In situ impedance spectroscopy study of the electrochemical corrosion of Ti and Ti-6Al-4V in simulated body fluid at 25 degrees C and 37 degrees C

The corrosion resistance of Ti and Ti-6Al-4V was investigated through electrochemical impedance spectroscopy, EIS, potentiodynamic polarisation curves and UV-Vis spectrophotometry. The tests were done in Hank solution at 25 degrees C and 37 degrees C. The EIS measurements were done at the open circuit potential at specific immersion times. An increase of the resistance as a function of the immersion time was observed, for Ti (at 25 degrees C and 37 degrees C), and for Ti-6Al-4V (at 25 degrees C), which was interpreted as the formation and growth of a passive film on the metallic surfaces. (C) 2009 Elsevier Ltd. All rights reserved.

Análise e síntese de antenas e superfícies seletivas de frequência utilizando computação evolucionária e inteligência de enxames

The frequency selective surfaces, or FSS (Frequency Selective Surfaces), are structures consisting of periodic arrays of conductive elements, called patches, which are usually very thin and they are printed on dielectric layers, or by openings perforated on very thin metallic surfaces, for applications in bands of microwave and millimeter waves. These structures are often used in aircraft, missiles, satellites, radomes, antennae reflector, high gain antennas and microwave ovens, for example. The use of these structures has as main objective filter frequency bands that can be broadcast or rejection, depending on the specificity of the required application. In turn, the modern communication systems such as GSM (Global System for Mobile Communications), RFID (Radio Frequency Identification), Bluetooth, Wi-Fi and WiMAX, whose services are highly demanded by society, have required the development of antennas having, as its main features, and low cost profile, and reduced dimensions and weight. In this context, the microstrip antenna is presented as an excellent choice for communications systems today, because (in addition to meeting the requirements mentioned intrinsically) planar structures are easy to manufacture and integration with other components in microwave circuits. Consequently, the analysis and synthesis of these devices mainly, due to the high possibility of shapes, size and frequency of its elements has been carried out by full-wave models, such as the finite element method, the method of moments and finite difference time domain. However, these methods require an accurate despite great computational effort. In this context, computational intelligence (CI) has been used successfully in the design and optimization of microwave planar structures, as an auxiliary tool and very appropriate, given the complexity of the geometry of the antennas and the FSS considered. The computational intelligence is inspired by natural phenomena such as learning, perception and decision, using techniques such as artificial neural networks, fuzzy logic, fractal geometry and evolutionary computation. This work makes a study of application of computational intelligence using meta-heuristics such as genetic algorithms and swarm intelligence optimization of antennas and frequency selective surfaces. Genetic algorithms are computational search methods based on the theory of natural selection proposed by Darwin and genetics used to solve complex problems, eg, problems where the search space grows with the size of the problem. The particle swarm optimization characteristics including the use of intelligence collectively being applied to optimization problems in many areas of research. The main objective of this work is the use of computational intelligence, the analysis and synthesis of antennas and FSS. We considered the structures of a microstrip planar monopole, ring type, and a cross-dipole FSS. We developed algorithms and optimization results obtained for optimized geometries of antennas and FSS considered. To validate results were designed, constructed and measured several prototypes. The measured results showed excellent agreement with the simulated. Moreover, the results obtained in this study were compared to those simulated using a commercial software has been also observed an excellent agreement. Specifically, the efficiency of techniques used were CI evidenced by simulated and measured, aiming at optimizing the bandwidth of an antenna for wideband operation or UWB (Ultra Wideband), using a genetic algorithm and optimizing the bandwidth, by specifying the length of the air gap between two frequency selective surfaces, using an optimization algorithm particle swarm

