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Low and medium temperature fuel cells: experimental tests and economic assessment / Low and medium temperature fuel cells: experimental tests and economic assessmentGiorgio Spagarino 11 December 2012 (has links)
A presente pesquisa foi desenvolvida para avaliar as potencialidades das células de combustível como tecnologia em si, inclusive os beneficios econômicos que se podem ter por meio do suprimento de energia elétrica se comparada com o aproveitamento da mesma por meio da rede pública. Além de uma parte descritiva do estado de arte da tecnologia, a presente dissertação foi focada em duas partes: a primeira trata de um estudo experimental onde uma célula, a membrana polimérica, foi conectada a um inversor, permitindo assim de fornecer energia elétrica na rede pública. Na segunda parte foi realizada uma avaliação engenhero-econômica com uma Célula de Combustível de Ácido Fosfórico para o aproveitamento da energia elétrica com cogeração de calor para as condições de mercado brasileiro. O primeiro estudo mostrou como seja possível abastecer uma célula (neste caso alimentada por hidrogênio) para fornecer continuamente energia elétrica na rede, onde necessário ou onde seja impossível para o usuário se conectar a rede pública. O segundo estudo, por sua vez, mostrou que atualmente a células de combustível de média temperatura de Ácido Fosfórico (PAFC) não é uma tecnologia ainda madura e que é viável economicamente somente em aplicações de nicho, por exemplo setores indústriais eletro-intensivos e com necessidade de energia termica também. Todavia, projeções futuras baseadas em curvas de aprendizados e a queda do preço do gás natural mostram como a expansão da tecnologia e a possibilidade de acessar um combustível barato podem abrir futuro para a PAFC mundialmente. / This Masters dissertation aims to study technical potentialities of Fuel Cell technology, including the economical benefits that can provide compared with public grid as well. Thus, the dissertation has been focused in two main parts: the first concerns in an experimental approach to supply electrical power to the public grid using a Polymer Electrolyte Membrane Fuel Cell (PEMFC), while the second one presents a global (from an engineering and economic point-of-view) assessment of a Phosphoric Acid Fuel Cell (PAFC) for the co-generation of heat with electrical energy in Brazil. The first study has been accomplished connecting a PEMFC with a power inverter to the public grid. It has been proved experimentally that Fuel Cell is an alternative device that, as long as fuel is fed, may provide electrical energy continuously and more efficiently than traditional devices. The second study has been focused in the so-called Phosphoric Acid Fuel Cell (PAFC) that, being a Medium Temperature Fuel Cell, beyond to supply electrical energy, may be used for co-generation of thermal energy. Through this study it has been showed that, at the current state-of-art, PAFC is is not already a mature technology and it becomes economically viable only for niche market applications, represented by the industrial sectors with high base load power and continuous thermal energy demand. However, accumulated knowledge expressed by learning curve and natural gas shock price caused by possible LNG supplying and shale gas recovery are the two main factors that may turn investment in PAFC profitable worldwide.
