Control of integrated unit operations

As a thermal separation method, distillation is one of the most important technologies in the chemical industry. Given its importance, it is no surprise that increasing efforts have been made in reducing its energy inefficiencies. A great deal of research is focused in the design and optimization of the Divided-Wall Column. Its applications are still reduced due to distrust of its controllability. Previous references studied the decentralized control of DWC but still few papers deal about Model Predictive Control. In this work we present a decentralized control of both a DWC column along with its equivalent MPC schema.

Proyecto de evaluación de un yacimiento de gas mediante fracturación hidráulica

En este proyecto se evalúa la posibilidad de mejorar la producción de gas en un yacimiento en el que las reservas son todavía suficientes para ser explotadas. Para realizar esta evaluación se estudia en primer lugar la cantidad de gas que se extrae sin ningún método de mejoramiento de producción, y después se evalúa la cantidad de gas que se extraería si se aplicase el método de estimulación de yacimientos llamado fracturación hidráulica mediante unos ensayos de calibración que se han realizado en uno de los pozos que hay en el yacimiento de gas. Finalmente se hace una comparación económica de cómo mejoraría la producción de gas cuando el yacimiento no está estimulado y cuando lo está. Además, se aprovecha también para hacer una sucinta revisión de la base teórica de la fracturación hidráulica y de la ingeniería de yacimientos, así como un breve estudio de impacto ambiental de la fracturación. ABSTRACT This project is trying to assess the possibility to improve the gas production of a reservoir in which there are still enough reserves to be exploited. To do that, it is necessary to evaluate the quantity of gas that is producing without any type of stimulation method and then assess how the production will grow if a stimulation method called hydraulic fracturing is applied though some calibration tests, subsequently compare how much the incomes will be increased in case of application of the stimulation method. In addition, some of the basis and concepts of reservoir stimulation and reservoir engineering are reviewed in order to understand the project. Finally, a brief environmental impact is also assessed.

Detection of exocytosis at individual pancreatic beta cells by amperometry at a chemically modified microelectrode.

Amperometry at a carbon fiber microelectrode modified with a composite of ruthenium oxide and cyanoruthenate was used to monitor chemical secretions of single pancreatic beta cells from rats and humans. When the insulin secretagogues glucose, tolbutamide, and K+ were applied to the cell, a series of randomly occurring current spikes was observed. The current spikes were shown to be due to the detection of chemical substances secreted from the cell. Chromatography showed that the primary secreted substance detected by the electrode was insulin. The current spikes were strongly dependent on external Ca2+, had an average area that was independent of the stimulation method, and had an area distribution which corresponded to the distribution of vesicle sizes in beta cells. It was concluded that the spikes were due to the detection of concentration pulses of insulin secreted by exocytosis.

The stimulus-response curve and motor unit variability in normal subjects and subjects with amyotrophic lateral sclerosis

The behavior and stability of motor units (MUs) in response to electrical stimulation of different intensities can be assessed with the stimulus-response curve, which is a graphical representation of the size of the compound muscle action potential (CMAP) in relation to stimulus intensity. To examine MU characteristics across the whole stimulus range, the variability of CMAP responses to electrical stimulation, and the differences that occur between normal and disease states, the curve was studied in 11 normal subjects and 16 subjects with amyotrophic lateral sclerosis (ALS). In normal subjects, the curve showed a gradual increase in CMAP size with increasing stimulus intensity, although one or two discrete steps were sometimes observed in the upper half of the curve, indicating the activation of large MUs at higher intensities. In ALS subjects, large discrete steps, due to loss of MUs and collateral sprouting, were frequently present. Variability of the CMAP responses was greater than baseline variability, indicating variability of MU responses, and at certain levels this variability was up to 100 mu Vms. The stimulus-response curve shows differences between normal and ALS subjects and provides information on MU activation and variability throughout the curve.

