Intermediate motions as studied by solid-state separated local field NMR experiments

In this report, the application of a class of separated local field NMR experiments named dipolar chemical shift correlation (DIPSHIFT) for probing motions in the intermediate regime is discussed. Simple analytical procedures based on the Anderson-Weiss (AW) approximation are presented. In order to establish limits of validity of the AW based formulas, a comparison with spin dynamics simulations based on the solution of the stochastic Liouville-von-Neumann equation is presented. It is shown that at short evolution times (less than 30% of the rotor period), the AW based formulas are suitable for fitting the DIPSHIFT curves and extracting kinetic parameters even in the case of jumplike motions. However, full spin dynamics simulations provide a more reliable treatment and extend the frequency range of the molecular motions accessible by DIPSHIFT experiments. As an experimental test, molecular jumps of imidazol methyl sulfonate and trimethylsulfoxonium iodide, as well as the side-chain motions in the photoluminescent polymer poly[2-methoxy-5-(2(')-ethylhexyloxy)-1,4-phenylenevinylene], were characterized. Possible extensions are also discussed. (c) 2008 American Institute of Physics.

Crystallization and preliminary X-ray diffraction analysis of a glutathione S-transferase from Xylella fastidiosa

Glutathione S-transferases (GSTs) form a group of multifunctional isoenzymes that catalyze the glutathione-dependent conjugation and reduction reactions involved in the cellular detoxification of xenobiotic and endobiotic compounds. GST from Xylella fastidiosa (xfGST) was overexpressed in Escherichia coli and purified by conventional affinity chromatography. In this study, the crystallization and preliminary X-ray analysis of xfGST is described. The purified protein was crystallized by the vapour-diffusion method, producing crystals that belonged to the triclinic space group P1. The unit-cell parameters were a = 47.73, b = 87.73, c = 90.74 angstrom, alpha = 63.45, beta = 80.66, gamma = 94.55 degrees. xfGST crystals diffracted to 2.23 angstrom resolution on a rotating-anode X-ray source.

Energy spectra for quantum wires and two-dimensional electron gases in magnetic fields with Rashba and Dresselhaus spin-orbit interactions

We introduce an analytical approximation scheme to diagonalize parabolically confined two-dimensional (2D) electron systems with both the Rashba and Dresselhaus spin-orbit interactions. The starting point of our perturbative expansion is a zeroth-order Hamiltonian for an electron confined in a quantum wire with an effective spin-orbit induced magnetic field along the wire, obtained by properly rotating the usual spin-orbit Hamiltonian. We find that the spin-orbit-related transverse coupling terms can be recast into two parts W and V, which couple crossing and noncrossing adjacent transverse modes, respectively. Interestingly, the zeroth-order Hamiltonian together with W can be solved exactly, as it maps onto the Jaynes-Cummings model of quantum optics. We treat the V coupling by performing a Schrieffer-Wolff transformation. This allows us to obtain an effective Hamiltonian to third order in the coupling strength k(R)l of V, which can be straightforwardly diagonalized via an additional unitary transformation. We also apply our approach to other types of effective parabolic confinement, e. g., 2D electrons in a perpendicular magnetic field. To demonstrate the usefulness of our approximate eigensolutions, we obtain analytical expressions for the nth Landau-level g(n) factors in the presence of both Rashba and Dresselhaus couplings. For small values of the bulk g factors, we find that spin-orbit effects cancel out entirely for particular values of the spin-orbit couplings. By solving simple transcendental equations we also obtain the band minima of a Rashba-coupled quantum wire as a function of an external magnetic field. These can be used to describe Shubnikov-de Haas oscillations. This procedure makes it easier to extract the strength of the spin-orbit interaction in these systems via proper fitting of the data.

Studies on the Electrocatalytic Reduction of Hydrogen Peroxide on a Glassy Carbon Electrode Modified With a Ruthenium Oxide Hexacyanoferrate Film

The electrocatalytic reduction of hydrogen peroxide on a glassy carbon (GC) electrode modified with a ruthenium oxide hexacyanoferrate (RuOHCF) was investigated using rotating disc electrode (RDE) voltammetry aiming to improve the performance of the sensor for hydrogen peroxide detection. The influence of parameters such as rotation speed, film thickness and hydrogen peroxide concentration indicated that the rate of the cross-chemical reaction between Ru(II) centres immobilized into the film and hydrogen peroxide controls the overall process. The kinetic regime could be classified as LSk mechanism, according to the diagnostic table proposed by Albery and Hillman, and the kinetic constant of the mediated process was found to be 706 mol(-1) cm(3) s(-1). In the LSk case the reaction layer is located at a finite layer close to the modifier layer/solution interface

