ordenado, y la superficie del implante. La mejora de la osteointegración a corto y largo plazo es función de múltiples factores, de entre los cuales, la calidad superficial del implante (fisicoquímica y topográfica) es de gran importancia. De hecho, todas las interacciones biológicas y mecánicas que se dan entre el implante y los tejidos circundantes son a través de la interfaz creada entre dichos tejidos y la superficie del material implantado.En este trabajo se estudian y desarrollan distintos tratamientos aplicados sobre la superficie de los implantes dentales con el objetivo final de obtener implantes con una mejor osteointegración, tanto a corto como a largo plazo. En la primera parte se obtienen superficies rugosas por medio del tratamiento del granallado.La rugosidad de las superficies de Ti c.p. granalladas depende no sólo del tamaño de las partículas abrasivas de proyección empleadas (125 - 300 &#61549;m; 425 - 600 &#61549;m; 1000 - 1400 &#61549;m), sino también de su naturaleza química (Al2O3, SiC, TiO2 y ZrO2) y su forma. Esta rugosidad se debe cuantificar con, al menos, dos parámetros, uno de altura (Ra) y otro de espaciado (Pc). Además, cualquiera que sea la naturaleza química de las partículas empleadas, quedan restos de las mismas sobre las superficies tratadas. Con estas premisas, las propiedades de la superficie del Ti c.p. granallado se han podido optimizar, ya que la respuesta de adhesión y diferenciación de los osteoblastos está influenciada por la rugosidad y la naturaleza de las partículas de proyección. Además, aunque el aumento de rugosidad y las tensiones residuales que se inducen con el granallado influyen sobre el comportamiento electroquímico del material, éste es adecuado con respecto a su resistencia a la corrosión, de acuerdo a su posible utilización como material para la fabricación de implantes dentales.En la segunda parte se obtienen superficies rugosas y bioactivas por medio de un tratamiento en dos pasos: en primer lugar se granalla el implante (con las condiciones óptimas determinadas en la primera parte); y después se aplica un tratamiento termoquímico. El tratamiento termoquímico consiste en atacar el metal con NaOH y obtener en su superficie un gel hidratado de titanato de sodio. Este gel se deshidrata y densifica con un tratamiento térmico a 600 oC. En estas condiciones, el Ti c.p. es bioactivo.Las superficies de Ti c.p. granalladas con Al2O3 y tratadas termoquímicamente, demuestran su potencial bioactividad porque hacen crecer por vía química in vitro, sobre su superficie, una capa de apatita; y la confirman, al crecer también in vivo. Sin embargo, la presencia de los restos de partículas de SiC sobre la superficie del metal inhibe su bioactividad. Estas superficies rugosas y bioactivas se estudian de forma comparativa, in vitro e in vivo, con otras no rugosas y/o bioinertes. La respuesta de diferenciación de los osteoblastos y la osteointegración a corto y medio plazo se ven favorecidas por la combinación sinérgica de la rugosidad y la bioatividad del metal. Como consecuencia, los implantes rugosos y bioactivos son candidatos preferenciales para ser utilizados en los procedimientos clínicos de carga inmediata.
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Electrochemically actuated capillary flow control for the development of integrated microfluidic devices

Washe, Alemayehu Paulos 21 March 2013 (has links)
Dispositivos microfluidos operados por fuerzas capilares son fáciles de operar plataformas para realizar herramientas Lab-On-a-Chip (LOC). Si estas “simplistas” aplicaciones LOC tengan éxito, la operación unitaria del control de flujo hay que desarrollarse. Esto es particularmente verdad para herramientas “ASSURED” (término introducido por A. Guiseppi-Elie: Affordable, Sensitive, Specific, User-friendly, Rapid and robust, Equipment-free and Deliverable) y aplicaciones bioanalíticas en las cuales la respuesta depende de la disolución de los reactivos previamente depositados, la cinética de afinidad biológica y enzimática, y el transporte en materia de productos a un transductor en los microcanales. En esta tesis el diseño, fabricación e implementación de tres alternativas electroquímicas para el control del flujo capilar se han desarrollado basadas en electrowetting usando i) superficies superhidrófobas basándose a polímeros que responden inteligentemente a los estímulos eléctricos, ii) superficies nanoporosas superhidrófobas de electrodos de carbono, y iii) electrodos con superficies superhidrófobas acoplados a otros electrodos que facilitan la generación de gradientes que pueden propulsar el líquido. La tesis estudia el mecanismo de la respuesta en cada caso en estos sistemas y demuestra opciones para la reducción a la práctica de herramientas que pueden “democratizar” la “teranostica” (theranostics). / Capillary force-operated microfluidic devices are easy to use, low cost realization platforms for Lab-on-a-Chip (LOC) configurations. If such “simplistic” LOC applications are to have success, flow control is an important unit operation to develop. This is particularly true for ASSURED (a term introduced by A. Guiseppi-Elie: Affordable, Sensitive, Specific, User-friendly, Rapid and robust, Equipment-free and Deliverable) devices for bioanalytical applications where an analytical response depends on the dissolution of previously deposited reagents, the kinetics of biological affinity and enzymatic reactions, and mass transport of products to a transducer in the microchannels. In this thesis the design, fabrication and implementation of three different electrochemically actuated capillary flow control schemes have been developed through low voltage electrowetting/ electrochemical actuation of the flow using i) electrical stimuli responsive superhydrophobic surfaces based on intelligent polymers ii) superhydrophobic nanoporous carbonaceous surfaces, and iii) superhydrophobic electrodes coupled to other electrodes that facilitate the generation of gradients to propel the liquid. The thesis unravels the mechanism of response of such systems and demonstrates ways for reduction to practice of such devices for the “democratization” of theranostics.

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