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Sintese e marcacao com P-32 de fosfatos de monoalquila e do fosfato de monofenila sob forma de sais de bis-ciclohexilamonio. Determinacao de espectros de absorcao em infra-vermelho e de ressonancia nuclear magneticaALMEIDA, MARIA A.T.M. de 09 October 2014 (has links)
Made available in DSpace on 2014-10-09T12:23:11Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:56:29Z (GMT). No. of bitstreams: 1
00636.pdf: 4746331 bytes, checksum: 49aa6e0eb3bdd9da261862a04bcb4b58 (MD5) / Dissertacao (Mestrado) / IEA/D / Instituto de Quimica, Universidade de Sao Paulo - IQ/USP
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A influência do ferro e do óxido de cério sobre a condutividade elétrica e a resistência à corrosão do alumínio anodizado / The iron and cerium oxide influence on the electric conductivity and the corrosion resistance of anodized aluminumSOUZA, KELLIE P. de 09 October 2014 (has links)
Made available in DSpace on 2014-10-09T12:51:44Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:08:36Z (GMT). No. of bitstreams: 0 / Investiga-se a influência de diferentes tratamentos sobre o sistema alumínio com cobertura de óxido de alumínio. A anodização do alumínio em meio de ácido sulfúrico e meio misto de sulfúrico e fosfórico foi empregada para alterar a resistência à corrosão, a espessura, o grau de cobertura e a microdureza do óxido anódico; e a eletrodeposição de ferro no interior óxido anódico em meio de sulfato com tratamento químico de selagem com cério, para alterar a sua condutividade elétrica e a sua resistência à corrosão. Para a eletrodeposição de ferro aplicou-se corrente contínua e pulsada e diversificou-se a composição do eletrólito de Fe(SO4)2(NH4)2.6H2O, com a adição dos ácidos bórico e ascórbico e para o tratamento de selagem, variou-se a concentração do CeCl3. A espectroscopia de energia dispersiva de raios X (EDS), a fluorescência de raios X (FRX) e a análise morfológica por microscopia eletrônica de varredura (MEV) permitiram verificar que, a corrente pulsada eleva o teor de ferro na camada anódica e a presença dos aditivos inibe a oxidação do ferro. As curvas cronopotenciométricas obtidas durante a eletrodeposição de ferro indicaram que a mistura dos ácidos bórico e ascórbico aumentaram a eficiência do processo de eletrodeposição. A espectroscopia de impedância eletroquímica (EIE), medidas de microdureza Vickers (H) e análise morfológica evidenciaram que o tratamento de selagem melhora a resistência à corrosão do filme óxido modificado com ferro. As medidas de impedância elétrica por duas pontas permitiram comprovar o aumento da condutividade elétrica do alumínio anodizado com ferro, mesmo após o tratamento com baixas concentrações de cério. Nanofios de ferro foram preparados utilizando os poros do óxido anódico como matriz. / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP
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Estudo da influência das soluções desmineralizadoras na atividade proteolítica da dentina humana sadia / The influence of demineralizing solutions in the proteolytic activity of human dentin healthyAndré Guaraci De Vito de Moraes 25 October 2012 (has links)
A degradação da interface adesiva em dentina pode acometer tanto a porção resinosa como a porção orgânica da camada híbrida. Evidências indicam que a degradação da porção orgânica pode ocorrer em parte devido a atividade enzimática de proteases da própria dentina. As metaloproteinases da matriz (MMPs) constituem a primeira classe de enzimas relacionada com a degradação da matriz orgânica. É possível que as MMPs, possam ser reativadas durante o procedimento adesivo em conseqüência da queda do pH do meio. Objetivo: Esta investigação teve como objetivos avaliar a influência de soluções desmineralizadoras com diferentes concentrações de ácido fosfórico (AF1%, AF10% e AF37%) na atividade proteolítica da dentina humana sadia, na degradação do colágeno exposto pela desmineralização, além de identificar imunologicamente as metaloproteinases. Material e Métodos: Vinte dentes molares permanentes foram triturados para obtenção de um pó de dentina. Alíquotas de 1g do pó foram acondicionadas em tubos plásticos para que a desmineralização do substrato pudesse ser realizada de acordo com as três diferentes concentrações de ácido fosfórico testadas. Após a neutralização do ácido com NaOH, as amostras foram centrifugadas. O sobrenadante foi utilizado para mensuração espectrofotométrica do conteúdo de Cálcio (Ca) liberado pela desmineralização. O precipitado obtido foi incubado com tampão de extração de proteínas por 24h a 4°C sob agitação. Nova centrifugação foi realizada e o sobrenadante utilizado para avaliação da