Synthesis of novel and stable g-C3N4/N-doped SrTiO3 hybrid nanocomposites with improved photocurrent and photocatalytic activity under visible light irradiation

Hybrid nanocomposites based on N-doped SrTiO3 nanoparticles wrapped in g-C3N4 nanosheets were successfully prepared by a facile and reproducible polymeric citrate and thermal exfoliation method. The results clearly indicated that the N-doped SrTiO3 nanoparticles are successfully wrapped in layers of the g-C3N4 nanosheets. The g-C3N4/N-doped SrTiO3 nanocomposites showed absorption edges at longer wavelengths compared with the pure g-C3N4 as well as N-doped SrTiO3. The hybrid nanocomposites exhibit an improved photocurrent response and photocatalytic activity under visible light irradiation. Interestingly, the hybrid nanocomposite possesses high photostability and reusability. Based on experimental results, the possible mechanism for prolonged lifetime of the photoinduced charge carrier was also discussed. The high performance of the g-C3N4/N-doped SrTiO3 photocatalysts is due to the synergic effect at the interface of g-C3N4 and N-doped SrTiO3 hetero/nanojunction including the high separation efficiency of the charge carrier, band energy matching and the suppressed recombination rate. Therefore, the hybrid photocatalyst could be of potential interest for water splitting and environmental remediation under natural sunlight.

Early transplantation of mesenchymal stem cells after spinal cord injury relieves pain hypersensitivity through suppression of pain-related signaling cascades and reduced inflammatory cell recruitment

Bone marrow-derived mesenchymal stem cells (BMSC) modulate inflammatory/immune responses and promote motor functional recovery after spinal cord injury (SCI). However, the effects of BMSC transplantation on central neuropathic pain and neuronal hyperexcitability after SCI remain elusive. This is of importance because BMSC-based therapies have been proposed for clinical treatment. We investigated the effects of BMSC transplantation on pain hypersensitivity in green fluorescent protein (GFP)-positive bone marrow-chimeric mice subjected to a contusion SCI, and the mechanisms of such effects. BMSC transplantation at day 3 post-SCI improved motor function and relieved SCI-induced hypersensitivities to mechanical and thermal stimulation. The pain improvements were mediated by suppression of protein kinase C-γ and phosphocyclic AMP response element binding protein expression in dorsal horn neurons. BMSC transplants significantly reduced levels of p-p38 mitogen-activated protein kinase and extracellular signal-regulated kinase (p-ERK1/2) in both hematogenous macrophages and resident microglia and significantly reduced the infiltration of CD11b and GFP double-positive hematogenous macrophages without decreasing the CD11b-positive and GFP-negative activated spinal-microglia population. BMSC transplants prevented hematogenous macrophages recruitment by restoration of the blood-spinal cord barrier (BSCB), which was associated with decreased levels of (a) inflammatory cytokines (tumor necrosis factor-α, interleukin-6); (b) mediators of early secondary vascular pathogenesis (matrix metallopeptidase 9); (c) macrophage recruiting factors (CCL2, CCL5, and CXCL10), but increased levels of a microglial stimulating factor (granulocyte-macrophage colony-stimulating factor). These findings support the use of BMSC transplants for SCI treatment. Furthermore, they suggest that BMSC reduce neuropathic pain through a variety of related mechanisms that include neuronal sparing and restoration of the disturbed BSCB, mediated through modulation of the activity of spinal-resident microglia and the activity and recruitment of hematogenous macrophages.

