Background: More than 90 % of anal cancers are caused by high-risk human papillomavirus (HR HPV) infection and a history of cervical intraepithelial neoplasia (CIN) and cervical cancer is established as possible risk factor. The aim of this study was to demonstrate relationship between anal and cervical HPV infection in women with different grades of CIN and microinvasive cervical cancer and to determinate potential risk factors for concurrent cervical-anal HPV infection. Methods: A total of 272 women were enrolled in the study. The study group included 172 women who underwent conization for high-grade CIN or microinvasive cervical cancer. The control group consisted of 100 women with non-neoplastic gynecologic diseases or biopsy- confirmed CIN 1. All participants completed a questionnaire detailing their medical history and sexual risk factors and were subjected to anal and cervical HPV genotyping using Lynear array test (Roche). Results: Cervical, anal, and concurrent cervical-anal HPV infections were detected in 82.6 %, 48.3 % and 42.4 % of women in the study group, and in 28.0 %, 26.0 % and 8.0 % of women in the control group, respectively. The prevalence of the HR HPV genotypes was higher in the study group and significantly increased with the severity of cervical lesion. Concurrent infections...

Pour améliorer la caractérisation et le dimensionnement des disques de turbines pour les moteurs d’avion, le motoriste Safran Aircraft Engines (SAE) développe des modèles de comportement, des lois d’endommagement et des critères de fatigue plus adaptés aux chargements réels. Pour aider à cette démarche, le but de cette étude est de développer un modèle de plasticité adapté à l'Inco718DA (un alliage à base nickel utilisé dans la fabrication des turbines haute pression), capable de représenter différents chargements (monotone, cyclique symétrique et non-symétrique). La proposition puis l'identification du modèle a été possible grâce à une campagne expérimentale favorisant des tests complexes et innovants aux essais de fatigue nombreux et coûteux. Les essais faits incluent un essai monotone avec décharges élastiques, un essai multi-niveau à Rε=-1 et deux essais multi-niveau à Rε=0 pour mieux caractériser la relaxation de la contrainte moyenne et un essai pour quantifer le rochet. Le comportement cyclique du matériau a été identifié en utilisant un écrouissage cinématique non saturant avec des éléments s'inspirant de la surface mémoire de Chaboche. Un des défis a été d'obtenir des boucles stabilisées "pointues" dans un régime de plasticité cyclique saturante, en utilisant une évolution du paramètre Γ en fonction de la déformation plastique équivalente maximale (prefacteur du terme de rappel de la loi d'écrouissage cinématique).Une deuxième difficulté apparaît dans la description de la relaxation de la contrainte moyenne, phénomène complexe avec un impact considérable sur la durée de vie en fatigue. Dans le chapitre 3, un modèle est proposé pour la caractérisation de la relaxation partielle de la contrainte moyenne. Une originalité du modèle est l'idée que la relaxation incomplète est une conséquence directe de la différence entre la charge et la décharge de la boucle de hystérésis. Le paramètre choisi pour décrire cette différence a été le préfacteur du terme de rappel Γ, pour lequel la thermodynamique donne de la liberté. Par rapport à d'autres lois d'écrouissage confirmées, notre modèle présente l'avantage d'utiliser un seul terme de rappel, mais avec une formulation plus complexe. En plus, le modèle est incrémental (écrit en taux/en vitesse), il peut donc prendre en compte des chargements complexes tels que aléatoires ou plus simplement tels que dans les essais multi-niveaux pilotés en déformation. Dans le dernier chapitre de la thèse, une campagne biaxiale vaste est présentée, avec les développements pour réaliser des essais biaxiaux pilotés en déformation. La campagne biaxiale a été réalisée sur des éprouvettes cruciformes en utilisant des capteurs LASER et des mesures de champs mono et stéréo analysées en utilisant la Corrélation d'Images Numeriques (CIN). Pour analyser la relaxation