Contribution to assessing the stiffness reduction of structural elements in the global stability analysis of precast concrete multi-storey buildings

This study deals with the reduction of the stiffness in precast concrete structural elements of multi-storey buildings to analyze global stability. Having reviewed the technical literature, this paper present indications of stiffness reduction in different codes, standards, and recommendations and compare these to the values found in the present study. The structural model analyzed in this study was constructed with finite elements using ANSYS® software. Physical Non-Linearity (PNL) was considered in relation to the diagrams M x N x 1/r, and Geometric Non-Linearity (GNL) was calculated following the Newton-Raphson method. Using a typical precast concrete structure with multiple floors and a semi-rigid beam-to-column connection, expressions for a stiffness reduction coefficient are presented. The main conclusions of the study are as follows: the reduction coefficients obtained from the diagram M x N x 1/r differ from standards that use a simplified consideration of PNL; the stiffness reduction coefficient for columns in the arrangements analyzed were approximately 0.5 to 0.6; and the variation of values found for stiffness reduction coefficient in concrete beams, which were subjected to the effects of creep with linear coefficients from 0 to 3, ranged from 0.45 to 0.2 for positive bending moments and 0.3 to 0.2 for negative bending moments.

Hydrothermally stable, conformal, sulfated zirconia monolayer catalysts for glucose conversion to 5-HMF

The grafting and sulfation of zirconia conformal monolayers on SBA-15 to create mesoporous catalysts of tunable solid acid/base character is reported. Conformal zirconia and sulfated zirconia (SZ) materials exhibit both Brönsted and Lewis acidity, with the Brönsted/Lewis acid ratio increasing with film thickness and sulfate content. Grafted zirconia films also exhibit amphoteric character, whose Brönsted/Lewis acid site ratio increases with sulfate loading at the expense of base sites. Bilayer ZrO2/SBA-15 affords an ordered mesoporous material with a high acid site loading upon sulfation and excellent hydrothermal stability. Catalytic performance of SZ/SBA-15 was explored in the aqueous phase conversion of glucose to 5-HMF, delivering a 3-fold enhancement in 5-HMF productivity over nonporous SZ counterparts. The coexistence of accessible solid basic/Lewis acid and Brönsted acid sites in grafted SZ/SBA-15 promotes the respective isomerization of glucose to fructose and dehydration of reactively formed fructose to the desired 5-HMF platform chemical.

Molecular Sieve Silica (MSS) Membranes for Gas Separation and Reaction Processes

Weakly branched silica films formed by the two-step sol-gel process allow for the formation of high selectivity membranes for gas separation. 29Si NMR and gas permeation showed that reduced crosslinking leads to He/CH4 selectivity improvement from 300 to 1000. Applied in membrane reactor for cyclohexane conversion to benzene, conversions were achieved at 14 fold higher than a conventional reactor at 250°C. Hydrothermal stability studies showed that carbon templating of silica is required for hydrothermally stable membranes. From our work it was shown that with correct application of chemistry, practical membrane systems can be built to suit gas separation (e. g. hydrogen fuel) and reactor systems.

Estudo da estabilidade térmica da pele

Mestrado em Engenharia Química

Recuperação do cromo contido nas cinzas provenientes da incineração de resíduos sólidos das indústrias coureira e calçadista visando a obtenção de cromato de sódio (VI)

