Estudo de complexos de ferro e de cobre com a base de Shiff 3-Meosalen e ligantes de relevância biológica

The goal set for this work was to synthesize and to characterize new iron and copper complexes with the Schiff base 3-MeOsalen and ligands of biological relevance, whose formulas are [Fe(3-MeOsalen)NO2], [Fe(3-MeOsalen)(etil2-dtc)], [Fe(3-MeOsalen)NO] and Na[Cu(3-MeOsalen)NO2]. The compounds were characterized by vibrational spectroscopy in the infrared region (IV) and Electronic spectroscopy in the ultraviolet and visible region (Uv-Vis). From the analysis of infrared spectra, they proved to formation of precursor complexes, as evidenced by changes in the vibrationals frequencies ν(C=N) e ν(C-O) and the emergence of vibrationals modes metal-oxygen and metal-nitrogen. For nitro complexes of iron and copper were observed ν(NO2)ass around 1300 cm-1 e ν(NO2)sim in 1271 cm-1 , indicating that the coordination is done via the nitrogen atom. The complex spectrum [Fe(3-MeOsalen)(etil2-dtc)] exhibited two bands, the ν(C-NR2) in 1508 cm-1 e ν(C-S) in 997 cm-1 , the relevant vibrational modes of coordinating ligand in the bidentate form. For the complex [Fe(3-MeOsalen)NO] was observed a new intense band in 1670 cm-1 related to the ν(NO). With the electronic spectra, the formation of complexes was evidenced by shifts of bands intraligands transitions and the emergence of new bands such as LMCT (p Cl-  d* Fe3+) in [Fe(3-MeOsalen)Cl] and the d-d in [Cu(3-MeOsalen)H2O]. As for the [Fe(3-MeOsalen)NO2] has highlighted the absence of LMCT band present in the precursor complex as for the [Cu(3-MeOsalen)NO2] found that the displacement of the band hipsocrômico d-d on 28 nm. The electronic spectrum of [Fe(3-MeOsalen)(etil2-dtc)] presented LMCT band shifts and changes in intraligantes transitions. With regard to [Fe(3-MeOsalen)NO], revealed a more energetic transitions intraligands regions from the strong character π receiver NO and MLCT band of transition dπFe(II)π*(NO).

Síntese e caracterização de NiO-CGO para anodo e eletrólitos sólidos e base de Céria para SOFC

The direct use of natural gas makes the Solid Oxide Fuel Cell (SOFC) potentially more competitive with the current energy conversions technologies. The Intermediate Temperature SOFC (IT-SOFC) offer several advantages over the High Temperature SOFC (HT-SOFC), which includes better thermal compatibility among components, fast start with lower energy consumption, manufacture and operation cost reduction. The CeO2 based materials are alternatives to the Yttria Stabilized Zirconia (YSZ) to application in SOFC, as they have higher ionic conductivity and less ohmic losses comparing to YSZ, and they can operate at lower temperatures (500-800°C). Ceria has been doped with a variety of cations, although, the Gd3+ has the ionic radius closest to the ideal one to form solid solution. These electrolytes based in ceria require special electrodes with a higher performance and chemical and termomechanical compatibility. In this work compounds of gadolinia-doped ceria, Ce1-xGdxO2-δ (x = 0,1; 0,2 and 0,3), used as electrolytes, were synthesized by polymeric precursors method, Pechini, as well as the composite material NiO - Ce0,9Gd0,1O1,95, used as anode, also attained by oxide mixture method, mixturing the powders of the both phases calcinated already. The materials were characterized by X ray diffraction, dilatometry and scanning electronic microscopy. The refinement of the diffraction data indicated that all the Ce1-xGdxO2-δ powders were crystallized in a unique cubic phase with fluorite structure, and the composite synthesized by Pechini method produced smaller crystallite size in comparison with the same material attained by oxide mixture method. All the produced powders had nanometric characteristics. The composite produced by Pechini method has microstructural characteristics that can increase the triple phase boundaries (TPB) in the anode, improving the cell efficiency, as well as reducing the mass transport mechanism effect that provokes anode degradation

Plásticos reforçados a base de tecidos híbridos: efeitos da anisotropia e geometria normativa na caracterização mecânica e da fratura

As most current studies, reinforced plastics have been, in recent years, a viable alternative in building structural elements of medium and large, since the lightness accompanied by high performance possible. The design of hybrid polymer composites (combination of different types of reinforcements) may enable structural applications thereof, facing the most severe service conditions. Within this class of composite materials, reinforced the underlying tissues hybrid high performance are taking space when your application requires high load bearing and high rigidity. The objective of this research work is to study the challenges in designing these fabrics bring these materials as to its mechanical characterization and fracture mechanisms involved. Some parameters associated with the process and / or form of hybridization stand out as influential factors in the final performance of the material such as the presence of anisotropy, so the fabric weave, the process of making the same, normative geometry of the specimens, among others. This sense, four laminates were developed based hybrid reinforcement fabrics involving AS4 carbon fiber, kevlar and glass 49-E as the matrix epoxy vinyl ester resin (DERAKANE 411-350). All laminates were formed each with four layers of reinforcements. Depending on the hybrid fabric, all the influencing factors mentioned above have been studied for laminates. All laminates were manufactured industrially used being the lamination process manual (hand-lay-up). All mechanical characterization and study of the mechanism of fracture (fracture mechanics) was developed for laminates subjected to uniaxial tensile test, bending in three and uniaxial compression. The analysis of fracture mechanisms were held involving the macroscopic, optical microscopy and scanning electron microscopy