de la contrainte moyenne en biaxial un moyen de mesure et de contrôle fiable a dû être développé, adapté aux déformations plastiques élevées qui apparaissent dans la région d'intérêt de l'éprouvette. En utilisant la corrélation d'images intégrée (I-CIN) avec des fonctions de forme adaptées sur un seul élément et des calculs sur GPU, on a obtenu des fréquences de mesure de 100~Hz. En plus, avec sa précision et vitesse, I-CIN a été une technique adaptée pour contrôler une machine d'essais multiaxiale hydraulique. Un résultat important obtenu quand on a réalisé des essais equi-biaxiaux pilotés en déformation a été l'observation d'une relaxation de la contrainte moyenne très faible par rapport au cas uniaxial. Ce résultat doit être pris en compte dans les études futures avec des calculs éléments finis sur l'éprouvette complète. / To improve the characterization and design of aircraft engine turbine disks, the propulsion systems manufacturer Safran Aircraft Engines (SAE) develops constitutive equations, damage laws and fatigue criteria that are more adapted to real loadings. As part of this effort, the purpose of the current study is to develop a plasticity model for Inco718DA (a nickel-based alloy used in the manufacturing of high-pressure turbine disks), capable of representing several loading conditions (monotonic, symmetrical and non-symmetrical cyclic loading). The identification of the model was possible thanks to a uniaxial campaign, favoring a few but complex, innovative, tests to numerous costly fatigue tests. The tests we performed include a monotonic test with elastic discharges, a multi-level Rε = -1 test and two multi-level Rε = 0 tests that better quantify the mean stress relaxation and a test to identify ratcheting. The cyclic behavior was identified using a non-saturating kinematic hardening law with elements of Chaboche's memory surface. One of the challenges was to obtain sharp stabilized loops in a saturated cyclic plasticity regime, which was possible using parameter Γ evolving with respect to the maximum equivalent plastic strain, in the back-stress of kinematic hardening rule.A second difficulty appears in the description of mean stress relaxation, which has a considerable impact on fatigue lifetime. In chapter 3, a model is proposed for the description of the incomplete mean stress relaxation. One of the originalities is the idea that incomplete mean stress relaxation is a direct consequence of the difference between the loading and the unloading part of the hysteresis loop. The parameter we used to describe this difference, was the prefactor of the back-stress term Γ, for which the thermodynamics allows liberty. When compared to confirmed kinematic hardening laws that model non-zero mean stress relaxation, our model presents the advantage of using only one backstress, even if its description is more complex. Moreover, the model is incremental (written in a rate form in chapter 3 section 5) so it can take into account complex loadings such as multi-level strain-controlled tests.In the last chapter of the thesis, a vast biaxial campaign is presented, along with developments to make biaxial strain-controlled tests. The biaxial campaign was performed on cross-shaped samples using LASER sensors, mono and stereo full-field measurements using Digital Image Correlation (DIC). In order to analyze biaxial mean stress relaxation, a reliable measurement and control method had to be developed for the high plastic strains occurring in the region of interest of the sample. By using an Integrated-DIC (I-DIC) algorithm with adequate shape functions on one element and GPU computations we were able to obtain measurement frequencies of 100 Hz. Moreover, with its precision and speed, I-DIC proved to be a suitable technique for controlling a biaxial hydraulic machine. An important result obtained when performing equi-biaxial I-DIC strain-controlled tests was that there was very little biaxial mean stress relaxation, with respect to the uniaxial case. This result will have to be taken into account in future studies when performing finite element computations of the whole sample.