O processo de transformação da pele em couro envolve uma seqüência complexa de reações químicas e processos mecânicos, no qual o curtimento representa fundamental estágio, por propiciar à pele características como qualidade, estabilidade hidrotérmica e excelentes propriedades para uso. O sulfato básico de cromo trivalente é o agente curtente predominantemente empregado no curtimento de peles em todo o mundo. É produzido a partir do cromato de sódio, industrialmente obtido do minério de cromo. Consideráveis quantidades de resíduos sólidos contendo cromo são geradas pelas indústrias coureira e calçadista. Estes resíduos tem sido motivo de preocupação constante, uma vez que são considerados perigosos devido a presença do cromo. O processo de incineração destes resíduos é uma importante alternativa a ser considerada, em decorrência de suas características de redução de massa, volume e possibilidade de aproveitamento da energia térmica dos gases de combustão. O processo de incineração dos resíduos das indústrias coureira e calçadista dá origem a cinzas contendo cerca de 40% de cromo que pode ser submetida a um processo de recuperação. Este trabalho apresenta os resultados da pesquisa sobre a utilização das cinzas, provenientes da incineração dos resíduos sólidos da indústria coureira e da indústria calçadista, para a produção de cromato de sódio(VI). No processo de planejamento e de condução dos experimentos foram utilizadas as técnicas de Planejamento Fatorial 2k, Metodologia de Superfície de Resposta e Análise de Variância na avaliação da produção de cromato de sódio(VI). Os fatores investigados foram: temperatura, taxa de aquecimento, tempo de reação, vazão de ar e quantidade de dolomita. A partir das variáveis selecionadas identificaram-se como parâmetros importantes a temperatura e a taxa de aquecimento. As superfícies de resposta tridimensionais obtidas a partir dos modelos de segunda ordem ajustados aos dados experimentais, apresentaram o comportamento do efeito conjugado dos fatores temperatura e taxa de aquecimento sobre a variável resposta grau de oxidação, desde a temperatura de inicio da reação química até a temperatura limite utilizada industrialmente. As condições de operação do processo de produção de cromato de sódio(VI) foram otimizadas. Os níveis ótimos dos fatores de controle aplicados as cinzas dos resíduos da indústria calçadista, geradas em uma planta piloto com incinerador de leito fixo, com tecnologia de gaseificação e combustão combinadas, apresentaram um grau de oxidação superior a 96% para as cinzas coletadas no ciclone e de 99,5% para as cinzas coletas no reator de gaseificação. Os resíduos sólidos, as cinzas e o produto de reação foram caracterizados por análises químicas, fluorescência de raio-X, microscopia eletrônica de varredura e difração de raio-X.

Desenvolvimento de sistemas de pastas leves para aplicação em cimentação de poços petrolíferos com baixo gradiente de fratura

All around the world, naturally occurring hydrocarbon deposits, consisting of oil and gas contained within rocks called reservoir rocks , generally sandstone or carbonate exists. These deposits are in varying conditions of pressure and depth from a few hundred to several thousand meters. In general, shallow reservoirs have greater tendency to fracture, since they have low fracture gradient, ie fractures are formed even with relatively low hydrostatic columns of fluid. These low fracture gradient areas are particularly common in onshore areas, like the Rio Grande do Norte basin. During a well drilling, one of the most favorable phases for the occurrence of fractures is during cementing, since the cement slurry used can have greater densities than the maximum allowed by the rock structure. Furthermore, in areas which are already naturally fractured, the use of regular cement slurries causes fluid loss into the formation, which may give rise to failures cementations and formation damages. Commercially, there are alternatives to the development of lightweight cement slurries, but these fail either because of their enormous cost, or because the cement properties were not good enough for most general applications, being restricted to each transaction for which the cement paste was made, or both reasons. In this work a statistical design was made to determine the influence of three variables, defined as the calcium chloride concentration, vermiculite concentration and nanosilica concentration in the various properties of the cement. The use of vermiculite, a low density ore present in large amounts in northeastern Brazil, as extensor for cementing slurries, enabled the production of stable cements, with high water/cement ratio, excellent rheological properties and low densities, which were set at 12.5 lb / gal, despite the fact that lower densities could be achieved. It is also seen that the calcium chloride is very useful as gelling and thickening agent, and their use in combination with nanosilica has a great effect on gel strength of the cement. Hydrothermal Stability studies showed that the pastes were stable in these conditions, and mechanical resistance tests showed values of the order of up to 10 MPa

Estudo comparativo entre a pirólise do polietileno de baixa densidade, utilizando vermiculita modificada e SBA-15

