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No. of bitstreams: 2 Dissertação - Mário Henrique Gomes Brito - 2013.pdf: 6257761 bytes, checksum: 3ff568c727b44a8a7e645c8475216a03 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) Previous issue date: 2013-04-30 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / The overall objective of this research, which was essentially experimental, is to study the influence of the isothermal period and the maximum temperature of the thermal cure cycle steam under atmospheric pressure in the development of compressive strength of concrete blocks over time. The influences of two other types of curing are also being investigated; curing by enveloping with plastic sheet and open air curing, considered the last case scenario for reference. This study specifically aimed to further our understanding on how to; a) evaluate and quantify the importance of adopting procedures for curing the average resistance (Fbm) and characteristic (fbk) strength to compression of concrete blocks, comparing the processes of thermal curing and curing by enveloping plastic sheet to open air curing; b) evaluate statistically the aging effect of blocks over its compressive strength; c) evaluate the interaction effects of the variables "type of cure" and "age analysis" of the results of compressive strength of concrete blocks; and d) identify the main changes in the microstructure of the blocks subjected to a thermal curing process, especially observing eventual delayed ettringite formation in the internal structure of the material. To examine the influence of maximum curing temperature, two levels were adopted; 65°C and 85°C. As for analyzing the influence of isothermal period, three levels were adopted; 3 hours, 4 hours and 5 hours. The age analysis was evaluated in five levels; 1, 3, 7, 28 and 91 days. The results showed that the worst condition for curing, or curing type, was the open air curing (curing time approximately equal to 24 hours), which led to a lower overall average result of compressive strength of concrete blocks, proving the importance of adopting procedures of curing to optimize the mechanical performance of concrete blocks. Furthermore, it was also determined that the best curing conditions were the curing with enveloping plastic sheet (curing time approximately equal to 24 hours) and the thermal curing with steam under atmospheric pressure isotherm of 65°C and isothermal period of 3 hours (curing time approximately equals 8.5 hours), which were considered statistically equal. It was also observed that there was no significant influence of the curing in maximum temperature in relation to the compressive strength of the blocks. In the other hand, the isothermal period was very significant; the best condition was 3 hours, while 4 hours and 5 hours were considered statistically equal. Regarding the delayed ettringite formation, it was only verified for thermal curing conditions of isothermal of 85°C and isothermal period of 4 hours and 5 hours. / O objetivo geral desta pesquisa, de caráter essencialmente experimental, é estudar a influência do período isotérmico e da temperatura máxima do ciclo de cura térmica a vapor sob pressão atmosférica no desenvolvimento da resistência à compressão de blocos de concreto ao longo do tempo. Paralelamente, foram investigadas ainda as influências de dois outros tipos de cura, a saber: cura por envelopamento com lona plástica e cura ao ar livre, considerada esta última a situação de referência. De modo específico, o estudo visou ainda: a) avaliar e quantificar a importância da adoção de procedimentos de cura nas resistências média (fbm) e característica (fbk) à compressão de blocos de concreto, comparando os processos de cura térmica e cura por envelopamento com lona plástica com a cura ao ar livre; b) avaliar estatisticamente o efeito da idade dos blocos sobre a sua resistência à compressão; c) avaliar a interação dos efeitos das variáveis “tipo de cura” e “idade de análise” sobre os resultados de resistência à compressão dos blocos de concreto; e d) identificar as principais transformações ocorridas na microestrutura dos blocos submetidos aos processos de cura térmica, em especial observando eventual formação de etringita tardia na estrutura interna do material. Para analisar a influência da temperatura máxima de cura, foram adotados dois níveis: 65°C e 85°C. Já para analisar a influência do período isotérmico, foram adotados três níveis: 3 horas, 4 horas e 5 horas. Por sua vez, a idade de análise foi avaliada em cinco níveis: 1, 3, 7, 28 e 91 dias. Os resultados mostraram que a pior condição de cura, ou seja, o tipo de cura que conduziu ao menor resultado médio global de resistência à compressão dos blocos de concreto, foi a cura ao ar livre (tempo de cura aproximadamente igual a 24 horas), comprovando a importância da adoção de procedimentos de cura para a otimização do desempenho mecânico dos blocos de concreto. Além disso, foi verificado ainda que as melhores condições de cura foram a cura por envelopamento com lona plástica (tempo de cura aproximadamente igual a 24 horas) e a cura térmica a vapor sob pressão atmosférica com isoterma de 65°C e período isotérmico de 3 horas (tempo de cura aproximadamente igual a 8,5 horas), os quais foram considerados, estatisticamente, iguais. Também foi verificado que não houve influência significativa da temperatura máxima de cura em relação à resistência à compressão dos blocos. Já o período isotérmico foi significativo, de modo que a melhor condição foi 3 horas, enquanto 4 horas e 5 horas foram considerados, estatisticamente, iguais. Quanto à formação de etringita tardia, esta só foi verificada para as condições de cura térmica com isoterma de 85°C e períodos isotérmicos de 4 horas e 5 horas.