Evaluation of Several Carbon-Supported Nanostructured Ni-Doped Manganese Oxide Materials for the Electrochemical Reduction of Oxygen

Physical and electrochemical properties of nanostructured Ni-doped manganese oxides (MnO(x)) catalysts supported on different carbon powder substrates were investigated so as to characterize any carbon substrate effect toward the oxygen reduction reaction (ORR) kinetics in alkaline medium. These NiMnO(x)/C materials were characterized using physicochemical analyses. Small insertion of Ni atoms in the MnO(x) lattice was observed, which consists of a true doping of the manganese oxide phase. The corresponding NiMnO(x) phase is present in the form of needles or agglomerates, with crystallite sizes in the order of 1.5-6.7 nm (from x-ray diffraction analyses). Layered manganite (MnOOH) phase has been detected for the Monarch 1000-supported NiMnO(x) material, while different species of MnO(x) phases are present at the E350G and MM225 carbons. Electrochemical studies in thin porous coating active layers in the rotating ring-disk electrode setup revealed that the MnO(x) catalysts present better ORR kinetics and electrochemical stability upon Ni doping. The ORR follows the so-called peroxide mechanism on MnO(x)/C catalysts, with the occurrence of minority HO(2)(-) disproportionation reaction. The HO(2)(-) disproportionation reaction progressively increases with the Ni content in NiMnO(x) materials. The catalysts supported on the MM225 and E350G carbons promote faster disproportionation reaction, thus leading to an overall four-electron ORR pathway. (C) 2011 The Electrochemical Society. [DOI: 10.1149/1.3528439] All rights reserved.

Mechanistic studies of the 'blue' Cu enzyme, bilirubin oxidase, as a highly efficient electrocatalyst for the oxygen reduction reaction

The 'blue copper' enzyme bilirubin oxidase from Myrothecium verrucaria shows significantly enhanced adsorption on a pyrolytic graphite 'edge' (PGE) electrode that has been covalently modified with naphthyl-2-carboxylate functionalities by diazonium coupling. Modified electrodes coated with bilirubin oxidase show electrocatalytic voltammograms for the direct, four-electron reduction of O(2) by bilirubin oxidase with up to four times the current density of an unmodified PGE electrode. Electrocatalytic voltammograms measured with a rapidly rotating electrode (to remove effects of O(2) diffusion limitation) have a complex shape (an almost linear dependence of current on potential below pH 6) that is similar regardless of how PGE is chemically modified. Importantly, the same waveform is observed if bilirubin oxidase is adsorbed on Au(111) or Pt(111) single-crystal electrodes (at which activity is short-lived). The electrocatalytic behavior of bilirubin oxidase, including its enhanced response on chemically-modified PGE, therefore reflects inherent properties that do not depend on the electrode material. The variation of voltammetric waveshapes and potential-dependent (O(2)) Michaelis constants with pH and analysis in terms of the dispersion model are consistent with a change in rate-determining step over the pH range 5-8: at pH 5, the high activity is limited by the rate of interfacial redox cycling of the Type 1 copper whereas at pH 8 activity is much lower and a sigmoidal shape is approached, showing that interfacial electron transfer is no longer a limiting factor. The electrocatalytic activity of bilirubin oxidase on Pt(111) appears as a prominent pre-wave to electrocatalysis by Pt surface atoms, thus substantiating in a single, direct experiment that the minimum overpotential required for O(2) reduction by the enzyme is substantially smaller than required at Pt. At pH 8, the onset of O(2) reduction lies within 0.14 V of the four-electron O(2)/2H(2)O potential.

Failure analysis of low velocity impact on thin composite laminates: Experimental and numerical approaches

The dynamic behavior of composite laminates is very complex because there are many concurrent phenomena during composite laminate failure under impact load. Fiber breakage, delaminations, matrix cracking, plastic deformations due to contact and large displacements are some effects which should be considered when a structure made from composite material is impacted by a foreign object. Thus, an investigation of the low velocity impact on laminated composite thin disks of epoxy resin reinforced by carbon fiber is presented. The influence of stacking sequence and energy impact was investigated using load-time histories, displacement-time histories and energy-time histories as well as images from NDE. Indentation tests results were compared to dynamic results, verifying the inertia effects when thin composite laminate was impacted by foreign object with low velocity. Finite element analysis (FEA) was developed, using Hill`s model and material models implemented by UMAT (User Material Subroutine) into software ABAQUS (TM), in order to simulate the failure mechanisms under indentation tests. (C) 2007 Elsevier Ltd. All rights reserved.