Catalytic processes are widely present in everyday life. This results in large number of studies seeking materials that may combine the low cost catalytic efficiency. Based on this assumption, the clays have long been used as catalysts, with its huge availability, diversity and possibility of improving their properties from structural changes, primarily responsible for this great use. Among the natural clays, vermiculite due to their characteristic properties (high cation exchange capacity and expansion), is suitable for various applications including as catalysts and catalyst supports. In this work, the acid leaching of clay vermiculite was performed, coming from Santa Luzia-PB, with nitric acid (2, 3 and 4 mol / L) and subsequent calcination of the materials obtained. The materials were named as Vx/400, where x is the acid concentration employed and 400 used in calcination temperature. The effectiveness of changes made was determined by XRD techniques, FT-IR, EDS, TG/DTG, nitrogen physisorption and DTP of n-butylamine. Acid leaching has improved some properties of the clay - specific area and acidity - but the control of the acid concentration used is of vital importance, since the highest concentration caused the partial destruction of vermiculite entailing a decline in their properties. For analysis of the catalytic activity of the modified clay was made a comparative study with the SBA -15 mesoporous materials, synthesized via hydrothermal method, using the pyrolysis of low density polyethylene (LDPE). The results showed that the acid plays a fundamental role in the conversion of the polymer into smaller molecules, the material V3/400 was more selective for the source monomer (ethylene) due to their increased acidity, which promotes more breaks bonds in the polymeric chain, while materials and V0/400 V2/400, lower acidity, showed higher selectivity to light hydrocarbons, the range of fuel (41.96 and 41.23%, respectively), due to less breakage and secondary condensation reactions chains; already V4/400 SBA-15/550 and resulted in lower percentages of light hydrocarbons and the partial destruction of the structure and low acidity, respectively, responsible for the inefficiency of materials

Avaliação do PH e da densidade óptica do corante azul de metileno tamponado e não tamponado após o contato com diferentes cimentos endodônticos

O objetivo deste trabalho foi avaliar o pH e a densidade óptica das soluções de azul de metileno a 1% e 2% (tamponadas e não tamponadas) após a imersão de três cimentos endodônticos. Foram preparados oitenta espécimes de cada cimento endodôntico (Endofill, AH Plus e Sealapex), os quais foram imersos nas soluções corantes. As soluções foram analisadas antes e após a imersão dos materiais nos períodos de tempo de 0, 24, 48 e 72h. Foram realizadas avaliações do pH utilizando um pHmetro e da densidade óptica utilizando um espectofotômetro ajustado em 596nm. Os dados de pH foram analisados através de estatística descritiva e os dados da densidade óptica foram analisados pela ANOVA e teste de Tukey 5%. Pôde-se verificar que as soluções corantes de azul de metileno tamponadas e não tamponadas apresentaram pequena variação nos valores de pH e densidade óptica antes do contato com os cimentos endodônticos. As soluções corantes não tamponadas apresentaram valores de pH menores que as tamponadas, independentemente do contato com qualquer cimento endodôntico. Os cimentos endodônticos promoveram alterações nos valores de pH das soluções corantes, sendo que as maiores alterações ocorreram nas soluções não tamponadas. Ocorreram alterações nos valores da densidade óptica das soluções corantes tamponadas e não tamponadas nos diferentes períodos de tempo de análise, sendo diferentes para cada cimento endodôntico utilizado

Numerical modelling of fluid-structure interaction with application in hemodynamics

The thesis deals with numerical algorithms for fluid-structure interaction problems with application in blood flow modelling. It starts with a short introduction on the mathematical description of incompressible viscous flow with non-Newtonian viscosity and a moving linear viscoelastic structure. The mathematical model consists of the generalized Navier-Stokes equation used for the description of fluid flow and the generalized string model for structure movement. The arbitrary Lagrangian-Eulerian approach is used in order to take into account moving computational domain. A part of the thesis is devoted to the discussion on the non-Newtonian behaviour of shear-thinning fluids, which is in our case blood, and derivation of two non-Newtonian models frequently used in the blood flow modelling. Further we give a brief overview on recent fluid-structure interaction schemes with discussion about the difficulties arising in numerical modelling of blood flow. Our main contribution lies in numerical and experimental study of a new loosely-coupled partitioned scheme called the kinematic splitting fluid-structure interaction algorithm. We present stability analysis for a coupled problem of non-Newtonian shear-dependent fluids in moving domains with viscoelastic boundaries. Here, we assume both, the nonlinearity in convective as well is diffusive term. We analyse the convergence of proposed numerical scheme for a simplified fluid model of the Oseen type. Moreover, we present series of experiments including numerical error analysis, comparison of hemodynamic parameters for the Newtonian and non-Newtonian fluids and comparison of several physiologically relevant computational geometries in terms of wall displacement and wall shear stress. Numerical analysis and extensive experimental study for several standard geometries confirm reliability and accuracy of the proposed kinematic splitting scheme in order to approximate fluid-structure interaction problems.