Envelhecimento ambiental acelerado em PRF a base de tecidos híbridos kevlar/vidro: propriedades e instabilidade estrutural

There are a number of damaging mechanisms that various materials can suffer in service. However, when working with polymer composite materials, this is something that requires analysis, especially when exposed to adverse environmental conditions. Thus, the objective of the present thesis is the study of the direct influence of environmental aging and the form of hybridization of the reinforcement woven on the structural stability, surfacedegradation and fracture process of polymer composites laminates. For this, the development of two polymer composite laminates was necessary, where one of them was reinforced with a bi-directional woven with hybrid strandsofkevlar-49/glass-Efibers, and the other also with a bi-directionalwoven, however with weft and warpformed of alternating strandsof Kevlar-49 fibers and glass-E fiber The reinforcementwoven are industrially manufactured. Both laminates use a polyester resin as a matrixand are made up of four layers each. All laminates were industrially prepared by the hand lay-up method of manufacturing. To do this, test specimens were manufactured of the respective laminates and submitted to environmental aging accelerated through the aging chamber. They were exposed to alternating cycles of UV radiation and moisture (heated steam) for a standard defined period. At the end of the exposure period the specimens were subjected to mechanical tests of uniaxial tensile and bending in three points and to the characterizationsof the fracture and surface deterioration. In addition, they were submitted to a structural degradation assessment by the measurement of mass variation technique (MMVT) and the measurement of thickness variation technique (MTVT), this last technique being developed in this thesis. At the end of the analysis it was observed that the form of hybridization of the reinforcement woven and the aging process directly influence with losses or gain in mechanical properties, with losses in the structural degradation and in the formation and propagation of damage mechanism of the developedcomposite laminates

Envelhecimento ambiental em compósitos poliméricos à base de tecidos de reforços híbridos

The utilization of synthetic fibers for plastic reinforcement is more and more frequent and this growing interest requires that their mechanic behavior under the most variable conditions of structural applications be known. The use of such materials in the open and exposed to the elements is one of them. In this case, it becomes extremely necessary to study their mechanical properties (strength, stiffness) and the mechanism of fracture by which the environment aging them out. In order to do that, the material must be submitted to hot steam and ultraviolet radiation exposure cycles, according to periods of time determined by the norms. This study proposal deals with the investigation of accelerated environmental aging in two laminated polymeric composites reinforced by hybrid woven made up of synthetic fibers. The configurations of the laminated composites are defined as: one laminate reinforced with hybrid woven of glass fibers/E and Kevlar fibers/49 (LHVK) and the other laminate is reinforced with hybrid tissue of glass fibers/E and of carbon fibers AS4 (LHVC). The woven are plane and bidirectional. Both laminates are impregnated with a thermofix resin called Derakane 470-300 Epoxy Vinyl-Ester and they form a total of four layers. The laminates were industrially manufactured and were made through the process of hand-lay-up. Comparative analyses were carried out between their mechanical properties by submitting specimen to uniaxial loading tractions and three-point flexion. The specimen were tested both from their original state, that is, without being environmentally aging out, and after environmental aging. This last state was reached by using the environmental aging chamber

Evolução dos sistemas de falhas de borda do Rifte Potiguar com base em curvas de crescimento de falhas

The discussion about rift evolution in the Brazilian Equatorial margin during the South America-Africa breakup in the Jurassic/Cretaceous has been focused in many researches. But rift evolution based on development and growth of faults has not been well explored. In this sense, we investigated the Cretaceous Potiguar Basin in the Equatorial margin of Brazil to understand the geometry of major faults and the influence of crustal heterogeneity and preexisting structural fabric in the evolution of the basin internal architecture. Previous studies pointed out that the rift is an asymmetrical half-graben elongated along the NE-SW direction. We used 2D seismic, well logs and 3D gravity modeling to analyze four major border fault segments and determine their maximum displacement (Dmax) and length (L) ratio in the Potiguar Rift. We constrained the 3D gravity modeling with well data and the interpretation of seismic sections. The difference of the fault displacement measured in the gravity model is in the order of 10% compared to seismic and well data. The fault-growth curves allowed us to divide the faulted rift border into four main fault segments, which provide roughly similar Dmax/L ratios. Fault-growth curves suggest that a regional uniform tectonic mechanism influenced growth of the rift fault segments. The variation of the displacements along the fault segments indicates that the fault segments were formed independently during rift initiation and were linked by hard and soft linkages. The latter formed relay ramps. In the interconnection zones the Dmax/L ratios are highest due to interference of fault segment motions. We divided the evolution of the Potiguar Rift into five stages based on these ratios and correlated them with the major tectonic stages of the breakup between South America and Africa in Early Cretaceous.