Background: The light-cured resin-based pit and fissure sealants success and longevity are enhanced by sufficient curing. Multiple emission peak Light Emitting Diode Light Curing Units offer a wider range of wavelengths and different levels of irradiances to ensure sufficient curing.The irradiance is considered a main curing factor that can affect the material properties. Purpose: The aim of this study was to assess the effect of different settings of a multiwave LED LCU on the degree of conversion and microhardness of a pit and fissure sealant comparing the irradiance of 1000 mW/cm2 to 1400 mW/cm2 and 3200 mW/cm2 irradiances of the LCU using manufacturer’s guidelines for curing times at 2, 4 and, 6 mm distances. Methods: A multiwave LED light curing unit was evaluated on three different irradiance levels 1000 mW/cm2 (S), 1400 mW/cm2 (H), and 3200 mW/cm2 (X). A total of 90 samples made from the fissure sealant were fabricated and divided into eighteen groups (n=5/group). Samples were cured following manufacturer’s guidelines of curing times for each curing mode at 2, 4, or 6 mm distance between the light tip and top of samples. The DC was measured using (ATR-FTIR) spectroscopy. The KHN test was performed on five different locations of each specimen using a hardness tester (Leco LM247AT, MI, USA, software; Confident V 2.5.2). Results: The top DC for H-8 was significantly higher than S-10 at 2 and 4mm, H-20 DC was significantly lower than S-30 at only 2mm. The bottom DC for H-8 was significantly higher than S-10 at 2mm only, H-20 DC was significantly lower than S-30 at 4 and 6mm only. H-8 KHN at top surface was significantly lower than S-10 at 2mm only, H-20 was significantly lower than S-30 at 2 and 6mm only. H-8 KHN at bottom surface was significantly lower than S-10 at 4 and 6mm but significantly higher at 2mm. H-20 was significantly lower than S-30 at 2mm but significantly higher at 4 and 6mm. The top DC for X-3 was significantly lower than S-10 at all curing distances with no significant difference at all curing distances between X-9 and S-30. The bottom DC for X-3 was significantly higher than S-10 at all curing distances with no significant difference between X-9 and S-30. X-3 KHN at top surface was significantly lower than S-10s at all curing distances. X-9 was significantly lower than S-30 at 6mm only. X-3 KHN at bottom surface was significantly lower than S-10 at 2 and 4mm only with no significant difference at all curing distances between X-9 and S-30. Conclusions: Using a multiwave LED LCU to polymerize Delton Opaque resin-based fissure sealants will result in an optimal DC and KHN values for any irradiance level if the curing distance is kept at 4 mm or less and with at least two cycles of the shortest curing time recommended by the manufacturer. Using a multiwave LED LCU with 1000, 1400 or 3200 mW/cm2 irradiance levels with shortest curing times recommended resulted in unsatisfactory DC and KHN levels. LED LCU with high and extra high irradiance levels (1400 and 3200 mW/cm2) can result in high DC and KHN levels when used adequately. Xtra Power mode (3200 mW/cm2) used on shortest curing time (3 seconds) resulted in significantly lower mechanical properties and for that reason it is not recommended to be used.