atividade da MMP-2 e MMP-9 por zimografia e para a identificação imunológica das metaloproteinases por western blot. O precipitado obtido pela centrifugação foi liofilizado e separado em alíquotas de 40mg (n=10) de pó de dentina para cada condição experimental. As alíquotas foram incubadas em saliva artificial por 24h a 37°C sob agitação e hidrolisadas em autoclave. Após incubação a 65°C por 40 min, as amostras foram avaliadas por espectrofotometria para que a mensuração da concentração do aminoácido hidroxiprolina (HYP) liberado pela degradação do colágeno exposto pudesse ser obtida. Fatias de 0.3 mm da dentina coronária de outro dente foram obtidas e desmineralizadas, de acordo com as diferentes concentrações de ácido fosfórico para avaliação da atividade enzimática através do método da zimografia in situ. Os resultados foram submetidos à análise de variância de um fator sem vinculação ou teste de Kruskal-Wallis para identificação das diferenças existentes entre os grupos experimentais. Para contraste das médias foi realizado o teste de Student-Newman-Keuls com nível de significância de 5% (=0,05). Resultados: A atividade enzimática de MMP-2 foi estatisticamente maior quando a dentina foi desmineralizada com AF 1% ou 10%. O uso do ácido fosfórico 37% diminuiu consideravelmente a atividade desta enzima, em relação ao AF10% (<0,05). Em nenhuma das amostras desmineralizadas com AF foi detectada a atividade enzimática da MMP-9. A identidade da MMP-2 foi confirmada pelo immunoblotting da enzima com anticorpo específico. A MMP-9 não foi expressa nos extratos analisados. A expressão de MMP-2 foi maior quando utilizado AF 1% ou 10% e menor quando foi utilizado o AF 37%. A utilização do AF 37% liberou valores de Ca, em g/mL, estatisticamente superiores aos valores determinados para os demais grupos (<0,05). A maior concentração de HYP, em g/mL, foi encontrada nos extratos desmineralizados com AF 10%. Em seguida, aparecem os valores encontrados com o uso do AF1%. Os menores valores da concentração de HYP aparecem no grupo em que foi utilizado o AF 37% (<0,05). A concentração de HYP em função do peso de dentina utilizado (40mg) também foi calculada. A maior concentração de HYP por mg de dentina foi obtida com AF 10%, seguida pelos extratos desmineralizados com AF1%. Os menores valores foram detectados com AF 37% (<0,05). O uso do AF10% demonstrou ser responsável pela maior taxa de degradação de colágeno exposto (20,13%). Em seguida, aparecem valores intermediários (11,34%) obtidos com AF1%. Por último, surgem os menores valores (0,68%) com AF37%. A análise das imagens obtidas após a realização da zimografia in situ demonstrou maior atividade enzimática quando a dentina foi desmineralizada com AF10%. Conclusão: O uso do AF37% para o condicionamento da dentina durante a realização do procedimento adesivo pode minimizar os efeitos degradantes das proteases endógenas sobre o colágeno. Em contrapartida, estudos realizados com pó de dentina desmineralizado com AF1% ou 10% podem estar sobreestimando a atividade das MMPs, em relação à prática clínica. / The dentin adhesive interface degradation can occur in resin and in organic portion of the hybrid layer. Evidence indicates that the degradation of organic matrix may partially occur due to the enzymatic activity of proteases own dentin. The matrix metalloproteinases (MMPs) have been described as the first class of enzymes associated with degradation of the organic matrix. It is possible that MMPs may be reactivated during the adhesive procedure as a result of the fall of pH. Purpose: The objectives of the present investigation are to evaluate the influence of different demineralizing phosphoric acid solutions (PA1%, PA10% and PA37%) on the proteolytic activity of human sound dentin, on the collagen degradation that was exposed after demineralization, as well as to identify the metaloproteases immunologically. Material and Methods: Dentin powder was obtained from twenty human molars. One gram aliquots were placed in polyestyrene tubes and the dentin demineralization was performed using the three different phosphoric acid concentrations tested in this study. After neutralization with NaOH, the samples were centrifuged. The supernatant was used for the spectrophotometrically quantification of calcium (Ca) released by the demineralization while the precipitate was re-suspended and incubated with a protein extraction buffer for 24h at 4ºC under agitation. The sample was centrifuged and the supernatant was used for the identification of MMP-2 and MMP-9 by western blot and for the evaluation of gelatinolytic activity by zymography. The pellet was lyophilized and 40 mg aliquots of the dentin powder (n=10) were incubated in artificial