978 resultados para spin-relaxation processes
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Defatted rumen protein and soy protein concentrate were extruded in a 15.5:1 L/D single-screw extruder at the optimum conditions for their expansion (150A degrees C and 35% moisture, and 130A degrees C and 35% moisture, respectively). Emulsions were produced with these proteins and studied by rheology and time domain low-resolution (1)H nuclear magnetic resonance (TD-NMR). Extrusion increased storage modulus of rumen protein emulsions. The opposite was observed for soy protein. Mechanical relaxation showed the existence of three relaxing components in the emulsions whose relative contributions were changed by extrusion. Likewise, spin-spin relaxation time constants (T (2)) measured by TD-NMR also showed three major distinct populations of protons in respect to their mobility that were also altered by extrusion. Extrusion increased surface hydrophobicity of both rumen and soy protein. Solubility of rumen protein increased with extrusion whereas soy protein had its solubility decreased after processing. Extrusion promoted molecular reorganization of protein, increasing its superficial hydrophobicity, affecting its interfacial properties and improving its emulsifying behavior. The results show that extrusion can promote the use of rumen, a by-product waste from the meat industry, in human nutrition by replacing soy protein in food emulsions.
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The discovery of the superconductivity of MgB(2) was of great importance, because this material is one of the few known binary compounds and has one of the highest critical temperatures (39 degrees K). As MgB(2) is a granular compound, it is fundamentally important to understand the mechanisms of the interaction of the defects and the crystalline lattice, in addition to the eventual processes involving the grain boundaries that compose the material. In this sense, the mechanical spectroscopy measurements constitute a powerful tool for this study, because through them we can obtain important information about phase transitions, the behavior of interstitial or substitutional elements, dislocations, grain boundaries, diffusion, instabilities, and other imperfections of the lattice. For this paper, the samples were prepared using the PIT method and were characterized by density, X-ray diffraction, scanning electron microscopy, electric resistivity, magnetization, and mechanical spectroscopy. The samples were measured in their as-cast condition and after an ultra-high-vacuum heat treatment. The results showed complex spectra, in which were identified relaxation processes due to dislocation movement, interaction among interstitial elements and dislocations, auto-diffusion, and movement of grain boundaries. Some of these processes disappeared with the heat treatment.
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The compound SmBa(2)Cu(3)O(7-delta) (SBCO)-obtained by substituting rare-earth Sm for Y in the well-known and most studied YBa(2)Cu(3)O(6+delta) (YBCO)-is potentially attractive to study in order to understand the superconductivity mechanism in physics and in electronic device applications. For SBCO, the possibility of variable stoichiometry and the high mobility of oxygen in CuO(x) planes give rise to a rich phase diagram. This study reports on the effect of heat treatments in an oxygen atmosphere on the anelastic properties of this oxide, in which relaxation processes were observed, attributed to oxygen atom jumps present in the Cu-O planes during the orthorhombic phase.
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The complex reaction between VO2+ ((1)A(1)/(3)A) and C2H4 (Ag-1(g)/(3)A(1)) to yield VO+ ((1)Delta/(3)Sigma) and CH3CHO ('A'/(3)A) has been studied by means of B3LYP/6-31G* and B3LYP/6-311G(2d,p) calculations. The structures of all reactants, products, intermediates, and transition structures of this reaction have been optimized and characterized at the fundamental singlet and first excited triplet electronic states. Crossing points are localized, and possible spin inversion processes are discussed by means of the intrinsic reaction coordinate approach. Relevant stationary points along the most favorable reaction pathways have been studied at the CCSD/6-311G(2d,p)//B3LYP/6-311G(2d,p) calculation level. The theoretical results allow the development of thermodynamic and kinetic arguments about the reaction pathways of the title process. In the singlet state, the first step is the barrierless obtention of a reactant complex associated with the formation of a V-C bond, while in the triplet state a three-membered ring addition complex with the V bonded to the two C atoms is obtained. Similar behavior is found in the exit channels: the product complexes can be formed from isolated products without barriers. The reactant and product complexes are the most stable stationary points in the singlet and triplet electronic states. From the singlet state reactant complex, two reaction pathways are posssible to reach the triplet state product complex. (i) A mechanism in which a hydrogen transfer process is the first and rate limiting step and the second step is an oxygen transfer between vanadium and carbon atoms with a concomitant change in the spin state. The crossing point between singlet and triplet spin states is not kinetically relevant because it takes place at a later stage occurring in the exit channel. (ii) A mechanism in which the first stage renders a four-membered ring between vanadyl cation and the ethylene fragment and an oxygencarbon bond is formed; on going from this minimum to the second transition structure, associated with a carbon-vanadium bond breaking process, the crossing point between singlet and triplet spin states is reached. The final step is the hydrogen transfer between both carbon atoms to yield the product complex. In this case the spin change opens a lower barrier pathway. The transition structures with larger values of relative energies for both reactive channels of VO2+ ((1)A(1)) + C2H4 (Ag-1) --> VO+ ((3)Sigma) + CH3CHO ((1)A') present similar energies, and the two reaction pathways can be considered as competitive.