Made available in DSpace on 2014-12-17T15:42:04Z (GMT). No. of bitstreams: 1 CamilaRML_DISSERT.pdf: 3932876 bytes, checksum: 4cacf8f7fc64136e2ecb15a917a88b97 (MD5) Previous issue date: 2013-01-25 / Universidade Federal do Rio Grande do Norte / Among the polymers that stand out most in recent decades, chitosan, a biopolymer with physico-chemical and biological promising properties has been the subject of a broad field of research. Chitosan comes as a great choice in the field of adsorption, due to their adsorbents properties, low cost and abundance. The presence of amino groups in its chain govern the majority of their properties and define which application a sample of chitosan may be used, so it is essential to determine their average degree of deacetylation. In this work we developed kinetic and equilibrium studies to monitor and characterize the adsorption process of two drugs, tetracycline hydrochloride and sodium cromoglycate, in chitosan particles. Kinetic models and the adsorption isotherms were applied to the experimental data. For both studies, the zeta potential analyzes were also performed. The adsorption of each drug showed distinct aspects. Through the studies developed in this work was possible to describe a kinetic model for the adsorption of tetracycline on chitosan particles, thus demonstrating that it can be described by two kinetics of adsorption, one for protonated tetracycline and another one for unprotonated tetracycline. In the adsorption of sodium cromoglycate on chitosan particles, equilibrium studies were developed at different temperatures, allowing the determination of thermodynamic parameters / Dentre os pol?meros que mais se destacam nas ?ltimas d?cadas, a quitosana, um biopol?mero com propriedades f?sico-qu?micas e biol?gicas promissoras, tem sido alvo de um campo amplo de pesquisa. A quitosana se apresenta como uma ?tima escolha no campo de adsor??o, devido a suas propriedades adsorventes, baixo custo e abund?ncia. A presen?a de grupos aminos em sua cadeia governam a maioria das suas propriedades e definem em qual aplica??o dada amostra de quitosana poder? ser utilizada, assim torna-se imprescind?vel a determina??o do seu grau de desacetila??o m?dio. Neste trabalho foram desenvolvidos estudos cin?ticos e de equil?brio a fim de monitorar e caracterizar o processo de adsor??o de dois f?rmacos, o cloridrato de tetraciclina e o cromoglicato de s?dio, em part?culas de quitosana. Modelos cin?ticos e de isotermas de adsor??o foram aplicados nos dados experimentais. Para ambos os estudos, an?lises no potencial zeta tamb?m foram realizadas. A adsor??o de cada f?rmaco apresentou aspectos distintos. Atrav?s dos estudos desenvolvidos neste trabalho foi poss?vel descrever um modelo cin?tico para a adsor??o de tetraciclina em part?culas de quitosana, demonstrando que o mesmo pode ser descrito por duas cin?ticas de adsor??o, uma para a tetraciclina protonada e outra para a tetraciclina n?o protonada. Na adsor??o de cromoglicato de s?dio em part?culas de quitosana, estudos de equil?brio foram desenvolvidos a diferentes temperaturas, permitindo a determina??o de par?metros termodin?micos

Made available in DSpace on 2014-12-17T15:42:05Z (GMT). No. of bitstreams: 1 AnaLPFC.pdf: 1922699 bytes, checksum: c82e91dbc8eb0d49eecb97284bc06938 (MD5) Previous issue date: 2009-08-14 / Due to its physico-chemical and biological properties, related to the abundance and low cost of raw material, chitosan has been recognized as a material of wide application in various fields, such as in drug delivery systems. Many of these properties are associated with the presence of amino groups in its polymer chain. A proper determination of these amino groups is very important, in order to properly specify if a given chitosan sample can be used in a particular application. Thus, in this work, initially, a comparison between the determination of the deacetylation degree by conductometry and elemental analysis was carried out using a detailed analysis of error propagation. It was shown that the conductometric analysis resulted in a simple and safe method for the determining the degree of deacetylation of chitosan. Subsequently, experiments were performed to monitor and characterize the adsorption of tetracycline on chitosan particles through kinetic and equilibrium studies. The main models of kinetics and adsorption isotherms, widely used to describe the adsorption on wastewater treatment systems and the drug loading, were used to treat the experimental data. Firstly, it was shown that an apparent linear t/q(t) ? t relationship did not imply in a pseudo-second-order adsorption kinetics, differently of what has been repeatedly reported in the literature. It was found that this misinterpretation can be avoided by using non-linear regression. Finally, the adsorption of tetracycline on chitosan particles was analyzed using insights obtained from theoretical analysis, and the parameters generated were used to analyze the kinetics of adsorption, the