The effect of the generation and handling in the acquired electrostatic charge in airborne particles

The measurement of the charge distribution in laboratory generated aerosols particles was carried out. Four cases of electrostatic charge acquisition by aerosol particles were evaluated. In two of these cases. the charges acquired by the particles were naturally derived from the aerosol generation procedure itself, without using any additional charging method. Ill the other two cases, a corona charger and an impact charger were utilized as Supplementary methods for charge generation. Two types of aerosol generators were used in the dispersion of particles in the gas Stream: the vibrating orifice generator TSI model 3450 and the rotating plate generator TSI model 3433. In the vibrating orifice generator. a Solution of methylene blue Was used and the generated particles were mono-dispersed. Different mono-aerosols were generated with particle diameters varying from 6.0 x 10(-6) m to 1.4 x 10(-5) m. In the rotating plate generator, a poly-dispersed phosphate rock concentrate with Stokes mean diameter of 1.30 x 10(-6) m and size range between 1.5 x 10(-7) m and 8.0 x 10(-6) m Was utilized as powder material in all tests. In the tests performed with the mono-dispersed particles. the median charges of the particles varied between -3.0 x 10-(16) C and -5.0 x 10(-18) degrees C and a weak dependence between particle size and charge was observed. The particles were predominantly negatively charged. In the tests with the poly-dispersed particles the median charges varied fairly linearly with the particle diameter and were negative. The order of magnitude of the results obtained is in accordance with data reported in the literature. The charge distribution, in this case, was wider, so that an appreciable amount of particles were positively charged. The relative spread of the distribution varied with the charging method. It was also noticed that the corona charger acted very effectively in charging the particles. (C) 2008 Elsevier BY. All rights reserved.

A Study of Influence of Configurations of the Windings on the Performance of Single Phase Induction Motor with Capacitor Start

The single phase induction motors needs two stator windings to produce rotating magnetic field : one main winding and the other auxiliary winding. The aim of the auxiliary winding is to create the rotating electromagnetic field when the machine is started-up and is afterwards turned off, generally through the centrifugal switch coupled together with the shaft of the machine rotor. The main purpose of this document is to evaluate the influence that the two windings have on the external characteristics of the single phase induction motor. For this purpose, two different kinds of windings were carried out and simulated, with the proposal to obtain some benefits. The main winding and the auxiliary winding were prepared and mounted on a prototype. The simulation was done via software based FEM, to make the extraction and results analysis possible. This results are shown at the end this document.

2D evaluation of crack openings using smeared and embedded crack models

This work deals with the determination of crack openings in 2D reinforced concrete structures using the Finite Element Method with a smeared rotating crack model or an embedded crack model In the smeared crack model, the strong discontinuity associated with the crack is spread throughout the finite element As is well known, the continuity of the displacement field assumed for these models is incompatible with the actual discontinuity However, this type of model has been used extensively due to the relative computational simplicity it provides by treating cracks in a continuum framework, as well as the reportedly good predictions of reinforced concrete members` structural behavior On the other hand, by enriching the displacement field within each finite element crossed by the crack path, the embedded crack model is able to describe the effects of actual discontinuities (cracks) This paper presents a comparative study of the abilities of these 2D models in predicting the mechanical behavior of reinforced concrete structures Structural responses are compared with experimental results from the literature, including crack patterns, crack openings and rebar stresses predicted by both models

Friction coefficient and abrasive wear modes in ball-cratering tests conducted at constant normal force and constant pressure-Preliminary results

The micro-scale abrasive wear test by rotative ball has gained large acceptance in universities and research centers, being widely used in studies on the abrasive wear of materials. Two wear modes are usually observed in this type of test: ""rolling abrasion"" results when the abrasive particles roll on the surface of the tested specimen, while ""grooving abrasion"" is observed when the abrasive particles slide; the type of wear mode has a significant effect on the overall behaviour of a tribological system. Several works on the friction coefficient during abrasive wear tests are available in the literature, but only a few were dedicated to the friction coefficient in micro-abrasive wear tests conducted with rotating ball. Additionally, recent works have identified that results may also be affected by the change in contact pressure that occurs when tests are conducted with constant applied force. Thus, the purpose of this work is to study the relationship between friction coefficient and abrasive wear modes in ball-cratering wear tests conducted at ""constant normal force"" and ""constant pressure"". Micro-scale abrasive wear tests were conducted with a ball of AISI52100 steel and a specimen of AISIH10 tool steel. The abrasive slurry was prepared with black silicon carbide (SiC) particles (average particle size of 3 mu m) and distilled water. Two constant normal force values and two constant pressure values were selected for the tests. The tangential and normal loads were monitored throughout the tests and their ratio was calculated to provide an indication of the friction coefficient. In all cases, optical microscopy analysis of the worn craters revelated only the presence of grooving abrasion. However, a more detailed analysis conducted by SEM has indicated that different degrees of rolling abrasion have also occurred along the grooves. The results have also shown that: (i) for the selected values of constant normal force and constant pressure, the friction coefficient presents, approximately, the same range of values and (ii) loading conditions play an important role on the occurrence of rolling abrasion or grooving abrasion and, consequently, on the average value and scatter of the friction coefficient in micro-abrasive wear tests. (C) 2009 Elsevier B.V. All rights reserved.