Evolução dos sistemas de falhas de borda do Rifte Potiguar com base em curvas de crescimento de falhas

The discussion about rift evolution in the Brazilian Equatorial margin during the South America-Africa breakup in the Jurassic/Cretaceous has been focused in many researches. But rift evolution based on development and growth of faults has not been well explored. In this sense, we investigated the Cretaceous Potiguar Basin in the Equatorial margin of Brazil to understand the geometry of major faults and the influence of crustal heterogeneity and preexisting structural fabric in the evolution of the basin internal architecture. Previous studies pointed out that the rift is an asymmetrical half-graben elongated along the NE-SW direction. We used 2D seismic, well logs and 3D gravity modeling to analyze four major border fault segments and determine their maximum displacement (Dmax) and length (L) ratio in the Potiguar Rift. We constrained the 3D gravity modeling with well data and the interpretation of seismic sections. The difference of the fault displacement measured in the gravity model is in the order of 10% compared to seismic and well data. The fault-growth curves allowed us to divide the faulted rift border into four main fault segments, which provide roughly similar Dmax/L ratios. Fault-growth curves suggest that a regional uniform tectonic mechanism influenced growth of the rift fault segments. The variation of the displacements along the fault segments indicates that the fault segments were formed independently during rift initiation and were linked by hard and soft linkages. The latter formed relay ramps. In the interconnection zones the Dmax/L ratios are highest due to interference of fault segment motions. We divided the evolution of the Potiguar Rift into five stages based on these ratios and correlated them with the major tectonic stages of the breakup between South America and Africa in Early Cretaceous.

Síntese e caracterização de NiO-CGO para anodo e eletrólitos sólidos e base de Céria para SOFC

The direct use of natural gas makes the Solid Oxide Fuel Cell (SOFC) potentially more competitive with the current energy conversions technologies. The Intermediate Temperature SOFC (IT-SOFC) offer several advantages over the High Temperature SOFC (HT-SOFC), which includes better thermal compatibility among components, fast start with lower energy consumption, manufacture and operation cost reduction. The CeO2 based materials are alternatives to the Yttria Stabilized Zirconia (YSZ) to application in SOFC, as they have higher ionic conductivity and less ohmic losses comparing to YSZ, and they can operate at lower temperatures (500-800°C). Ceria has been doped with a variety of cations, although, the Gd3+ has the ionic radius closest to the ideal one to form solid solution. These electrolytes based in ceria require special electrodes with a higher performance and chemical and termomechanical compatibility. In this work compounds of gadolinia-doped ceria, Ce1-xGdxO2-δ (x = 0,1; 0,2 and 0,3), used as electrolytes, were synthesized by polymeric precursors method, Pechini, as well as the composite material NiO - Ce0,9Gd0,1O1,95, used as anode, also attained by oxide mixture method, mixturing the powders of the both phases calcinated already. The materials were characterized by X ray diffraction, dilatometry and scanning electronic microscopy. The refinement of the diffraction data indicated that all the Ce1-xGdxO2-δ powders were crystallized in a unique cubic phase with fluorite structure, and the composite synthesized by Pechini method produced smaller crystallite size in comparison with the same material attained by oxide mixture method. All the produced powders had nanometric characteristics. The composite produced by Pechini method has microstructural characteristics that can increase the triple phase boundaries (TPB) in the anode, improving the cell efficiency, as well as reducing the mass transport mechanism effect that provokes anode degradation

Plásticos reforçados a base de tecidos híbridos: efeitos da anisotropia e geometria normativa na caracterização mecânica e da fratura

As most current studies, reinforced plastics have been, in recent years, a viable alternative in building structural elements of medium and large, since the lightness accompanied by high performance possible. The design of hybrid polymer composites (combination of different types of reinforcements) may enable structural applications thereof, facing the most severe service conditions. Within this class of composite materials, reinforced the underlying tissues hybrid high performance are taking space when your application requires high load bearing and high rigidity. The objective of this research work is to study the challenges in designing these fabrics bring these materials as to its mechanical characterization and fracture mechanisms involved. Some parameters associated with the process and / or form of hybridization stand out as influential factors in the final performance of the material such as the presence of anisotropy, so the fabric weave, the process of making the same, normative geometry of the specimens, among others. This sense, four laminates were developed based hybrid reinforcement fabrics involving AS4 carbon fiber, kevlar and glass 49-E as the matrix epoxy vinyl ester resin (DERAKANE 411-350). All laminates were formed each with four layers of reinforcements. Depending on the hybrid fabric, all the influencing factors mentioned above have been studied for laminates. All laminates were manufactured industrially used being the lamination process manual (hand-lay-up). All mechanical characterization and study of the mechanism of fracture (fracture mechanics) was developed for laminates subjected to uniaxial tensile test, bending in three and uniaxial compression. The analysis of fracture mechanisms were held involving the macroscopic, optical microscopy and scanning electron microscopy