Multifunctional nanoparticles in cancer: In vitro characterization, in vivo distribution, and cellular response after laser-NIR dye-induced heating

A novel biocompatible and biodegradable polymer, termed poly(Glycerol malate co-dodecanedioate) (PGMD), was prepared by thermal condensation method and used for fabrication of nanoparticles (NPs). PGMD NPs were prepared using the single oil emulsion technique and loaded with an imaging/hyperthermia agent (IR820) and a chemotherapeutic agent (doxorubicin, DOX). The size of the void PGMD NPs, IR820-PGMD NPs and DOX-IR820-PGMD NPs were approximately 90 nm, 110 nm, and 125 nm respectively. An acidic environment (pH=5.0) induced higher DOX and IR820 release compared to pH=7.4. DOX release was also enhanced by exposure to laser, which increased the temperature to 42°C. Cytotoxicity of DOX-IR820-PGMD NPs was comparable in MES-SA but was higher in Dx5 cells compared to free DOX plus IR820 (p<0.05). The combination of hyperthermia (HT) and chemotherapy improved cytotoxicity in both cell lines. We also explored the cellular response after rapid, short-term and low thermal dose (laser/Dye/NP) induced-heating, and compared it to slow, long-term and high thermal dose cell incubator heating by investigating the reactive oxygen species (ROS) level, hypoxia-inducible factor-1&agr; (HIF-1&agr;) and vascular endothelial growth factor (VEGF) expression. The cytotoxicity of IR820-PGMD NPs after laser/Dye/NP HT resulted in higher cancer cell killing compared to incubator HT. ROS level, HIF-1&agr; and VEGF expression were elevated under incubator HT, while maintained at the baseline level under the laser/Dye/NP HT. In vivo mouse studies showed that NP formulation significantly improved the plasma half-life of IR820 after tail vein injection. Significant lower IR820 content was observed in kidney in DOX-IR820-PGMD NP treatment as compared to free IR820 treatment in our biodistribution studies (p<0.05). In conclusion, both IR820-PGMD NPs and DOX-IR820-PGMD NPs were successfully developed and used for both imaging and therapeutic purposes. Rapid and short-term laser/Dye/NP HT, with a low thermal dose, did not up-regulate HIF-1&agr; and VEGF expression, whereas slow and long-term incubator HT, with a high thermal dose, can enhance expression of both HIF-1&agr; and VEGF.^

Crystallization on the Mesoscale : Self-Assembly of Iron Oxide Nanocubes into Mesocrystals

Self-assembly of nanoparticles is a promising route to form complex, nanostructured materials with functional properties. Nanoparticle assemblies characterized by a crystallographic alignment of the nanoparticles on the atomic scale, i.e. mesocrystals, are commonly found in nature with outstanding functional and mechanical properties. This thesis aims to investigate and understand the formation mechanisms of mesocrystals formed by self-assembling iron oxide nanocubes. We have used the thermal decomposition method to synthesize monodisperse, oleate-capped iron oxide nanocubes with average edge lengths between 7 nm and 12 nm and studied the evaporation-induced self-assembly in dilute toluene-based nanocube dispersions. The influence of packing constraints on the alignment of the nanocubes in nanofluidic containers has been investigated with small and wide angle X-ray scattering (SAXS and WAXS, respectively). We found that the nanocubes preferentially orient one of their {100} faces with the confining channel wall and display mesocrystalline alignment irrespective of the channel widths.  We manipulated the solvent evaporation rate of drop-cast dispersions on fluorosilane-functionalized silica substrates in a custom-designed cell. The growth stages of the assembly process were investigated using light microscopy and quartz crystal microbalance with dissipation monitoring (QCM-D). We found that particle transport phenomena, e.g. the coffee ring effect and Marangoni flow, result in complex-shaped arrays near the three-phase contact line of a drying colloidal drop when the nitrogen flow rate is high. Diffusion-driven nanoparticle assembly into large mesocrystals with a well-defined morphology dominates at much lower nitrogen flow rates. Analysis of the time-resolved video microscopy data was used to quantify the mesocrystal growth and establish a particle diffusion-based, three-dimensional growth model. The dissipation obtained from the QCM-D signal reached its maximum value when the microscopy-observed lateral growth of the mesocrystals ceased, which we address to the fluid-like behavior of the mesocrystals and their weak binding to the substrate. Analysis of electron microscopy images and diffraction patterns showed that the formed arrays display significant nanoparticle ordering, regardless of the distinctive formation process.  We followed the two-stage formation mechanism of mesocrystals in levitating colloidal drops with real-time SAXS. Modelling of the SAXS data with the square-well potential together with calculations of van der Waals interactions suggests that the nanocubes initially form disordered clusters, which quickly transform into an ordered phase.