isotherm of adsorption and to ropose a mechanism of adsorption / Devido ?s suas propriedades f?sico-qu?micas e biol?gicas, associadas ? abund?ncia e ao baixo custo da mat?ria-prima, a quitosana tem sido considerada um material de ampla aplica??o em diversos campos, tais como em sistemas de libera??o de f?rmacos. Muitas dessas propriedades est?o associadas ? presen?a de grupos amino em sua cadeia polim?rica. Uma determina??o apropriada desses grupos amino ? muito importante, com o objetivo de especificar adequadamente se uma dada amostra de quitosana pode ser usada em uma particular aplica??o. Dessa forma, neste trabalho, inicialmente, foi realizada uma compara??o entre a determina??o do grau m?dio de desacetila??o atrav?s de an?lises condutim?trica e elementar usando uma minuciosa an?lise de propaga??o erro. Foi mostrado que a an?lise condutim?trica resultou em um m?todo simples e seguro para determina??o do grau m?dio de desacetila??o da quitosana. Posteriormente, foram realizados experimentos a fim de monitorar e caracterizar o processo de adsor??o de tetraciclina em part?culas de quitosana, atrav?s de estudos cin?ticos e de equil?brio. Os principais modelos cin?ticos e de isotermas de adsor??o, amplamente usados para descrever a adsor??o em sistemas de tratamento de efluentes e de incorpora??o de f?rmacos, foram utilizados nos dados experimentais. Primeiramente, foi mostrado que uma aparente rela??o linear t/q(t) ? t n?o implica em um mecanismo de adsor??o de pseudo-segunda-ordem, diferentemente do que tem sido repetitivamente relatado na literatura. Foi encontrado que esta interpreta??o err?nea pode ser evitada atrav?s do uso de uma regress?o n?o-linear. Finalmente, a adsor??o de tetraciclina em part?culas de quitosana foi analisada, utilizando os conhecimentos obtidos de uma an?lise te?rica, e os par?metros gerados foram usados para analisar a cin?tica de adsor??o, a isoterma de adsor??o e para propor um mecanismo de adsor??o

Background: O câncer de colo uterino é um grande problema de saúde pública no Brasil e no mundo. Atinge cerca de meio milhão de mulheres, sendo que 50 % destas morrem. Os métodos visuais, alternativos á citologia e viáveis para países em desenvolvimento, têm sido avaliados mais intensamente na última década. Objetivos: Avaliar o desempenho da Fotografia Cervical Digital (FCD) na detecção do câncer do colo de útero e de suas lesões precursoras. Métodos: 176 mulheres foram avaliadas pelos métodos de Inspeção Visual com ácido acético (VIA), Inspeção Visual com lugol (VILI), Fotografia Cervical Digital com ácido acético (FCDA) e Fotografia Cervical Digital com lugol (FCDL). Destas, 36 foram classificadas pela histologia. Resultados: A concordância entre avaliadores observou valores de Kappa: Fotografia Cervical Digital com ácido acético, K=0,441, e Fotografia Cervical Digital com lugol, K=0,533. A concordância entre as inspeções a olho nu e as fotografias cervicais digitais após a utilização de ácido acético no colo uterino, K=0,559, e a concordância após a utilização da solução de lugol, K=0,507, considerada como concordância moderada em ambos os casos. Das 36 pacientes com avaliações histológicas, 20 dos 25 casos positivos foram corretamente avaliados tanto pela FCDA, como pela FCDL, demonstrando resultados similares aos descritos anteriormente. Conclusão: A FCD é um método promissor para o rastreamento do câncer de colo de útero e suas lesões precursoras, para países em desenvolvimento. / Background: Uterine cervix cancer is a major public health problem in Brazil and in the world. It affects half a million women with a death rate of 50%. The visual, alternative methods to cytology, considered viable for developing countries, are being assessed more intensively in the last decade. Objective: To evaluate the performance of Cervical Digital Photography (CDP) in detecting cervical cancer and its precursory lesions. Methods: A total of 176 women were evaluated by the following methods: Visual Inspection with Acetic Acid (VIA), Visual Inspection with Lugol’s Iodine (VILI), Cervical Digital Photography with Acetic Acid (CDPA) and Cervical Digital Photography with Lugol’s Iodine (CDPL). Among these, 36 were classified by histology. Results: The correlation between evaluators observed Kappa values: Cervical Digital Photography with acetic acid, K = 0.441, and Cervical Digital Photography with Lugol's Iodine, K = 0.533. The correlation between the naked eye and cervical digital photography inspection after using acetic acid in the uterine cervix, K = 0.559, and the correlation after using Lugol's Iodine solution, K = 0.507, were regarded as moderate in both cases. Of the 36 patients with histological evaluation, 20 of the 25 positive cases were correctly assessed both by the CDPA as well as by CDPL, showing similar results than those described previously. Conclusion: CDP is considered a more promising method for screening the uterine cervix cancer and its precursory lesions in developing countries.