Organic coatings are widely used to lower the corrosion rate of metallic structures. However, penetration of water, oxygen and corrosive ions through pores present in the coating results in corrosion initiation and propagation once these species reach the metal substrate. Considering the need for systems that offer active protection with self-healing functionality, composite coatings containing polyaniline (PANI) conducting polymer are proposed in this study. In the first phase of my work, PANI was synthesized by various methods and characterized. The rapid mixing synthesis method was chosen for the rest of this study, providing PANI with high electrical conductivity, molecular structure of emeraldine salt, and morphology of spherical nanoparticles. PANIs doped with phosphoric and methane sulfonic acid revealed hydrophilic nature, and I showed that by incorporating a long-chain alkylphosphonic acid a hydrophobic PANI could be prepared. The second phase of my project was dedicated to making homogenous dispersions of PANI in a UV-curable resin based on polyester acrylate (PEA). Interfacial energy studies revealed the highest affinity of PEA to PANI doped with phosphoric acid (PANI-PA), and no attractive or long-range repulsive forces were measured between the PANI-PA surfaces in PEA.This is ideal for making conductive composites as, along withno aggregation tendency, the PANI-PA particles might come close enough to form an electrically connected network. Highly stable PEA/PANI-PA dispersions were prepared by pretreatment of PANI-PA in acetone followed by mixing in PEA in small portions under pearl-milling. The third phase of my project dealt with kinetics of the free radical polymerization that was utilized to cure the PEA/PANI-PA mixture. UV-vis absorption studies suggested a maximum allowed PANI-PA content of around 4 wt.% in order not to affect the UV curing behavior in the UV-C region. Real-time FTIR spectroscopy studies, using a laboratory UV source, revealed longer initial retardation of the photocuring and lower rates of crosslinking reactions for dispersions containing PANI-PA of higher than 3 wt.%. The presence of PANI-PA also made the formulations more sensitive to changes in UV light intensity and oxygen inhibition during UV curing. Nevertheless, curing of the dispersions with high PANI-PA content, of up to 10 wt.%, was demonstrated to be possible at either low UV light intensities provided the oxygen replenishment into the system was prevented, or by increasing the UV light intensity to very high levels. In the last phase of my project, the PEA and PEA/PANI-PA coatings, cured under high intensity UV lamps, were characterized. SEM analysis showed small PANI-PA particles to be closely packed within the matrix, and the electrical conductivity of the composite films was measured to be in the range of semiconductors. This suggested the presence of a connected network of PANI-PA, as confirmed by investigations of mechanical and electrical variations at the nanoscale by PeakForce TUNA AFM. The data revealed the presence of a PEA-rich layer at the composite-air interface, and a much higher population of the conductive network within the polymer matrix. High current signal was correlated with a high elastic modulus, consistent with the level measured for PANI-PA, and current-voltage studies on the conductive network showed non-Ohmic characteristics. Finally, the long-term protective property of the coatings was characterized by OCP and impedance measurements. Short-term barrier-type corrosion protection provided by the insulating PEA coating was turned into a long-term and active protection by addition of as little as 1 wt.% PANI-PA. A large and stable ennoblement was induced by the coatings containing PANI-PA of up to 3 wt.%. Higher content of PANI-PA led to poorer protection, probably due to the hydrophilicity of PANI-PA facilitating water transport in the coating and the presence of potentially weaker spots in the film. An iron oxide layer was found to fully cover the metal surface beneath the coatings containing PANI-PA after final failure observed by electrochemical testing. / <p>QC 20141103</p>

Master of Science / Department of Civil Engineering / Kyle Riding / Concrete is the most widely used construction material. Concrete strength and durability develop from a series of exothermic reactions involving water called hydration. Long-term durability and performance of concrete is very much dependent on the early hydration behavior of cementitious materials. This study examined the effects of curing temperature and access to moisture on the early age reaction rate of cementitious materials, and methods for quantifying these effects. Apparent activation energy (Ea) relates the effects of temperature on the cement hydration reaction. There are various methods and calculation techniques for estimating Ea that result in greatly varying values. Cement paste and mortar are often used to calculate Ea and used later for concrete. Ea values were calculated using cement mortar and paste by isothermal calorimetry and showed excellent correlation. This validates the use of Ea based on cement paste in modeling concrete behavior. Ea values were also calculated by chemical shrinkage and it showed potential for use in calculating Ea. Cementitious materials need free water to be available for hydration to continue. Curing with either waxy curing compounds or ponded water are common practices. The thickness of distilled water, lime-saturated water, and cement pore water used as a curing method affects the rate of hydration. Water-cementitious material ratio (w/cm) and sample depth affect the performance of water curing, with low w/cm being the most significant. Partial replacement of sand by fine lightweight aggregate also improves the hydration of cementitious material much more than conventional water ponding. Curing compounds showed improvements in cement hydration compared to uncured samples.