Análise de métodos de predição de conforto térmico de habitação em clima quente-úmido com condicionamento passivo

The assessment of building thermal performance is often carried out using HVAC energy consumption data, when available, or thermal comfort variables measurements, for free-running buildings. Both types of data can be determined by monitoring or computer simulation. The assessment based on thermal comfort variables is the most complex because it depends on the determination of the thermal comfort zone. For these reasons, this master thesis explores methods of building thermal performance assessment using variables of thermal comfort simulated by DesignBuilder software. The main objective is to contribute to the development of methods to support architectural decisions during the design process, and energy and sustainable rating systems. The research method consists on selecting thermal comfort methods, modeling them in electronic sheets with output charts developed to optimize the analyses, which are used to assess the simulation results of low cost house configurations. The house models consist in a base case, which are already built, and changes in thermal transmittance, absorptance, and shading. The simulation results are assessed using each thermal comfort method, to identify the sensitivity of them. The final results show the limitations of the methods, the importance of a method that considers thermal radiance and wind speed, and the contribution of the chart proposed

Nanocząstki tlenków żelaza w hipertermii magnetycznej

Wydział Fizyki

Análise de métodos de predição de conforto térmico de habitação em clima quente-úmido com condicionamento passivo

The assessment of building thermal performance is often carried out using HVAC energy consumption data, when available, or thermal comfort variables measurements, for free-running buildings. Both types of data can be determined by monitoring or computer simulation. The assessment based on thermal comfort variables is the most complex because it depends on the determination of the thermal comfort zone. For these reasons, this master thesis explores methods of building thermal performance assessment using variables of thermal comfort simulated by DesignBuilder software. The main objective is to contribute to the development of methods to support architectural decisions during the design process, and energy and sustainable rating systems. The research method consists on selecting thermal comfort methods, modeling them in electronic sheets with output charts developed to optimize the analyses, which are used to assess the simulation results of low cost house configurations. The house models consist in a base case, which are already built, and changes in thermal transmittance, absorptance, and shading. The simulation results are assessed using each thermal comfort method, to identify the sensitivity of them. The final results show the limitations of the methods, the importance of a method that considers thermal radiance and wind speed, and the contribution of the chart proposed

Incorporação de resíduo cerâmico para prevenção da retrogressão da resistência de cimentos de poços de petróleo submetidos à injeção de vapor

Steam injection is the most used thermal recovery method of oil nowadays because of the high degree of development of the technique that allows high recovery factors. However, injection of superheated steam into the reservoir affects the entire structure of the well, including the cemented layer that presents a retrogression of compressive strength and increases the permeability due to formation of more crystalline and denser phases at temperatures above 110 °C. These changes result in failures in the cement that favor the entrance of formation fluids into the annulus space resulting in unsafe operations and restrictions in the economic life of the well. But the strength retrogression can be prevented by partial replacement of cement by silica-based materials that reduce the CaO/SiO2 ratio of cement slurries changing the trajectory of the reactions, converting those deleterious phases in phases with satisfactory mechanical strength and permeability. The aim of this study was to evaluate the behavior of a ceramic waste material rich in silica in partial and total substitution of a mineral additive used to fight the strength retrogression of cement slurries subjected to high temperatures. The evaluation was made by compression, X-ray diffraction (XRD) and thermogravimetry (TG/DTG). The samples were submitted to a cycle of low temperature (38 °C) for 28 days and a cycle of low temperature followed by exposure to 280 ºC and 1000 psi by 3 days. The results showed that slurries with additions of up to 30% of the waste material are not enough to prevent the strength retrogression, while slurries with additions of the waste material combined with silica flour in various proportions produced hydrated products of low Ca/Si ratios that maintained the compressive strength at satisfactory levels