Avaliação da molhabilidade de soluções de tensoativos em aço inoxidável

With the increasing industrialization of the planet caused by globalization, it has become increasingly common to search for highly resistant and durable materials for many diverse branches of activities. Thus, production and demand for materials that meet these requirements have constantly increased with time. In view of this, stainless steel is presented as one of the materials which are suitable applications, due to many features that are interesting for several segments of the industry. Concerns of oil companies over heavy oil reservoirs have grown steadily for the last decades. Rheological properties of these oils impair their transport in conventional flow systems. This problem has created the need to develop technologies to improve flow and transport, reducing operation costs so as to enable oil production in the reservoir. Therefore, surfactant-based chemical systems are proposed to optimize transport conditions, effected by reduction of interfacial tensions, thereby enhancing the flow of oil in ducts and reducing load losses by friction. In order to examine such interactions, a study on the wettability of metallic surfaces has been undertaken, represented by measuring of contact angle of surfactant solutions onto flat plates of 304 stainless steel. Aqueous solutions of KCl, surfactants and mixtures of surfactants, with linear and aromatic hydrocarbon chain and ethoxylation degrees ranging between 20 to 100, have been tested. The wettability was assessed by means of a DSA 100 krüss goniometer. The influence of roughness on the wettability was also investigated by machining and polished the stainless steel plates with sandpapers of references ranging between 100 of 1200. The results showed that sanding and polishing plates result in decrease of wettability. As for the solutions, they have provided better wettability of the stainless steel than the KCl solutions tested. It was also been concluded that surfactant mixtures is an option to be considered, since they promote interactions that generate satisfactory contact angles for a good wettability on the stainless steel plate. Another conclusion refers to the influence of the ethoxylation degree of the nonionic surfactant molecules on wettability. It has been observed that contact angles decrease with decreasing ethoxylation degrees. This leads us to conclude that molecules with higher ethoxylation degree, being more hydrophobic, decrease the interaction of water with the ducts, thereby reducing friction and improving the flow

STM probing of local oscillations of the Fano-Kondo effect: a Doniach-Sunjic approach for the Kondo peak

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Altering the adsorptive and electronic properties of Pt through poly(vinyl alcohol) adsorption

In the present paper we investigated the effect of adsorbed PVA on Pt electrodes on classic electrochemical processes such as hydrogen UPD, oxygen reduction and CO electro-oxidation. Upon adsorption PVA blocks roughly 50% of the hydrogen sites and can not be removed from the Pt surface through cycling in the potential range of 0.05-1.0 V vs. RHE. Potentiodynamic experiments under controlled hydrodynamic conditions provided by rotating disk electrode experiments showed a negative impact of the adsorbed PVA on the oxygen reduction reaction (ORR). Cyclic-voltammetry results revealed that not even CO was able to remove PVA from the Pt surface. Regarding the oxidation of CO, the adsorbed polymer positively shifted the CO oxidation peak potential, therefore higher potentials are required to free the Pt surface from CO poisoning. In situ Fourier transform infrared spectroscopy evidenced that the presence of PVA shifted the linearly bound CO frequency toward higher wavenumbers, a process found to be independent of the Pt surface orientation. In situ electrochemical X-ray absorption spectroscopy results showed that PVA also impacted the electronic properties of platinum by decreasing the occupancy of the Pt conducting 5d band. Our findings clearly support the efforts toward understanding the nature of the interaction between polymers and metallic surfaces as well as the impact on technological applications (e.g. in PEMFCs). © 2013 Elsevier Ltd. All rights reserved.

Alteração das propriedades superficiais do alumínio via eletrólise e plasma

Pós-graduação em Ciência e Tecnologia de Materiais - FC

Desenvolvimento de imunossensores para aflatoxina B1

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Ligas Ti-Al-Nb como biomaterial: elaboração, caracterização, modificação eletroquímica da superfície e estudo da biocompatibilidade utilizando culturas primárias de células da medula óssea humana

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Propriedades magnéticas de nanoestruturas de metais de transição 3d em superfícies de Pd