As a critical public safety-related structure, the long-term integrity of post-tensioned concrete containment buildings (PCCs) is necessary for continued operation of the reactors they house. In 2009, during preparations for a steam generator replacement, extensive subsurface laminar cracking was identified in a portion of the Crystal River 3 (CR3) PCC in Florida, and the plant was permanently shut down in 2013. This study investigates potential contributing factors to the identified cracking with particular focus on the effects of high early-age temperatures on the cracking risk of the concrete, on the development of the concrete properties, and on the late-age structural behavior of the concrete. Two planar, full-scale mock-ups of a portion of the CR3 PCC were constructed and instrumented with temperature and strain gauges to monitor the thermal and mechanical behavior during representative concrete curing and post-tensioning loading. Standard- and match-cured concrete specimens were tested for determination of the time- and temperature-dependent development of thermal and mechanical concrete properties, and hydration parameters were determined for the mock-up cement paste for modeling the heat generation in the concrete. These properties and parameters were utilized in 3D finite element analysis of the mock-ups in COMSOL Multiphysics and compared with experimental results. Non-destructive evaluation via shear wave tomography was conducted on the mock-ups to identify flaws and determine the effectiveness of the methods for identifying delaminations between post-tensioning ducts approximately 10 inches beneath the concrete surface. Though early-age thermal stresses were determined not to have caused cracking in the mock-ups, the high early-age concrete temperatures resulted in decreased late-age mechanical properties that were shown to contribute to greater concrete cracking risk when the mock-up was post-tensioned. Tensile stresses exceeding the tensile strength of the concrete were identified along the post-tensioning ducts when biaxial post-tensioning loads were applied in finite element analysis, but the stresses decreased rapidly with increased distance from the ducts. Through parametric modeling, increasing the tensile strength of the concrete was identified as an effective means of reducing the cracking risk in PCCs. Additionally, relationships between the mechanical properties for the standard- and match-cured specimens were identified that could enable prediction of in-place or match-cured concrete properties based only on the results of tests on fog-cured specimens.

Integration of dielectrics with increased porosity is required to reduce the capacitance of interconnects. However, the conventional dual damascene integration approach is causing negative effects to these materials avoiding their immediate implementation. A post-CMP curing approach could solve some of these issues. However, materials with porogens being stable at temperatures of the barrier-seed deposition process are not common, hindering this approach. Here, we report on an extended dual-damascene integration approach which permits post-CMP curing.

Depuis une dizaine d'années, les polymères hyperbranchés sont apparus dans la littérature. Ils possèdent un grand nombre de branchements ainsi qu'un grand nombre de groupes terminaux. La structure globulaire des polymères hyperbranchés les empêche de former des enchevêtrements. Il en résulte un avantage décisif pour leur application sous forme de revêtement de surface: les polymères hyperbranchés ont une viscosité plus faible à l'état fondu que les polymères linéaires. Cela permet aisément de les étaler sous forme de films minces sans utiliser de solvant. De plus, les polymères hyperbranchés possèdent un grand nombre de groupes terminaux qui peuvent être fonctionnalisés avec des monomères photoréticulables. Le but du travail de thèse est d'obtenir de nouveaux revêtements de surface, à partir de polymères hyperbranchés ou de polymères fortement branchés, qui trouveront leur application dans l'industrie chimique. La thèse s'articule autour de trois chapitres de synthèse suivis d'un chapitre traitant de la photoréactivité des oligomères linéaires, fortement branchés, et hyperbranchés. La première approche de synthèse envisagée est la copolymérisation alternante radicalaire. Divers maléimides ont été engagés dans des copolymérisations radicalaires avec des allyléthers sans succès. Lorsque ces derniers sont remplacés par des vinyls éthers, une copolymérisation alternante est observée. Néanmoins, une importante irreproductibilité est constatée, certains batchs donnant lieu à une gélification. La seconde voie de synthèse étudiée est l'approche classique de polycondensation de monomères de type AB2 . Le monomère AB2 est obtenu par addition de Michael de la diéthanolamine sur l'acrylate de méthyle. La polycondensation est concomitante avec l'acrylation des fonctions alcools. La compétition entre ces deux réactions limite les masses molaires accessibles bien que les réactions de transestérification soient catalysées par des dérivés du Zr et que la stoechiométrie ait été variée. La troisième voie de synthèse se base aussi sur la réaction de Michael. Des oligomères fortement branchés sont obtenus à partir de 1,6-hexanedioldiacrylate et d'éthylènediamine. Leurs analogues linéaires sont synthétisés en remplaçant l'éthylènediamine par la propylamine. Lors de ces synthèses, il est apparu que les oligomères fortement branchés ont une viscosité supérieure à celle des oligomères linéaires! Les oligomères hyperbranchés et acrylés, les oligomères linéaires et leurs analogues fortement branchés ont été étudiés du point de vue de leur photoréticulation sous rayonnement UV. Contrairement à ce qui était attendu, ils se sont montrés moins réactifs que les produits les plus performants de Cytec-Surface Specialties. Lors de cette étude, l'effet bénéfique des mines tertiaires sur l'inhibition par l'oxygène est apparu plus complexe que décrit dans la littérature.