saliva for 24h at 37°C under agitation and hydrolysed in autoclave after incubation at 65°C for 40 min. The samples were analyzed spectrophotometrically to measure the hydroxyproline (HYP) released after collagen degradation. Slices of 0.3 mm of the dentine crown of the another tooth were obtained and demineralized in accordance with the concentrations of phosphoric acid used in this study for evaluating the enzymatic activity by the method of in situ zymography.The data were analyzed by ANOVA one-way or Kruskal-Wallis test for the identification of differences between the experimental groups. The means were analyzed by Student-Newmans-Keulss test (=0,05). Results: The MMP-2 enzymatic activity was statistically higher when the dentin was demineralized with 1% or 10% PA. The 37% phosphoric acid decreased the activity of such enzyme relative to PA 10% (<0,05). MMP-9 activity was not detected in any demineralization condition (1%, 10% or 37% PA). MMP-2 identification was confirmed by immunoblotting while MMP-9 was not observed in any condition. MMP-2 identification was higher when 1% or 10% PA were used while 37% PA showed lower MMP-2 identification. The use of 37% PA resulted in higher release of Ca, which was significantly higher when compared to other PA concentrations (<0,05). The highest HYP concentration was observed when 10% PA was used, followed by 1% PA. The lowest values were observed for 37% PA (<0,05). The HYP concentration according to the dentin weight used (40 mg) was also calculated. Highest concentrations of HYP per mg of dentin were observed for 10% and 1% PA, while 37% PA resulted in the lowest HYP concentration (<0,05). The use of 10% PA showed to be responsible for the highest exposed collagen degradation after demineralization (20,13%) when compared to 1% PA (11,34%) and 37% PA (0,68%). The analysis of images obtained after the realization of in situ zymography showed greater enzyme activity when the dentin was demineralized in PA10%. Conclusion: The use of 37% PA for dentin etching during the restorative procedure might minimize collagen degradation by host-derived proteases. On the other hand, studies that have been using 1% or 10% PA might have overestimated MMPs activity when compared to the clinical situation.
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Cyclisation cascades via reactive iminium intermediatesGregory, Alexander William January 2014 (has links)
The aim of this D.Phil was to develop a range of cyclisation cascades, which initially form a reactive iminium intermediates that can then be attacked by a pendant nucleophile resulting in novel polycyclic structures. This concept has been applied to the development of three methodologies and has resulted in the discovery of new reactivity as well as the synthesis of a wide range of interesting novel structures <b>Chapter 1: Enantioselective chiral-BINOL-phosphoric acid catalysed reaction cascade</b> A highly enantioselective hydroamination / N-sulfonyliminium cyclisation cascade using a combination of Au(I) and chiral phosphoric acid catalysts has been developed. Proceeding by an initial 5-exo-dig hydroamination and a subsequent phosphoric acid catalysed Pictet- Spengler cyclisation, the reaction provides access to complex sulfonamide scaffolds in excellent yields and with high levels of enantiocontrol. The scope can be extended to lactam derivatives, with excellent yields and enantiomeric excesses of up to 93% ee. <b>Chapter 2: Iridium catalysed nitro-Mannich cyclisation</b> A new chemoselective reductive nitro-Mannich cyclisation reaction sequence of nitroalkyltethered lactams has been developed. An initial rapid and chemoselective iridium(I) catalysed reduction of lactams to the corresponding enamine is subsequently followed by intra molecular nitro-Mannich cyclisation. This methodology provides direct access to important alkaloid, natural product-like structures in yields up to 81% and in diastereoselectivities that are typically good to excellent. An in-depth understanding of the reaction mechanism has been gained through NMR studies and characterisation of reaction intermediates. The new methodology has been applied to the total synthesis of (±)-epi-epiquinamide in 4 steps. <b>Chapter 3: Iridium catalysed reductive interrupted Pictet-Spengler cyclisation</b> A novel reductive interrupted Pictet-Spengler cyclisation reaction cascade has been created. An iridium(I) catalyzed partial reduction of lactams/amides to the corresponding iminium is subsequently trapped by a pendant indole nucleophile. Interruption of the Pictet-Spengler reaction by indolium reduction provides a wide range of novel spirocyclic indoline moieties in excellent yield and diastereoselectivity.
