884 resultados para solid-state phase transformations
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In order to develop a method for use in investigations of spatial biomass distribution in solid-state fermentation systems, confocal scanning laser microscopy was used to determine the concentrations of aerial and penetrative biomass against height and depth above and below the substrate surface, during growth of Rhizopus oligosporus on potato dextrose agar. Penetrative hyphae had penetrated to a depth of 0.445 cm by 64 h and showed rhizoid morphology, in which the maximum biomass concentration, of 4.45 mg dry wt cm(-3), occurred at a depth of 0.075 cm. For aerial biomass the maximum density of 39.54 mg dry wt(-3) occurred at the substrate surface. For both aerial and penetrative biomass, there were two distinct regions in which the biomass concentration decayed exponentially with distance from the surface. For aerial biomass, the first exponential decay region was up to 0.1 cm height. The second region above the height of 0.1 cm corresponded to that in which sporangiophores dominated. This work lays the foundation for deeper studies into what controls the growth of fungal hyphae above and below the surfaces of solid substrates. (C) Wiley Periodicals, Inc.
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Microcrystalline silicon is a two-phase material. Its composition can be interpreted as a series of grains of crystalline silicon imbedded in an amorphous silicon tissue, with a high concentration of dangling bonds in the transition regions. In this paper, results for the transport properties of a mu c-Si:H p-i-n junction obtained by means of two-dimensional numerical simulation are reported. The role played by the boundary regions between the crystalline grains and the amorphous matrix is taken into account and these regions are treated similar to a heterojunction interface. The device is analysed under AM1.5 illumination and the paper outlines the influence of the local electric field at the grain boundary transition regions on the internal electric configuration of the device and on the transport mechanism within the mu c-Si:H intrinsic layer.
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A 10 kJ electromagnetic forming (EMF) modulator with energy recovery based on two resonant power modules, each containing a 4.5 kV/30-kA silicon controlled rectifier, a 1.11-mF capacitor bank and an energy recovery circuit, working in parallel to allow a maximum actuator discharge current amplitude and rate of 50 kA and 2 kA/mu s was successfully developed and tested. It can be plugged in standard single phase 230 V/16 A mains socket and the circuit is able to recover up to 32% of its initial energy, reducing the charging time of conventional EMF systems by up to 68%.
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This paper proposes a multifunctional architecture to implement field-programmable gate array (FPGA) controllers for power converters and presents a prototype for a pulsed power generator based on a solid-state Marx topology. The massively parallel nature of reconfigurable hardware platforms provides very high processing power and fast response times allowing the implementation of many subsystems in the same device. The prototype includes the controller, a failure detection system, an interface with a safety/emergency subsystem, a graphical user interface, and a virtual oscilloscope to visualize the generated pulse waveforms, using a single FPGA. The proposed architecture employs a modular design that can be easily adapted to other power converter topologies.
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New sensory materials based on p-phenylene ethynylene trimers integrating calix[4]arene receptors (CALIX-PET) and tert-butylphenol (TBP-PET) moieties have been synthesized and their sensitivity and selectivity for the detection of nitroaromatic compounds (NACs) such as nitrobenzene (NB), 2,4-dinitrotoluene (2,4-DNT), 2,4,6-trinitrotoluene (TNT) and picric acid (PA) investigated in fluid phase and solid-state. It was found that both fluorophores displayed high sensitivities toward NACs detection in solution as evaluated by the Stern-Volmer formalism. For all the tested explosives, the ratio of fluorescence intensities (F-0/F) is a linear function of the quencher concentration only after appropriate correction of fluorescence quenching data for inner-filter effects. The quenching efficiencies for CALIX-PET and TBP-PET follow the order PA >> TNT > DNT > NB, which correlate well with the quenchers electron affinities as evaluated from their LUMOs energies thereby suggesting a photoinduced electron transfer as the dominant mechanism of fluorescence quenching. The selectivity of these sensors was checked against exemplar interferents possessing differentiated electronic properties (benzoic acid, 2,4-dichlorophenol and benzoquinone) and reduced quenching activity was detected. The quenching efficiencies and response times of the two fluorophores in the solid-state toward NB, 2,4-DNT and TNT vapors were evaluated through steady-state fluorescence quenching experiments with the materials dispersed in polymeric matrices or as neat films. The most significant fluorescence quenching responses were achieved for drop-casted films of TBP-PET upon exposure to nitroaromatics.