Synthesis and characterization of mesoporous TiO2 nanostructured films prepared by a modified sol-gel method for application in dye solar cells

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

beta-ZnMoO4 microcrystals synthesized by the surfactant-assisted hydrothermal method: Growth process and photoluminescence properties

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Effect of the surfactant nature on the thermo-stability of surface modified SnO2 nanoparticles

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

On the specific filtration mechanism of a mesoporous silica membrane, prepared with non-connecting parallel pores

We report the singular filtration properties of an ultrafiltration membrane made with mesoporous silica that exhibits cylindrical pores aligned mostly normal to the support. This membrane supported on tubular commercial macroporous alumina supports was prepared by the interfacial growth mechanism between stable silica-surfactant hybrid micelles made of the association of silica oligomers with polyethyleneoxide-based (PEO) surfactants and sodium fluoride, a well-known silica condensation catalyst [Boissière et al., An ultrafiltration membrane made with mesoporous MSU-X silica, Chem. Mater. 15 (2003) 460-463]. It appears that the combined effect of the silica nature of the membrane, whose surface charge can be easily adjusted by changing the pH and the non-connected cylindrical shape of the pores provides a new behavior in the retention properties, as proved by the filtration of polyoxyethylene polymers (PEO) with different molecular weights. Depending on the filtration conditions, a rejection rate of 80% and a steep cut-off at 2000 Da can be obtained or, on the reverse, polymers three times bigger than the pore diameter can diffuse through the membrane. This new filtration mechanism, which opens up new modes of separation modes, is explained in the light of both topology of the porous network and pH-dependent interactions between PEO polymers and silica porous media. © 2004 Elsevier B.V. All rights reserved.

beta-ZnMoO4 microcrystals synthesized by the surfactant-assisted hydrothermal method: Growth process and photoluminescence properties

In this communication, we investigate the effect of different surfactants: cetyltrimethylammonium bromide (CTAB), sodium dodecyl sulfate (SDS) and polyvinylpyrrolidone (PVP-K40) on the growth process of zinc molybdate (beta-ZnMoO4) microcrystals synthesized under hydrothermal conditions at 140 degrees C for 8 h. These microcrystals were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), and photoluminescence (PL) measurements. XRD patterns proved that these crystals are monophasic and present a wolframite-type monoclinic structure. FE-SEM images revealed that the surfactants modified the crystal shapes, suggesting the occurrence of distinct crystal growth processes. The CTAB cationic surfactant promotes the hindrance of small nuclei that leads to the formation of rectangle-like crystals, SDS anionic surfactant induces a growth of irregular hexagons with several porous due to considerable size effect of counter-ions on the crystal facets, PVP-K40 non-ionic surfactant allows a reduction in size and thickness of plate-like crystals, while without surfactants have the formation of irregular plate-like crystals. Finally, the PL properties of beta-ZnMoO4 microcrystals were explained by means of different shape/size, surface defects and order-disorder into lattice. (C) 2011 Elsevier B.V. All rights reserved.

Investigating the role of cholesterol in the formation of non-ionic surfactant based bilayer vesicles:thermal analysis and molecular dynamics

The aim of this research was to investigate the molecular interactions occurring in the formulation of non-ionic surfactant based vesicles composed monopalmitoyl glycerol (MPG), cholesterol (Chol) and dicetyl phosphate (DCP). In the formulation of these vesicles, the thermodynamic attributes and surfactant interactions based on molecular dynamics, Langmuir monolayer studies, differential scanning calorimetry (DSC), hot stage microscopy and thermogravimetric analysis (TGA) were investigated. Initially the melting points of the components individually, and combined at a 5:4:1 MPG:Chol:DCP weight ratio, were investigated; the results show that lower (90 C) than previously reported (120-140 C) temperatures could be adopted to produce molten surfactants for the production of niosomes. This was advantageous for surfactant stability; whilst TGA studies show that the individual components were stable to above 200 C, the 5:4:1 MPG:Chol:DCP mixture show ∼2% surfactant degradation at 140 C, compared to 0.01% was measured at 90 C. Niosomes formed at this lower temperature offered comparable characteristics to vesicles prepared using higher temperatures commonly reported in literature. In the formation of niosome vesicles, cholesterol also played a key role. Langmuir monolayer studies demonstrated that intercalation of cholesterol in the monolayer did not occur in the MPG:Chol:DCP (5:4:1 weight ratio) mixture. This suggests cholesterol may support bilayer assembly, with molecular simulation studies also demonstrating that vesicles cannot be built without the addition of cholesterol, with higher concentrations of cholesterol (5:4:1 vs 5:2:1, MPG:Chol:DCP) decreasing the time required for niosome assembly. © 2013 Elsevier B.V.