Estudo dos parâmetros operacionais do processo de combustão in situ em reservatório de petróleo pesado

The occurrence of heavy oil reservoirs have increased substantially and, due to the high viscosity characteristic of this type of oil, conventional recovery methods can not be applied. Thermal methods have been studied for the recovery of this type of oil, with a main objective to reduce its viscosity, by increasing the reservoir temperature, favoring the mobility of the oil and allowing an increasing in the productivity rate of the fields. In situ combustion (ISC) is a thermal recovery method in which heat is produced inside the reservoir by the combustion of part of the oil with injected oxygen, contrasting with the injection of fluid that is heated in the surface for subsequent injection, which leads to loss heat during the trajectory to the reservoir. The ISC is a favorable method for recovery of heavy oil, but it is still difficult to be field implemented. This work had as an objective the parametric analysis of ISC process applied to a semi-synthetic reservoir with characteristics of the Brazilian Northeast reservoirs using vertical production and vertical injection wells, as the air flow injection and the wells completions. For the analysis, was used a commercial program for simulation of oil reservoirs using thermal processes, called Steam, Thermal and Advanced Processes Reservoir Simulator (STARS) from Computer Modelling Group (CMG). From the results it was possible to analyze the efficiency of the ISC process in heavy oil reservoirs by increasing the reservoir temperature, providing a large decrease in oil viscosity, increasing its mobility inside the reservoir, as well as the improvement in the quality of this oil and therefore increasing significantly its recovered fraction. Among the analyzed parameters, the flow rate of air injection was the one which had greater influence in ISC, obtaining higher recovery factor the higher is the flow rate of injection, due to the greater amount of oxygen while ensuring the maintenance of the combustion front

Multifunctional Nanoparticles in Cancer: in vitro Characterization, in vivo Distribution

A novel biocompatible and biodegradable polymer, termed poly(Glycerol malate co-dodecanedioate) (PGMD), was prepared by thermal condensation method and used for fabrication of nanoparticles (NPs). PGMD NPs were prepared using the single oil emulsion technique and loaded with an imaging/hyperthermia agent (IR820) and a chemotherapeutic agent (doxorubicin, DOX). The size of the void PGMD NPs, IR820-PGMD NPs and DOX-IR820-PGMD NPs were approximately 90 nm, 110 nm, and 125 nm respectively. An acidic environment (pH=5.0) induced higher DOX and IR820 release compared to pH=7.4. DOX release was also enhanced by exposure to laser, which increased the temperature to 42°C. Cytotoxicity of DOX-IR820-PGMD NPs was comparable in MES-SA but was higher in Dx5 cells compared to free DOX plus IR820 (pIn vivomouse studies showed that NP formulation significantly improved the plasma half-life of IR820 after tail vein injection. Significant lower IR820 content was observed in kidney in DOX-IR820-PGMD NP treatment as compared to free IR820 treatment in our biodistribution studies (p

Graded Meshes In Bio-thermal Problems With Transmission-line Modeling Method.

In this study, the transmission-line modeling (TLM) applied to bio-thermal problems was improved by incorporating several novel computational techniques, which include application of graded meshes which resulted in 9 times faster in computational time and uses only a fraction (16%) of the computational resources used by regular meshes in analyzing heat flow through heterogeneous media. Graded meshes, unlike regular meshes, allow heat sources to be modeled in all segments of the mesh. A new boundary condition that considers thermal properties and thus resulting in a more realistic modeling of complex problems is introduced. Also, a new way of calculating an error parameter is introduced. The calculated temperatures between nodes were compared against the results obtained from the literature and agreed within less than 1% difference. It is reasonable, therefore, to conclude that the improved TLM model described herein has great potential in heat transfer of biological systems.