Motivados por estudos experimentais acerca de monocamadas de metais de transição 3d sobre superfícies de Pd, nesta dissertação investigamos o complexo magnetismo de nanoestruturas, embebidas ou adsorvidas, em superfícies metálicas através de cálculos de primeiros princípios. Utilizamos o método RS-LMTO-ASA (Real Space - Linear MuffinTin Orbital - Atomic Sphere Approximation), o qual é baseado na teoria do funcional da densidade (DFT - Density Functional Theory) e implementado para o cálculo de estruturas magnéticas não colineares. Com este propósito, investigamos nanoestruturas embebidas e ligas (2 x 2) de metais 3d (Cr, Mn, Fe, Co e Ni) na superfície Pd (110), além de nanoestruturas de Cr adsorvidas sobre a superfície de Pd (111). Primeiro, para as nanoestruturas embebidas na superfície Pd (110), analisamos a variação do momento magnético de spin orbital com relação ao número de vizinhos e de valência dos metais 3d. Também mostramos que estas estruturas têm ordenamento magnético colinear, exceto as de Cr e Mn, que apresentam magnetismo não colinear associado à frustração geométrica. Para o caso de nanofios de Cr adsorvidos sobre a superfície de Pd (111), verificamos uma configuração colinear antiferromagnética para cadeias com até 9 átomos. Para o nanofio com 10 átomos obtivemos uma configuração tipo antiferromagnética inclinada (canted). No caso de nanoestruturas de Cr bidimensionais, verificamos complexas configurações magnéticas não colineares com diferentes quiralidades.

Propriedades magnéticas de nanoestruturas adsorvidas em superfícies metálicas

Neste trabalho, utilizamos o método de primeiros princípios RS-LMTO-ASA (Real Space – Linear Muffin-Tin Orbital - Atomic Sphere Approximation) baseado na Teoria do Funcional da Densidade (DFT - Density Functional Theory) e implementado para o cálculo de estruturas magnéticas não-colineares, para investigar as propriedades magnéticas de nanoestruturas adsorvidas em superfícies metálicas. Consideramos aglomerados com diferentes geometrias e tamanhos como adátomos, dímeros, trímeros, nanofios e nanoestruturas de geometria triangular de Fe, Fe-Co e Fe-Pt adsorvidos sobre a superfície de Pt(111) e tratamos também nanoestruturas de Mn sobre a superfície de Ag(111). Mostramos que os nanofios de Fe-Co sobre a superfície de Pt(111) apresentam um ordenamento ferromagnético. Devido à redução do número de coordenação presente na superfície, os momentos de spin e orbital nos sítios de Fe e Co mostram-se elevados comparados com os respectivos valores dos momentos destes metais como bulk. Analisamos também como estes momentos variam em função da concentração destes elementos nos nanofios. Para os sistemas compostos por nanofios Fe-Pt adsorvidos em Pt(111), mostramos que é possível sintonizar as interações de troca entre os adátomos magnéticos Fe através da introdução de um diferente número de átomos Pt para ligá-los. Por exemplo, a interação de troca entre os adátomos de Fe pode ser consideravelmente aumentada pela introdução de cadeias de Pt que os conectem e tanto configurações ferromagnéticas, antiferromagnéticas ou não-colineares entre os adátomos de Fe podem ser estabilizadas, dependendo da espessura do espaçador Pt. Para os aglomerados Mn sobre a Ag(111) mostramos que a interação de troca entre os sítios de Mn depende não somente da distância entre os átomos, mas também do número de coordenação de cada sítio. Desta forma, verificamos um magnetismo não-colinear nestas nanoestruturas causado tanto por frustração geométrica, quanto pela competição de interações de curto e longo alcance. Nossos resultados estão em boa concordância com os resultados experimentais da literatura e com os resultados teóricos obtidos por outros métodos, quando existentes.

Desenvolvimento de sistemas multifuncionais baseados em híbridos orgânico-inorgânicos dopados

Pós-graduação em Química - IQ

Efeitos da rugosidade superficial nas propriedades de passivação de monocamadas orgânicas automontadas

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

Ultra-precision face grinding with constant pressure, lapping kinematics, and SiC grinding wheels dressed with overlap factor