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Poly (2,5-benzimidazole) based polymer electrolyte membranes for high temperature fuel cell applicationsLiu, Qingting January 2010 (has links)
Polymer electrolyte membrane fuel cells (PEMFCs) are one of the most promising clean technologies under development. However, the main obstacles for commercialising PEMFCs are largely attributed to the technical limitations and cost of current PEM materials such as Nafion. Novel poly(2,5-benzimidazole) (ABPBI)/POSS based polymer composite electrolyte membranes with excellent mechanical and conductivity properties were developed in this project including (I) ABPBI, polybenzimidazole (PBI) and their copolymers were synthesised by solution polymerisation and their chemical structures were confirmed by FTIR and elemental analysis. ABPBI/ActaAmmonium POSS (ABPBI/AM) and ABPBI/TriSilanolPhenyl POSS (ABPBI/SO) composites were also synthesised in situ. High quality polymer and composite membranes were fabricated by a direct cast method; and (II) The mechanical and thermal properties, microstructure and morphology, water and H3PO4 absorbility and proton conductivity of phosphoric acid doped and undoped ABPBI and ABPBI/POSS composite membranes were investigated. SEM/TEM micrographs showed that a uniform dispersion of POSS nano particles in ABPBI polymer matrix was achieved. The best performances on both mechanical properties and proton conductivities were obtained from the ABPBI/AM composite membrane with 3 wt% of POSS (ABPBI/3AM). It was found that both the water and H3PO4 uptakes were increased significantly with the addition of POSS due to formation of hydrogen bonds between the POSS and H2O/H3PO4, which played a critical role in the improvement of the conductivity of the composite membranes at temperatures over 100oC. ABPBI/3AM membranes with H3PO4 uptake above 117% showed best proton conductivities at both hydrous and anhydrous conditions from room temperature to 160oC, which is comparable with the conductivity of commercial Nafion 117 at 20oC in water-saturated condition, indicating that these composite membranes could be excellent candidates as a polymer electrolyte membrane for high temperature applications. A new mechanism for illustrating the improved proton conductivity of composite membranes was also developed.
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Pathophysiology of Respiratory Failure Following Acute Organophosphate Poisoning : A DissertationGaspari, Romolo Joseph 01 December 2009 (has links)
Organophosphate (OP) poisoning is a health issue worldwide with over 200,000 deaths per year. Although not a problem in most developed countries, in some third world countries, one third of a hospital’s population could be patients with OP exposure. Even with the most aggressive therapy, 10-40% of patients admitted to an intensive care unit will die. Research into the best practice for treating OP poisoning is lacking, due somewhat to a lack of detailed understanding of the physiology of OP poisoning. Our research uses animal models of acute OP poisoning to explore the mechanism of OP-induced respiratory failure.