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Dynamic light scattering was used to monitor relaxation processes in chitosan solutions at concentrations within the semi-dilute and concentrated regimes, Kowhlrausch-Williams-Watts (KWW) equation being successfully fitted to intensity correlation function data. The dependence of KWW equation parameters on chitosan concentration indicated that an increase in concentration from semi-dilute to concentrated regimes resulted in narrowing the distribution of relaxation rates; temperature dependence indicated the relaxation process as described as an energy activated process, whose parameters were function of the interaction between chitosan chains (enthalpy of activation) and rigidity of chitosan conformations (pre-exponential factor)
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In this work, GdAlO3:RE3+ (RE = Eu or Tb) was successfully prepared by the Pechini method at lower temperatures when compared to others methods as solid-state synthesis and sol-gel process. In accordance to the XRD data, the fully crystalline single-phase GdAlO3 could be obtained at 900 degrees C. The differential thermal analysis (DTA) shows a crystallization peak at 850 degrees C. The samples are composed by monocrystalline particles (50-120 nm) exhibiting the formation of aggregates among them, which indicates the beginning of the sinterization process. This feature indicates a strong tendency to the formation of aggregates, which is a suitable ability for the close-packing of particles, and hence a potential application in X-ray intensifying screens. Luminescence measurements indicate Gd3+ -> RE3+ energy transfer. The Eu3+ emission spectra exhibit all the characteristics D-5(0) -> F-7(j) transitions and the observed profile suggests that RE3+ ions occupy at least one site without center of symmetry. For terbium-doped samples, the D-5(3) -> F-7(j) (blue emission) and D-5(4) -> F-7(j) (green emission) transitions were observed and the ratio between them may depend on the Tb3+ content due to cross-relaxation processes. (C) 2009 Elsevier B.V. All rights reserved.
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
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The presence of interstitial elements in metals cause strong changes in their physical, chemical or mechanical properties. These interstitial impurities interact with the metallic matrix atoms by a relaxation process known as stress induced ordering. Relaxation processes give rise to a peak in the internal friction spectrum, known as Snock effect. The presence of substitutional solutes has a strong influence on Snoek effect, particularly if the substitutional solute element is the one, which interacts with the interstitial element. Anelastic spectroscopy measurements provide information of the behavior of these impurities in the metallic matrix. In this paper, polycrystalline samples of Nb-4.7 at.%Ta alloy have been analyzed in the as-received condition. Measurements of anelastic spectroscopy were carried out using an inverted torsion pendulum, operating with frequency of 2.0-30.0 Hz and in a temperature range between 300 and 700 K. It was observed the presence of a relaxation structure that have been attributed to stress induced ordering due to interstitial atoms around atoms of the metallic matrix. The relaxation structure have been decomposed in its constituent peaks, what it allowed to identify the following relaxation processes: Ta-O, Nb-O and Nb-N. (c) 2005 Elsevier B.V. All rights reserved.
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Red, green, and blue emission through frequency upconversion and energy-transfer processes in tellurite glasses doped with Tm3+ and Er3+ excited at 1.064 mum is investigated. The Tm3+/Er3+-codoped samples produced intense upconversion emission signals at around 480, 530, 550 and 660 nm. The 480 nm blue emission was originated from the (1)G(4)-->H-3(6) transition of the Tm3+ ions excited by a multiphoton stepwise phonon-assisted excited-state absorption process. The 5 30, 5 50 nm green and 660 mn red upconversion luminescences were identified as originating from the H-2(11/2), S-4(3/2) --> I-4(15/2) and F-4(9/2) --> I-4(15/2) transitions of the Er3+ ions, respectively, populated via efficient cross-relaxation processes and excited-state absorption. White light generation employing a single infrared excitation source is also examined. (C) 2003 Elsevier B.V. (USA). All rights reserved.