Made available in DSpace on 2014-12-17T15:41:39Z (GMT). No. of bitstreams: 1 MirnaFF.pdf: 726469 bytes, checksum: 081aa47437617ba8013fcd1faab3c2f1 (MD5) Previous issue date: 2006-12-18 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / In this work biodiesel was gotten through the transesterification reaction using the oil of castor as source of triglycerides and using the methylic route for obtaining of esters. For the characterization of biodiesel and its mixtures with mineral diesel oil, physical chemical parameters and several analytical techniques had been used, as well as: gas chromatography (GC), nuclear magnetic resonance of proton (1H NMR), infrared spectroscopy (IR) and thermal analysis. The chromatography confirmed the complete reaction of esters in biodiesel presenting a 97,08% conversion. The 1H - NMR presented singlet in 3,6 ppm corresponding to the hydrogen of the group ester RCOO CH3. The infrared presented a strong band in 1741 cm-1 referring to stretching C=O of ester and an average band in 1175 cm-1 referring C O deformation. With the data of thermal analysis it was possible to observe the thermal and oxidative stability of the samples changing the atmospheres of synthetic air and nitrogen, where stages of the thermal decomposition had been verified and had been attributed to the volatilization and/or decomposition of the triacylglycerides. The thermal degradation of the samples was carried through 150 and 210?C during 1, 12, 24 and 48 hours and was observed change in the thermogravimetric profile, therefore an increase in the number of stages of the thermal decomposition also occurred indicating characteristic intermediate composites of polymerization, being this confirmed through the rheological study that presented brusque increase of viscosity. The kinetic study showed that the activation energy has the following order: biodiesel > mineral diesel oil > mixtures biodiesel/diesel / Neste trabalho o biodiesel foi obtido atrav?s da rea??o de transesterifica??o usando o ?leo de mamona como fonte de triglicer?deos e utilizando a rota met?lica para obten??o dos ?steres. Para a caracteriza??o do biodiesel e das suas misturas com o diesel mineral foram utilizados par?metros f?sico qu?micos e v?rias t?cnicas anal?ticas, como: cromatografia em fase gasosa (CG), resson?ncia magn?tica nuclear de pr?tons (RMN 1H), espectrofotometria na regi?o do infravermelho (IV) e an?lise t?rmica. A cromatografia confirmou a rea??o completa dos ?steres em biodiesel apresentando uma convers?o de 97,08%. O RMN 1H apresentou o singlete em 3,6 ppm correspondente aos hidrog?nios do grupo ?ster RCOO CH3. J? o infravermelho apresentou uma banda forte em 1741 cm-1 referente ao estiramento C=O do ?ster e uma banda m?dia a 1175 cm-1 referente a deforma??o C-O. Com os dados de an?lise t?rmica foi poss?vel observar a estabilidade t?rmica e oxidativa das amostras variando as atmosferas de ar sint?tico e nitrog?nio, onde foram verificadas etapas da decomposi??o t?rmica que foram atribu?das ? volatiliza??o e/ou decomposi??o dos triacilglicer?deos. A degrada??o t?rmica das amostras foi realizada a 150 e 210?C por 1, 12, 24 e 48 horas e foi observado mudan?a no perfil termogravim?trico, pois ocorreu um aumento no n?mero de etapas da decomposi??o t?rmica indicando compostos intermedi?rios caracter?sticos de polimeriza??o, sendo este fato tamb?m confirmado atrav?s do estudo reol?gico que apresentou aumento brusco de viscosidade. O estudo cin?tico realizado mostrou que a energia de ativa??o tem a seguinte ordem: biodiesel do ?leo de mamona > diesel > misturas biodiesel/diesel mineral