Our research shows that animals poisoned with dichlorvos demonstrated a uniformly fatal central apnea that, if prevented, was followed immediately by a variable pulmonary dysfunction. Potential mechanisms for dichlorvos-induced central apnea can be divided into direct effects on the central respiratory oscillator (CRO) and feedback inhibition of the CRO. Two afferent pathways that can induce apnea include vagal feedback pathways and feed-forward pathways from the cerebral hemispheres. In our studies we found that vagal feedback and feed forward inhibition from the cerebral hemispheres were not required for OP-induced central apnea. The pre-Botzinger complex in the brainstem is thought to be the kernel of the CRO, but exposure of the pre-Botzinger complex to dichlorvos was not sufficient for apnea. Although OP induced central apnea was uniformly fatal, partial recovery of the CRO occurred post apnea with mechanical ventilation.
Central apnea was ubiquitous in our rat poisoning model, but pulmonary dysfunction was extremely variable, with a range of pulmonary effects from fulminate pulmonary failure with prominent pulmonary secretions to no pulmonary dysfunction at all. Vagal efferent activity is involved in neural control of pulmonary tissue but the vagus was not involved in OP-induced pulmonary dysfunction. Anti-muscarinic medications are the mainstay of clinical therapy and are commonly dosed by their effects on pulmonary secretions. Our studies found that atropine (the most common therapeutic agent for OP poisoning) resulted in a ventilation-perfusion mismatch secondary to effects on the pulmonary vasculature.
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Zum Einfluss textureller, struktureller und acider Eigenschaften phosphorsäuremodifizierter ZSM-5-Zeolithe auf die heterogen-katalysierte Umsetzung von GlycerolGöhlich, Maik 18 March 2011 (has links)
Die Nutzung von Kraftstoffen auf der Basis von Biodiesel erlaubt es, konventionelle, etablierte Antriebstechniken mit Nachhaltigkeit zu kombinieren. Daher kann in den nächsten Jahren mit einer weiteren weltweiten Steigerung der Biodieselproduktion gerechnet werden. Damit verbunden ist jedoch auch ein Anstieg der anfallenden Menge an Glycerol, das bei der Herstellung von Biodiesel als Koppelprodukt entsteht. Da traditionelle Märkte für Glycerol kaum mehr Wachstum zeigen, müssen neue Wege zur effizienten Verwertung von Glycerol gefunden werden. Die vorliegende Arbeit beschäftigt sich mit der heterogen-katalysierten Umsetzung von Glycerol zu Acrolein. Unter Verwendung von ZSM-5-Katalysatorproben mit unterschiedlichem Si/Al-Verhältnis und phosphorsäure-modifizierten Katalysatorproben konnte die Existenz von Synergieeffekten zwischen den texturellen, strukturellen und aciden Eigenschaften in der heterogen-katalysierten Glyceroldehydratisierung zu Gunsten der Acroleinselektivität eindeutig nachgewiesen werden. Eine selektive Umsetzung von Glycerol zu Acrolein wird daher an solchen Katalysatorproben ermöglicht, die ausgewogene texturelle, strukturelle und acide Eigenschaften aufweisen.
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The Effects Of Phosphate And Silicate Inhibitors On Surface Roughness And Copper Release In Water Distribution SystemsMacNevin, David 01 January 2008 (has links)
The effects of corrosion inhibitors on water quality and the distribution system were studied. This dissertation investigates the effect of inhibitors on iron surface roughness, copper surface roughness, and copper release. Corrosion inhibitors included blended poly/ortho phosphate, sodium orthophosphate, zinc orthophosphate, and sodium silicate. These inhibitors were added to a blend of surface water, groundwater, and desalinated brackish water. Surface roughness of galvanized iron, unlined cast iron, lined cast iron, and polyvinyl chloride was measured using pipe coupons exposed for three months. Roughness of each pipe coupon was measured with an optical surface profiler before and after exposure to inhibitors. For most materials, inhibitor did not have a significant effect on surface roughness; instead, the most significant factor determining the final surface roughness was the initial surface roughness. Coupons with low initial surface roughness tended to have an increase in surface roughness during exposure, and vice versa, implying that surface roughness tended to regress