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Intense red upconversion emission around 650 nm in PbGeO3-PbF2-CdF2 transparent glass ceramic containing beta-PbF2:Ho3+ nanocrystals, is presented. The holmium-doped vitroceramic samples were excited by a 980 nm diode laser source. The 650 nm upconversion signal was assigned to the F-5(5) --> I-5(8) transition of holmium ions. Very low intensity signals around 490 and 540 nm corresponding to the F-5(2,3) --> I-5(8) and S-4(2), F-5(4) --> I-5(8) transitions, respectively, were also detected. The upconversion excitation mechanism was achieved through a combination of stepwise phonon-assisted multiphoton absorption, cross-relaxation processes involving pairs of holmium ions, and excited-state absorption. Using a diode laser pump source around 850 nm green upconversion emission around 540 nm was the observed predominant signal. (C) 2004 Elsevier B.V. All rights reserved.
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Frequency upconversion luminescence in erbium-doped PbGeO3-PbF2-CdF2-based transparent glass ceramics (TGC) under 980 nm infrared excitation is investigated. Upconversion emission signals around 410, 525, 550, 660, and 850 nm were generated and identified as due to the H-2(9/2) H-2(11/2), S-4(3/2), and F-4(9/2) transitions to the I-4(15/2) ground-state, and S-4(3/2)-I-4(13/2), respectively. The erbium ions excited-state emitting levels were populated via a combination of stepwise ground-state absorption (GSA), excited-state absorption (ESA), and cross-relaxation processes. The results also disclosed that both blue (410 nm) and red (660 nm) upconversion emission signals in the transparent glass ceramic sample presented twice as much intensity as compared to its vitreous counterpart. (C) 2003 Elsevier B.V. All rights reserved.
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The anelastic spectrum (dynamic Young's modulus and elastic energy absorption) of La2CuO4+δ has been measured between 1 and 700 K with 0<δ<0.02. The spectrum of stoichiometric La2CuO4 in the low-temperature orthorhombic (LTO) phase is dominated by two intense relaxation processes which cause softenings of 16% around 150 K and 9% below 30 K at f∼1 kHz. The relaxation at 150 K is attributed to the presence of a fraction of the CuO6 octahedra which are able to change their tilted configuration by thermal activation between orientations which are nearly energetically equivalent, possibly within the twin boundaries. The relaxation below 30 K is governed by tunneling, and involves a considerable fraction of the lattice atoms. It is proposed that the double-well potentials for the low-temperature relaxation are created by the tendency of the LTO phase to form low-temperature tetragonal (LTT) domains, which however are not stabilized like when La is partially substituted with Ba. On doping with excess O, the relaxation rates of these processes are initially enhanced by hole doping, while their intensities are depressed by lattice disorder; an explanation of this behavior is provided. Excess O also causes two additional relaxation processes. The one appearing at lower values of δ is attributed to the hopping of single interstitial O2- ions, with a hopping rate equal to τ-1=2×10-14exp(-5600/T) s. The second process is slower and can be due to O pairs or other complexes containing excess O.
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A novel fractal model for grain boundary regions of ceramic materials was developed. The model considers laterally inhomogeneous distribution of charge carriers in the vicinity of grain boundaries as the main cause of the non-Debye behaviour and distribution of relaxation times in ceramic materials. Considering the equivalent circuit the impedance of the grain boundary region was expressed. It was shown that the impedance of the grain boundary region has the form of the Davidson-Cole equation. The fractal dimension of the inhomogeneous distribution of charge carriers in the region close to the grain boundaries could be calculated based on the relation ds = 1 + β, where β is the constant from the Davidson-Cole equation.
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Energy transfer processes between Er3+ and Tm3+ were investigated examining the frequency upconversion emissions in a fluoroindate glass pumped at 790 nm. A 60-fold enhancement in the emission at ≈670 nm originating from Er3+ was observed when Tm3+ at concentration of 2% was introduced in a sample containing 2% of Er3+. The results are explained considering the influence of cross-relaxation processes between the active ions. © 2002 Elsevier Science B.V. All rights reserved.