Made available in DSpace on 2014-12-17T15:41:58Z (GMT). No. of bitstreams: 1 AdrianaPBS_DISSERT.pdf: 2596487 bytes, checksum: f09071ef3141cb36b73492e4246e301b (MD5) Previous issue date: 2012-03-15 / O recente interesse em se obter materiais nanoporosos funcionalizados para aplica??es como calisadores heterog?neos e adsor??o de CO2, tem aumentado no meio industrial e cientifico. Nesta ?ltima aplica??o, a introdu??o de grupos aminas, como os presentes em quitosana, em materiais nanoporosos do tipo SBA-15 para gerar intera??es espec?ficas com o CO2 tem ganhado import?ncia. Assim, neste trabalho foram realizadas a s?ntese do SBA-15 e posterior impregna??o da CS no suporte mesoporoso atrav?s do m?todo de impregna??o por via ?mida. Os materiais obtidos foram caracterizados por meio DRX, TG, DSC, MEV, FTIR e adsor??o/dessor??o de N2. Os resultados de DRX indicaram que a estrutura ordenada do suporte SBA-15 foi preservada ap?s a impregna??o e os c?lculos mostraram que o di?metro m?dio do poro e/ou a espessura m?dia da parede (wt) foram alterados devido a introdu??o da quitosana nas amostras funcionalizadas. As curvas de TG e de DSC,corroboraram com os dados de DRX, indicando a presen?a da quitosana na estrutura mesoporosa do SBA-15, assim como as micrografias das amostras funcionalizadas, que possibilitou visualizar o estado de agrega??o do material obtido. As bandas caracter?sticas de absor??o da CS na regi?o IV foram identificadas e interpretadas nas amostras funcionalizadas confirmando as outras caracteriza??es. Foi visto tamb?m que a ?rea superficial diminuiu nas amostras funcionalizadas, indicando a sucessiva incorpora??o do pol?mero no suporte mesoporoso. A energia de ativa??o do processo de degrada??o t?rmica da quitosana impregnada no suporte foi determinada por meio do m?todo de cin?tica livre de Viazovkin e pelo m?todo de Ozawa-Flay-Wall com os resultados indicando que o aumento da quitosana diminui em aproximadamente 10% a energia de ativa??o para sua degrada??o.

Made available in DSpace on 2014-12-17T15:41:59Z (GMT). No. of bitstreams: 1 AdrianaPBS_DISSERT.pdf: 2596487 bytes, checksum: f09071ef3141cb36b73492e4246e301b (MD5) Previous issue date: 2012-03-15 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / The recent interest in obtaining functionalized nanoporous materials for applications such as heterogeneous catalysts and adsorption of CO2 has increased today. In the latter application, the introduction of amino groups such as present in the chitosan (CS), in the nanoporous materials like SBA-15 to generate specific interactions with CO2 has gained importance. In this work were performed to hydrothermal synthesis of SBA-15 and subsequent impregnation of the CS in the support mesoporous by the method of the wet impregnation. The materials were characterized by TG/DTG, DSC, XRD, SEM, FTIR and adsorption / desorption of N2. The XRD showed that the ordered structure of the support SBA-15 was preserved after the impregnation and calculations have shown that the average pore diameter (Dp) and / or the average wall thickness (wt) have been changed due to introduction of the CS in the samples functionalized. The curves of TG and DSC data corroborates the XRD, indicating the presence of CS in the nanoporous structure of SBA-15, as well as micrographs of samples, which allowed the display state of aggregation of the material obtained. The characteristics of bands absorption in the region of the CS in the FTIR were identified and interpreted in the samples functionalized, confirming the further characterization. Measurements showed that the BET surface area decreases in the functionalized samples, indicating the successive incorporation of the polymer in the nanoporous support. The activation energy apparent (Ea) for the process of thermal degradation of CS in the impregnated support was determined by the methods of kinetic freedom Vyazovkin and Ozawa-Flynn-Wall with the results indicating that the sample functionalized CS/SBA-15 2,5 % was decrease of the Ea in their degradation of about 10% compared to 1,0 % CS/SBA-15 sample / O recente interesse em se obter materiais nanoporosos