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Dissertação para obtenção do grau de mestre em Engenharia de Materiais
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Dissertação para obtenção do Grau de Mestre em Engenharia Mecânica
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This thesis was focused on the production, extraction and characterization of chitin:β-glucan complex (CGC). In this process, glycerol byproduct from the biodiesel industry was used as carbon source. The selected CGC producing yeast was Komagataella pastoris (formerly known as Pichia pastoris), due the fact that to achieved high cell densities using as carbon source glycerol from the biodiesel industry. Firstly, a screening of K. pastoris strains was performed in shake flask assays, in order to select the strain of K. pastoris with better performance, in terms of growth, using glycerol as a carbon source. K. pastoris strain DSM 70877 achieved higher final cell densities (92-97 g/l), using pure glycerol (99%, w/v) and in glycerol from the biodiesel industry (86%, w/v), respectively, compared to DSM 70382 strain (74-82 g/l). Based on these shake flask assays results, the wild type DSM 70877 strain was selected to proceed for cultivation in a 2 l bioreactor, using glycerol byproduct (40 g/l), as sole carbon source. Biomass production by K. pastoris was performed under controlled temperature and pH (30.0 ºC and 5.0, respectively). More than 100 g/l biomass was obtained in less than 48 h. The yield of biomass on a glycerol basis was 0.55 g/g during the batch phase and 0.63 g/g during the fed-batch phase. In order to optimize the downstream process, by increasing extraction and purification efficiency of CGC from K. pastoris biomass, several assays were performed. It was found that extraction with 5 M NaOH at 65 ºC, during 2 hours, associated to neutralization with HCl, followed by successive washing steps with deionised water until conductivity of ≤20μS/cm, increased CGC purity. The obtained copolymer, CGCpure, had a chitin:glucan molar ratio of 25:75 mol% close to commercial CGC samples extracted from A. niger mycelium, kiOsmetine from Kitozyme (30:70 mol%). CGCpure was characterized by solid-state Nuclear Magnetic Resonance (NMR) spectroscopy and Differential Scanning Calorimetry (DCS), revealing a CGC with higher purity than a CGC commercial (kiOsmetine). In order to optimize CGC production, a set of batch cultivation experiments was performed to evaluate the effect of pH (3.5–6.5) and temperature (20–40 ºC) on the specific cell growth rate, CGC production and polymer composition. Statistical tools (response surface methodology and central composite design) were used. The CGC content in the biomass and the volumetric productivity (rp) were not significantly affected within the tested pH and temperature ranges. In contrast, the effect of pH and temperature on the CGC molar ratio was more pronounced. The highest chitin: β-glucan molar ratio (> 14:86) was obtained for the mid-range pH (4.5-5.8) and temperatures (26–33 ºC). The ability of K. pastoris to synthesize CGC with different molar ratios as a function of pH and temperature is a feature that can be exploited to obtain tailored polymer compositions.(...)
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The aim of this thesis is to present a solution to the quantum phase problem of the single-mode optical field. The solution is based on the use of phase shift covariant normalized positive operator measures. These measures describe realistic direct coherent state phase measurements such as the phase measurement schemes based on eight-port homodyne detection or heterodyne detection. The structure of covariant operator measures and, more generally, covariant sesquilinear form measures is analyzed in this work. Four different characterizations for phase shift covariant normalized positive operator measures are presented. The canonical covariant operator measure is definded and its properties are studied. Finally, some other suggested phase theories are introduced to investigate their connections to the covariant sesquilinear form measures.