towards an average or equilibrium value. For unlined cast iron, increased alkalinity and increased temperature tended to correspond with increases in surface roughness. Unlined cast iron coupons receiving phosphate inhibitors were more likely to have a significant change in surface roughness, suggesting that phosphate inhibitors affect stability of iron pipe scales. Similar roughness data collected with new copper coupons showed that elevated orthophosphate, alkalinity, and temperature were all factors associated with increased copper surface roughness. The greatest increases in surface roughness were observed with copper coupons receiving phosphate inhibitors. Smaller increases were observed with copper coupons receiving silicate inhibitor or no inhibitor. With phosphate inhibitors, elevated temperature and alkalinity were associated with larger increases in surface roughness and blue-green copper (II) scales.. Otherwise a compact, dull red copper (I) scale was observed. These data suggest that phosphate inhibitor addition corresponds with changes in surface morphology, and surface composition, including the oxidation state of copper solids. The effects of corrosion inhibitors on copper surface chemistry and cuprosolvency were investigated. Most copper scales had X-ray photoelectron spectroscopy binding energies consistent with a mixture of Cu2O, CuO, Cu(OH)2, and other copper (II) salts. Orthophosphate and silica were detected on copper surfaces exposed to each inhibitor. All phosphate and silicate inhibitors reduced copper release relative to the no inhibitor treatments, keeping total copper below the 1.3 mg/L MCLG for all water quality blends. All three kinds of phosphate inhibitors, when added at 1 mg/L as P, corresponded with a 60% reduction in copper release relative to the no inhibitor control. On average, this percent reduction was consistent across varying water quality conditions in all four phases. Similarly when silicate inhibitor was added at 6 mg/L as SiO2, this corresponded with a 25-40% reduction in copper release relative to the no inhibitor control. Hence, on average, for the given inhibitors and doses, phosphate inhibitors provided more predictable control of copper release across changing water quality conditions. A plot of cupric ion concentration versus orthophosphate concentration showed a decrease in copper release consistent with mechanistic control by either cupric phosphate solubility or a diffusion limiting phosphate film. Thermodynamic models were developed to identify feasible controlling solids. For the no inhibitor treatment, Cu(OH)2 provided the closest prediction of copper release. With phosphate inhibitors both Cu(OH)2 and Cu(PO4)·2H2O models provided plausible predictions. Similarly, with silicate inhibitor, the Cu(OH)2 and CuSiO3·H2O models provided plausible predictions.
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Avaliação histológica da resposta pulpar humana a diferentes técnicas de instrumentação cavitária e de restauração / Histological evaluation of the human pulp response to different cavity instrumentation and restorative techniquesChiok Ocaña, Lourdes Rosa 27 November 2009 (has links)
Este estudo se propõe a analisar a resposta pulpar de dentes humanos a preparos cavitários de classe V, em função de duas diferentes técnicas de instrumentação e de duas diferentes técnicas de restauração. Para tal, cavidades classe V, nas superfícies vestibulares de 48 pré-molares hígidos de pacientes entre 11 e 25 anos, que estavam em tratamento ortodôntico, foram preparadas e restauradas de acordo com os seguintes grupos experimentais: G 1 (n=24) - preparos cavitários realizados com ponta diamantada em alta rotação, restaurados com guta-percha plastificada, cimento ionômero de vidro e verniz cavitário (G 1A; n=12) ou com técnicas adesivas (sistema restaurador adesivo aplicando-se o condicionamento ácido total) e cimento ionômero de vidro (G 1B; n=12); G 2 (n=24) - preparos cavitários com ponta CVD ativada por ultrassom, restaurados com gutapercha plastificada, cimento ionômero de vidro e verniz cavitário (G 2A; n=12) ou com técnicas adesivas (sistema restaurador adesivo aplicando-se o condicionamento ácido total) e cimento ionômero de vidro (G 2B; n=12); e G 3 (controle; n=4) - dentes que foram extraídos sem a realização de qualquer procedimento. Os preparos cavitários foram realizados