funcionalizados para aplica??es como catalisadores heterog?neos e na adsor??o de CO2 tem aumentado atualmente. Nesta ?ltima aplica??o, a introdu??o de grupos aminas, como os presentes na quitosana (CS), em materiais nanoporosos do tipo SBA-15 para gerar intera??es espec?ficas com o CO2 tem ganhado import?ncia. Assim, neste trabalho foram realizadas a s?ntese hidrot?rmica do SBA- 15 e posterior impregna??o da CS no suporte mesoporoso atrav?s do m?todo de impregna??o por via ?mida. Os materiais obtidos foram caracterizados por meio de TG/DTG, DSC, DRX, MEV, FTIR e adsor??o/dessor??o de N2. Os resultados de DRX indicaram que a estrutura ordenada do suporte SBA-15 foram preservada ap?s a impregna??o e os c?lculos mostraram que o di?metro m?dio do poro (Dp) e/ou espessura m?dia da parede (wt) foram alterados devido a introdu??o da CS nas amostras funcionalizadas. As curvas de TG e DSC corroboraram com os dados de DRX, indicando a presen?a da CS na estrutura mesoporosa do SBA-15, assim como as micrografias das amostras funcionalizadas, que possibilitou visualizar o estado de agrega??o do material obtido. As bandas caracter?sticas de absor??o da CS da regi?o IV foram identificadas e interpretadas nas amostras funcionalizadas, confirmando as outras caracteriza??es. As medidas de BET mostraram que a ?rea superficial diminui nas amostras funcionalizadas, indicando a sucessiva incorpora??o do pol?mero no suporte nanoporoso. A energia de ativa??o aparente (Ea) do processo de degrada??o t?rmica da CS impregnada no suporte foi determinada por meio dos m?todos de cin?tica livre de Vyazovkin e de Ozawa-Flynn-Wall com os resultados indicando que a amostra funcionalizada CS/SBA-15 2,5 % teve uma diminui??o da Ea para a sua degrada??o de aproximadamente de 10% em rela??o a amostra de CS/SBA-15 1,0 %

Made available in DSpace on 2014-12-17T15:42:17Z (GMT). No. of bitstreams: 1 PauloHAH_DISSERT.pdf: 4112425 bytes, checksum: ab842493afe72a340f238b1cac2bc18f (MD5) Previous issue date: 2014-01-24 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / The Layered Double Hydroxides has become extremely promising materials due to its range of applications, easily obtained in the laboratory and reusability after calcination, so the knowledge regarding their properties is of utmost importance. In this study were synthesized layered double hydroxides of two systems, Mg-Al and Zn-Al, and such materials were analyzed with X-ray diffraction and, from these data, we determined the volume density, planar atomic density, size crystallite, lattice parameters, interplanar spacing and interlayer space available. Such materials were also subjected to thermogravimetric analysis reasons for heating 5, 10, 20 and 25 ? C / min to determine kinetic parameters for the formation of metaphases HTD and HTB based on theoretical models Ozawa, Flynn-Wall Starink and Model Free Kinetics. In addition, the layered double hydroxides synthesized in this working ratios were calcined heating 2.5 ? C / min and 20 ? C / min, and tested for adsorption of nitrate anion in aqueous solution batch system at time intervals 5 min, 15 min, 30 min, 1h, 2h and 4h. Such calcined materials were also subjected to exposure to the atmosphere and at intervals of 1 week, 2 weeks and 1 month were analyzed by infrared spectroscopy to study the kinetics of regeneration determining structural called "memory effect" / Os Hidr?xidos Duplos Lamelares tem se tornado materiais extremamente promissores devido a sua gama de aplica??es, f?cil obten??o em laborat?rio e a possibilidade de reutiliza??o ap?s calcina??o, portanto o conhecimento referente ? suas propriedades ? de extrema relev?ncia. Neste estudo foram sintetizados hidr?xidos duplos lamelares de dois sistemas, Mg-Al e Zn-Al, e tais materiais foram submetidos a an?lise com difra??o de raios X e, a partir de tais dados, foram determinados a densidade volum?trica, densidade