Three sets of concrete blocks were cast to investigate the effects of natural exposure conditions, at the macro and microclimate scale, and field curing on the performance and durability of OPC and OPCjGGBS concretes. These are termed the Loughborough winter series, the Loughborough summer series and the Muscat summer series. Three concrete mixes were investigated in the two Loughborough series (30 and 50 MPa OPC concrete mixes and a 30 MPa OPCjGGBS concrete mix) and two in the Muscat weather series (the two 30 MPa concretes). A group of specimens were cast with each mix consisting of 600 x 500 x 150mm concrete blocks plus control cubes and prisms. The samples were cured in-situ and exposed to a range of curing methods and microclimates. Surface zone properties (up to 50mm depth) were evaluated by air permeability, sorptivity, carbonation, thermogravimetry (TG) and mercury intrusion porosimetry (MIP) tests, conducted after 3 and 12 months of site exposure. The results revealed distinct variations due to macroclimate, microclimate, curing, concrete type and age. The air permeability, sorptivity and carbonation of the concrete exposed under moderate and rainy conditions of a Loughborough summer season were lower than identical concrete cast and cured during a very cold and dry Loughborough winter season. Further, the sorptivity of concrete subjected to the hot and dry climatic conditions of Muscat was significantly higher than companion samples subjected to the temperate Loughborough climate. Significant variations in properties were observed within the two sides of the same concrete element, each subjected to a different microclimate. The air permeability, sorptivity, carbonation and porosity were reduced with increased hessian curing duration. However, premature drying of wet hessian during curing had an adverse effect on concrete quality as this produced concrete of higher permeability and carbonation than non-cured concrete. The application of controlled permeability formwork was effective in improving the concrete's sub-surface properties. The curing affected zone (CAZ) extended to approximately 20mm below the surface of the concrete that was exposed to the Loughborough winter and summer climate, and 40-50mm for the concrete exposed to the Muscat climate, with notable variation in properties due to climate and curing. The TG and MlP results provided insights into the mechanisms associated with the variations in the three concrete's properties due to natural field exposure.

This thesis examines how an integrative and preventative healing center is necessary for the wellness of our society and military personnel by understanding how food can react positively or negatively to someone's health depending on their blood type and the lifestyle they lead. The Health care profession predominantly focuses on curing disease while the preventative solutions are often overlooked and underestimated. Those who have food allergies' and what may seem to be a simple reoccurring sickness have very few places to go for guidance or real help since their problems are not considered a disease'. But the years of contamination could cause a complete immune system failure leading to cancer or some other life threatening disease. Our world once lived as one with nature relying on the earth's natural healing plants and foods. We were once fully dependent on it for healing but now we have isolated ourselves causing pain and confusion to not only our mind and body but to our earth and our environment. Misguided, lost and alone. This thesis responds to the problem of medical physicians overlooking or ignoring the natural healing aspects of plants and food and how our nation has become a fast food' processed nation that has caused an increase in health problems and blood disorders. A holistic healing arts center and resort. will combine the traditional medical practices with the alternative therapies to provide a treatment facility that is in search for the answers on an individual level. The patient or visitor will be the educated on their blood type and what types of food and fitness will be best to enhance their lives and create a daily balance for optimum wellness. / US Navy (USN) author.

Master of Science / Department of Chemical Engineering / J.R. Schlup / The curing reaction for the amine epoxy resin system of phenyl glycidyl ether (PGE) with metaphenylene diamine (mPDA) was investigated using two-dimensional correlation spectroscopy in the near-infared region (2DNIR). Synchronous and asynchronous correlation maps were generated using 2Dshige© software. The characteristic NIR band assignments were made, including the identification of new peaks for the O-H combination band in the 4825-4750 cm[superscript]-1 region and the CH stretching vibration overtone at 6018 cm[superscript]-1. Finally, the data suggests the reaction proceeds as follows: the appearance of the OH groups and C-H backbone vibrations occurs before the primary amine reactions and epoxide rings disappear.