mantendo o assoalho da cavidade o mais próximo possível da polpa, no entanto, sem provocar exposição pulpar. Os dentes foram extraídos após três períodos experimentais (imediato, sete e trinta dias após o preparo cavitário), fixados, descalcificados, e processados histologicamente. Cortes teciduais longitudinais seriados de 5 m foram obtidos, corados pelas técnicas de H & E e de Brown & Brenn, e examinados em microscopia ótica. As avaliações morfométricas e por escores foram realizadas e os resultados das mesmas, submetidos, respectivamente, aos testes estatísticos de Mann-Whitney e de Kruskal-Wallis/Dunn, adotando-se um nível de significância de 5%. No período inicial, todos os grupos experimentais (1A, 1B, 2A e 2B) exibiram ligeiro desarranjo da camada odontoblástica vacuolizada e leve invasão da zona acelular de Weil. Não houve diferença entre os grupos experimentais iniciais e o grupo controle. No intervalo de sete dias, pôde-se observar redução da camada odontoblástica, muitos núcleos de odontoblastos aspirados nos túbulos dentinários, alguns espécimes com ausência de pré-dentina e resposta inflamatória aguda com hemorragia. Trinta dias depois, cinco espécimes do total avaliado apresentaram dentina terciária; dois espécimes do grupo 1B apresentaram necrose relacionada com a presença de bactérias nos túbulos dentinários; e os demais mostraram graus variados de inflamação crônica, associados a restaurações adesivas ou a processos de reparo, com proliferação de vasos e persistência de focos de hemorragia. Portanto, os dois tipos de instrumentação cavitária promovem respostas pulpares similares entre si, mas as diferentes técnicas restauradoras promovem efeitos significativamente diferentes sobre o complexo dentinopulpar. / The aim of this study is to analyze the pulp response of human teeth to class V cavity preparation, in function of two different instrumentation and restorative techniques. Class V cavities were made on the buccal surfaces of 48 sound human pre-molars from orthodontic patients from 11 to 25 years, and were divided as follows: G1 (n=24) cavity preparations were made with diamond bur under high speed, restored with either plasticized gutta-percha, glass ionomer cement and surface coated with varnish (G1A) or adhesive protocol (total etch technique and adhesive system application) with glass ionomer filling (G1B); G2 (n=24) cavity preparations were made with diamond CVD point and ultrasonic device, restored with either plasticized gutta-percha, glass ionomer cement and surface coated with varnish (G2A) or adhesive protocol (total etch technique and adhesive system application) with glass ionomer filling (G2B); and control group G3 (n=4) extracted teeth with no previous cavity preparation. All avities were prepared with the cavity floor as close to the pulp as possible, without causing pulp exposure. Teeth extractions were made in three experimental periods (immediate, 7 and 30 days after cavity preparation) and right after extraction they were submitted to histological procedures. Longitudinal tissue serial sections of 5 mm were obtained, H&E and Brown&Brenn stained, and analyzed under optical microscope. Morphometric and score evaluations were carried out and data from both were, respectively, submitted to Mann-Whitney and Kruskal-Wallis/Dunn tests, with 5% significance. Immediately, all experimental groups (1A, 1B, 2A and 2B) exhibited a discrete disorganization of the odontoblastic layer and invasion of the Weil zone. There was no difference between experimental and control groups. At 7-day interval, a decrease of the odontoblastic layer was observed. Many odontoblasts nucleus were seen displaced into the dentinal tubules. Some specimens showed absence of pre-dentine and inflammatory pulp response with hemorrhage. Thirty days later, five specimens presented tertiary dentin formation; two specimens from group 1B presented necrosis coincident with bacteria inside the dentinal tubules; the other specimens showed various degrees of chronic inflammation, associated to adhesive restorations or repair processes, with blood vessels proliferation and persistent hemorrhagic areas. Therefore, both instrumentation techniques promoted similar pulp response, but different restoration procedures elicited significantly different responses of the dentinpulp complex.
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