Void fraction measurement and signal analysis from multiple-electrode impedance sensors

Void fraction sensors are important instruments not only for monitoring two-phase flow, but for furnishing an important parameter for obtaining flow map pattern and two-phase flow heat transfer coefficient as well. This work presents the experimental results obtained with the analysis of two axially spaced multiple-electrode impedance sensors tested in an upward air-water two-phase flow in a vertical tube for void fraction measurements. An electronic circuit was developed for signal generation and post-treatment of each sensor signal. By phase shifting the electrodes supplying the signal, it was possible to establish a rotating electric field sweeping across the test section. The fundamental principle of using a multiple-electrode configuration is based on reducing signal sensitivity to the non-uniform cross-section void fraction distribution problem. Static calibration curves were obtained for both sensors, and dynamic signal analyses for bubbly, slug, and turbulent churn flows were carried out. Flow parameters such as Taylor bubble velocity and length were obtained by using cross-correlation techniques. As an application of the void fraction tested, vertical flow pattern identification could be established by using the probability density function technique for void fractions ranging from 0% to nearly 70%.

The synergism between high superficial roughness and corrosive atmosphere in the fatigue behavior of the SAE 1045 steel

The fatigue behavior of the SAE 1045 steel in four different conditions is reported in this paper. Four treatments were tested: polished surface, corrosive atmosphere (sugar cane juice), low quality roughness (typical equivalent surface of the shaft cane mill) and the combined condition of the two last treatments involved. Fatigue tests were performed in rotating bending conditions and the values of fatigue strength for the different situations from tests were obtained. The diminution in fatigue strength for the synergy condition of rough surface and corrosive atmosphere was of 8.7%, result statistically representative with less than 0.01% of uncertainty.

A Short Note on Transverse Vibrations of a Shaft Carrying Two (or One) Disk Excited by a Nonideal Motor

The paper presents a number of numerical simulations of the transverse vibrations of two (or one) imbalanced rotors forced by an electric motor with limited power supply, during the passage through of the two resonance zones (increasing and decreasing input voltages). The predominant presence of the Sommerfeld effect. when the rotational velocity of the motor is captured, in the second resonance frequency is demonstrated. We have shown that the hysteretic jump phenomenon exists in a rotor system with two (or one) disks, and with this, we have shown that a torque is influenced by the dynamical behavior of die rotor [DOI: 10.1115/1.3007979]

Liquid distribution as a means to describing the granule growth mechanism

Copper concentrate (chalcopyrite) was granulated in a rotating drum with a diameter of 0.3 m and a length of 0.2 m. Water was used as the binder and it was sprayed onto the powder bed with a nozzle. This material exhibited induction type behaviour, which was defined by Iveson and Litster [AIChE J. 44 (1998) 1510]. Induction type behaviour is characterized by the occurrence of an induction stage, during which the granules are gradually being compacted and little or no growth occurs. At the end of this induction stage, binder liquid is squeezed from the interior of the granules onto the granule surface and the granules are then surface-wet. This results in a rapid growth rate of the granules. Different types of experiments were conducted. The influence of the nozzle pressure and the distance from the nozzle to the powder bed on the growth behaviour of the granules as well as on the binder distribution was examined. The results of these experiments led to the postulation of a modified mechanism for induction type behaviour: it was found that after the binder was delivered, there were large granules containing a high amount of binder and small granules containing less binder. During the induction stage, the granules are compacted and binder liquid continuously appears at the surface of the large granules. These wet spots that are continuously being formed pick up the dry and small granules. When all the small granules have been picked up, further expulsion of binder liquid onto the granules' surface results in granules that remain surface-wet. This phenomenon marks the end of the induction stage and it coincides with the disappearance of the small granules. The hypothesis was tested by selectively removing the smaller granules during an experiment. As expected, this resulted in a shorter induction time.