Several machining processes have been created and improved in order to achieve the best results ever accomplished in hard and difficult to machine materials. Some of these abrasive manufacturing processes emerging on the science frontier can be defined as ultra-precision grinding. For finishing flat surfaces, researchers have been putting together the main advantages of traditional abrasive processes such as face grinding with constant pressure, fixed abrasives for two-body removal mechanism, total contact of the part with the tool, and lapping kinematics as well as some specific operations to keep grinding wheel sharpness and form. In the present work, both U d-lap grinding process and its machine tool were studied aiming nanometric finishing on flat metallic surfaces. Such hypothesis was investigated on AISI 420 stainless steel workpieces U d-lap ground with different values of overlap factor on dressing (Ud=1, 3, and 5) and grit sizes of conventional grinding wheels (silicon carbide (SiC)=#800, #600, and #300) applying a new machine tool especially designed and built for such finishing. The best results, obtained after 10 min of machining, were average surface roughness (Ra) of 1.92 nm, 1.19-μm flatness deviation of 25.4-mm-diameter workpieces, and mirrored surface finishing. Given the surface quality achieved, the U d-lap grinding process can be included among the ultra-precision abrasive processes and, depending on the application, the chaining steps of grinding, lapping, and polishing can be replaced by the proposed abrasive process.

Detorque evaluation of dental abutment screws after immersion in a fluoridated artificial saliva solution

Purpose: Implant-abutment connections still present failures in the oral cavity due to the loosening of mechanical integrity by detorque and corrosion of the abutment screws. The objective of this study was to evaluate the detorque of dental abutment screws before and after immersion in fluoridated solutions. Materials and Methods: Five commercial implant-abutment assemblies were assessed in this investigation: (C) Conex˜aoR , (E) EmfilsR , (I) INPR , (S) SINR , and (T) Titanium FixR . The implants were embedded in an acrylic resin and then placed in a holding device. The abutments were first connected to the implants and torqued to 20Ncmusing a handheld torque meter. The detorque values of the abutments were evaluated after 10 minutes. After applying a second torque of 20 Ncm, implant-abutment assemblies were withdrawn every 3 hours for 12 hours in a fluoridated solution over a period of 90 days. After that period, detorque of the abutments was examined. Scanning electronicmicroscopy (SEM) associated to energy dispersive spectroscopy (EDS) was applied to inspect the surfaces of abutments. Results: Detorque values of systems C, E, and I immersed in the fluoridated solution were significantly higher than those of the initial detorque. ANOVA demonstrated no significant differences in detorque values between designs S and T. Signs of localized corrosion could not be detected by SEM although chemical analysis by EDS showed the presence of elements involved in corrosive processes. Conclusion: An increase of detorque values recorded on abutments after immersion in fluoridated artificial saliva solutions was noticed in this study. Regarding chemical analysis, such an increase of detorque can result from a corrosion layer formed between metallic surfaces at static contact in the implant-abutment joint during immersion in the fluoridated solutions.

Spectroscopic signatures from first principles calculations: from surface adsorbates to liquids and polymers

In dieser Arbeit werden drei wasserstoffverbrückte Systeme in der kondensierten Phase mit Hilfe von first-principles-Elektronenstruktur-Rechnungen untersucht, die auf der Dichtefunktionaltheorie (DFT) unter periodischen Randbedingungen basieren. Ihre lokalen Konformationen und Wasserstoffbrückenbindungen werden mittels ab-initio Molekulardynamiksimulationen berechnet und weiterhin durch die Bestimmung ihrer spektroskopischen Parameter charakterisiert. Der Schwerpunkt liegt dabei auf lokalen Strukturen und auf schnellen Fluktuationen der Wasserstoffbrückenbindungen, welche von zentraler Bedeutung für die physikalischen und chemischen Eigenschaften der betrachteten Systeme sind. Die für die lokalen, instantanen Konformationen berechneten Spektren werden verwendet, um die physikalischen Prozesse, die hinter den untersuchten Phänomenen stehen, zu erklären: die Wasseradsorption auf metallischen Oberflächen, die Ionensolvatisierung in wässrigen Lösungen und der Protonentransport in protonleitenden Polymeren, welche Prototypen von Membranen für Brennstoffzellen sind. Die Möglichkeit der Vorhersage spektroskopischer Parameter eröffnet vielfältige Möglichkeiten des Dialogs zwischen Experimenten und numerischen Simulationen. Die in dieser Arbeit vorgestellten Ergebnisse zeigen, dass die Zuverlässigkeit dieser theoretischen Berechnungen inzwischen für viele experimentell relevante Systeme ein quantitatives Niveau erreicht hat.