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We present strategies for chemical shift assignments of large proteins by magic-angle spinning solid-state NMR, using the 21-kDa disulfide-bond-forming enzyme DsbA as prototype. Previous studies have demonstrated that complete de novo assignments are possible for proteins up to approximately 17 kDa, and partial assignments have been performed for several larger proteins. Here we show that combinations of isotopic labeling strategies, high field correlation spectroscopy, and three-dimensional (3D) and four-dimensional (4D) backbone correlation experiments yield highly confident assignments for more than 90% of backbone resonances in DsbA. Samples were prepared as nanocrystalline precipitates by a dialysis procedure, resulting in heterogeneous linewidths below 0.2 ppm. Thus, high magnetic fields, selective decoupling pulse sequences, and sparse isotopic labeling all improved spectral resolution. Assignments by amino acid type were facilitated by particular combinations of pulse sequences and isotopic labeling; for example, transferred echo double resonance experiments enhanced sensitivity for Pro and Gly residues; [2-(13)C]glycerol labeling clarified Val, Ile, and Leu assignments; in-phase anti-phase correlation spectra enabled interpretation of otherwise crowded Glx/Asx side-chain regions; and 3D NCACX experiments on [2-(13)C]glycerol samples provided unique sets of aromatic (Phe, Tyr, and Trp) correlations. Together with high-sensitivity CANCOCA 4D experiments and CANCOCX 3D experiments, unambiguous backbone walks could be performed throughout the majority of the sequence. At 189 residues, DsbA represents the largest monomeric unit for which essentially complete solid-state NMR assignments have so far been achieved. These results will facilitate studies of nanocrystalline DsbA structure and dynamics and will enable analysis of its 41-kDa covalent complex with the membrane protein DsbB, for which we demonstrate a high-resolution two-dimensional (13)C-(13)C spectrum.
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We have investigated the different contributions to the entropy change at the martensitic transition of different families of Cu-based shape-memory alloys. The total entropy change has been obtained through calorimetric measurements. By measuring the evolution of the magnetic susceptibility with temperature, the entropy change associated with conduction electrons has been evaluated. The contribution of the anharmonic vibrations of the lattice has also been estimated using various parameters associated with the anharmonic behavior of these alloys, collected from the literature. The results found in the present work have been compared to values published for the martensitic transition of group-IV metals. For Cu-based alloys, both electron and anharmonic contributions have been shown to be much smaller than the overall entropy change. This finding demonstrates that the harmonic vibrations of the lattice are the most relevant contribution to the stability of the bcc phase in Cu-based alloys.
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We present numerical results of the deterministic Ginzburg-Landau equation with a concentration-dependent diffusion coefficient, for different values of the volume fraction phi of the minority component. The morphology of the domains affects the dynamics of phase separation. The effective growth exponents, but not the scaled functions, are found to be temperature dependent.
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A surface dielectric function of a semi-infinite plane-bounded metal is defined in the spirit of the plasmon-pole dielectric function of the bulk. It is modeled in such a way that the surface-plasmon dispersion relation is recovered for small momentum transfer. This function is employed to compute the image potential at all distances outside the surface. Interaction with bulk modes is neglected for simplicity and clarity. The interaction of a massive point charge with a metal surface is also considered in the context of a boson model for surface-plasmon excitation. We present a new definition of the image potential for this case.
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We present a study of the influence of atomic order on the relative stability of the bcc and the 18R martensitic structures in a Cu2.96Al0.92Be0.12 crystal. Calorimetric measurements have shown that disorder increases the stability of the 18R phase, contrary to what happens in Cu-Zn-Al alloys for which it is the bcc phase that is stabilized by disordering the system. This different behavior has been explained in terms of a model recently reported. We have also proved that the entropy change at the martensitic transition is independent of the state of atomic order of the crystal, as predicted theoretically. Our results suggest that differences in the vibrational spectrum of the crystal due to different states of atomic order must be equal in the bcc and in the close-packed phases.
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We study the behavior of the random-bond Ising model at zero temperature by numerical simulations for a variable amount of disorder. The model is an example of systems exhibiting a fluctuationless first-order phase transition similar to some field-induced phase transitions in ferromagnetic systems and the martensitic phase transition appearing in a number of metallic alloys. We focus on the study of the hysteresis cycles appearing when the external field is swept from positive to negative values. By using a finite-size scaling hypothesis, we analyze the disorder-induced phase transition between the phase exhibiting a discontinuity in the hysteresis cycle and the phase with the continuous hysteresis cycle. Critical exponents characterizing the transition are obtained. We also analyze the size and duration distributions of the magnetization jumps (avalanches).