at?mica planar, tamanho do cristalito, par?metros de rede cristalina, dist?ncia interplanar e espa?o interlamelar dispon?vel. Tais materiais tamb?m foram submetidos ? an?lise termogravim?trica em raz?es de aquecimento de 5, 10, 20 e 25 ?C/min para determina??o de par?metros cin?ticos durante a forma??o das metafases HTD e HTB com base nos modelos te?ricos de Ozawa, Flynn-Wall, Starink e Model Free Kinetics. Al?m disso, os hidr?xidos duplos lamelares sintetizados neste trabalhado foram calcinados em raz?es de aquecimento de 2,5 ?C/min e 20 ?C/min e submetidos a ensaios de adsor??o de ?nion nitrato em solu??o aquosa em sistema de batelada em intervalos de tempo de 5 min, 15 min, 30 min, 1h, 2h e 4h. Tais materiais calcinados tamb?m foram submetidos ? exposi??o com a atmosfera e em intervalos de tempo de 1 semana e 2 semanas foram analisados atrav?s de difra??o de raios X para estudo determina??o da cin?tica de regenera??o estrutural denominada efeito mem?ria

Made available in DSpace on 2014-12-17T15:42:26Z (GMT). No. of bitstreams: 1 WaldeniceAM.pdf: 1082421 bytes, checksum: bd7f6b4a35f59108d7807a3a68e163a3 (MD5) Previous issue date: 2007-03-27 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / Textile activity results in effluents with a variety of dyes. Among the several processes for dye-uptaking from these wastewaters, sorption is one of the most effective methods, chitosan being a very promising alternative for this end. The sorption of Methyl Orange by chitosan crosslinked particles was approached using equilibrium and kinetic analyses at different pH s. Besides the standard pseudo-order analysis normally effectuated (i.e. pseudo-first-order and pseudo-second-order), a novel approach involving a pseudo-nth-order kinetics was used, nbeing determined via non-linear regression, using the Levenberg-Marquardt method. Zeta potential measurements indicated that electrostatic interactions were important for the sorption process. Regarding equilibrium experiments, data were well fitted to a hybrid Langmuir-Freundlich isotherm, and estimated Gibbs free energy of adsorption as a function of mass of dye per area of chitosan showed that the process of adsorption becomes more homogeneous as the pH of the continuous phase decreased. Considering the kinetics of sorption, although a pseudo-nth-order description yielded good fits, a kinetic equation involving diffusion adsorption phenomena was found to be more consistent in terms of a physicochemical description of the sorption process / A atividade t?xtil resulta em efluentes com uma variedade de corantes. Dentre os v?rios processos para a remo??o de corantes destes efluentes, o de sor??o constitui um dos m?todos mais efetivos, sendo a quitosana um sorvente alternativo bastante promissor para este fim. A sor??o do corante alaranjado de metila em part?culas de quitosana reticulada foi avaliada atrav?s de estudos de equil?brio e cin?tica de sor??o em diferentes pHs. Al?m da an?lise com o modelo de pseudo-ordem normalmente adotado na literatura (por exemplo, pseudo-primeira-ordem e pseudo-segunda-ordem), um novo modelo envolvendo uma cin?tica de pseudo-n-ordem foi usada, sendo ndeterminado via regress?o n?o-linear, usando o m?todo de Levenberg-Marquardt. Medidas de potencial zeta indicaram intera??es eletrost?ticas importantes no processo de sor??o. Com rela??o aos estudos de equil?brio, os dados foram bem representados pela isoterma h?brida Langmuir-Freundlich, e a energia livre de Gibbs de sor??o como uma fun??o da massa de corante por ?rea de part?cula mostrou que este processo torna-se mais homog?neo ? medida que o pH da fase cont?nua diminui. Considerando a cin?tica de sor??o, apesar do modelo de pseudo-n-ordem descrever bem os dados experimentais, a equa??o cin?tica envolvendo difus?o-adsor??o foi mais consistente em termos de descri??o f?sico-qu?mica do processo de sor??o