Inverse surface melting in confined clusters: Ar-13 in zeolite L

Monte Carlo and molecular dynamics simulations on an Ar-13 cluster in zeolite L have been carried out at a series of temperatures to understand the rigid-nonrigid transition corresponding to the solid-liquid transition exhibited by the free Ar-13 cluster. The icosahedral geometry of the free cluster is no longer preferred when the cluster is confined in the zeolite. The root-mean-squared pair distance fluctuation, delta, exhibits a sharp, well-defined rigid-nonrigid transition at 17 K as compared to 27 K for the free cluster. Multiple peaks in the distribution of short-time averages of the guest-host interaction energy indicate coexistence of two phases.; It is shown that this transition is associated with the inner atoms becoming mobile at 17 K even while the outer layer atoms, which are in close proximity to the zeolitic wall, continue to be comparatively immobile. This may be contrasted with the melting of large free clusters of 40 or more atoms which exhibit surface melting. Guest-host interactions seem to play a predominant role in determining the properties of confined clusters. We demonstrate that the volume of the cluster increases rather sharply at 17 and 27 K respectively for the confined and the free cluster. Power spectra suggest that the motion of the inner atoms is generally parallel to the atoms which form the cage wall.

Temperature dependence of the levitation effect - Implications for separation of multicomponent mixtures

Sufficiently long molecular dynamics simulations have been carried out on spherical monatomic sorbates in NaY zeolite, interacting via simple Lennard-Jones potentials, to investigate the dependence of the levitation effect on the temperature. Simulations carried out in the range 100-300 K suggest that the anomalous peak in the diffusion coefficient (observed when the levitation parameter, gamma, is near unity) decreases in intensity with increase in temperature. The rate of cage-to-cage migrations also exhibits a similar trend. The activation energy obtained from Arrhenius plots is found to exhibit a minimum when the diffusion coefficient is a maximum, corresponding to the gamma approximate to 1 sorbate diameter. In the linear or normal regime, the activation energy increases with increase in sorbate diameter until it shows a sharp decrease in the anomalous regime. Locations and energies of the adsorption sites and their dependence on the sorbate size gives interesting insight into the nature of the underlying potential-energy surface and further explain the observed trend in the activation energy with sorbate size. Cage residence times, tau(c), show little or no change with temperature for the sorbate with diameter corresponding to gamma approximate to 1, whereas there is a significant decrease in tau(c) with increase in temperature for sorbates in the linear regime. The implications of the present study for the separation of mixtures of sorbates are discussed.

X-ray reflectivity study of semiconductor interfaces

The results of an X-ray reflectivity study of thick AlAs-AlGaAs and thin GeSi-Ge multilayers grown using metal-organic vapour-phase epitaxy and ion-beam sputtering deposition techniques, respectively, are presented. Asymmetry in interfaces is observed in both of these semiconductor multilayers. It is also observed that although the Si-on-Ge interface is sharp, an Si0.4Ge0.6 alloy is formed at the Ge-on-Si interface. In the case of the III-V semiconductor, the AlAs-on-AlGaAs interface shows much greater roughness than that observed in the AlGaAs-on-AlAs interface. For thin multilayers it is demonstrated that the compositional profile as a function of depth can be obtained directly from the X-ray reflectivity data.

Ising pyrochlore magnets: Low-temperature properties, "ice rules," and beyond

Pyrochlore magnets are candidates for what Harris et al. [Phys. Rev. Lett. 79, 2554 (1997)] call "spin-ice" behavior. We present theoretical simulations of relevance for the pyrochlore family R2Ti2O7 (R = rare earth) supported by magnetothermal measurements on selected systems. Ey considering long-ranged dipole-dipole as well as short-ranged superexchange interactions, we get three distinct behaviors: (i) an ordered doubly degenerate state, (ii) a highly disordered state with a broad transition to paramagnetism, and (iii) a partially ordered state with a sharp transition to paramagnetism. Closely corresponding behavior is seen in the real compounds.

Residence time distribution for a class of Gaussian Markov processes

We study the distribution of residence time or equivalently that of "mean magnetization" for a family of Gaussian Markov processes indexed by a positive parameter alpha. The persistence exponent for these processes is simply given by theta=alpha but the residence time distribution is nontrivial. The shape of this distribution undergoes a qualitative change as theta increases, indicating a sharp change in the ergodic properties of the process. We develop two alternate methods to calculate exactly but recursively the moments of the distribution for arbitrary alpha. For some special values of alpha, we obtain closed form expressions of the distribution function. [S1063-651X(99)03306-1].

Studies on grinding media wear and its effect on flotation of ferrugenous phosphate ore

Marked ball grinding rests were carried out in the laboratory with a low grade phosphate ore under different experimental conditions. Two types of balls were used, namely high carbon low alloy (HCLA) cast steel and high chrome cast iron. Results of marked ball grinding tests indicated that ball wear increased with time and showed a sharp increase for wet grinding over dry grinding. Ball wear under wet grinding conditions was also influenced by the gaseous atmosphere in the mill. The grinding ball materials could be arranged in the following order with respect to their overall wear resistance: High chrome cast iron > HCLA cast steel balls Methods to minimize ball wear through control of mill atmosphere and addition of flotation reagents are discussed. Effect of grinding media and additions of flotation reagents during grinding on phosphate ore flotation are also discussed. (C) 1999 Elsevier Science Ltd. All rights reserved.

Subquadratic quantum number dependence and other anomalies of vibrational dephasing in liquid nitrogen: Molecular dynamics simulation study from the triple point to the critical point and beyond

Vibrational phase relaxation near gas-liquid and liquid-solid phase coexistence has been studied by molecular dynamics simulations of N-N stretch in N-2. Experimentally observed pronounced insensitivity of phase relaxation from the triple point to beyond the boiling point is found to originate from a competition between density relaxation and resonant-energy transfer terms. The sharp rise in relaxation rate near the critical point (CP) can be attributed at least partly to the sharp, rise in vibration-rotation coupling contribution. Substantial subquadratic quantum number dependence of overtone dephasing rate is found near the CP and in supercritical fluids. [S0031-9007 (99)09318-7].

Fluorescence and visual sensing of nitroaromatic explosives using electron rich discrete fluorophores

Several pi-electron rich fluorescent aromatic compounds containing trimethylsilylethynyl functionality have been synthesized by employing Sonogashira coupling reaction and they were characterized fully by NMR (H-1, C-13)/IR spectroscopy. Incorporation of bulky trimethylsilylethynyl groups on the peripheral of the fluorophores prevents self-quenching of the initial intensity through pi-pi interaction and thereby maintains the spectroscopic stability in solution. These compounds showed fluorescence behavior in chloroform solution and were used as selective fluorescence sensors for the detection of electron deficient nitroaromatics. All these fluorophores showed the largest quenching response with high selectivity for nitroaromatics among the various electron deficient aromatic compounds tested. Quantitative analysis of the fluorescence titration profile of 9,10-bis(trimethylsilylethynyl) anthracene with picric acid provided evidence that this particular fluorophore detects picric acid even at ppb level. A sharp visual detection of 2,4,6-trinitrotoluene was observed upon subjecting 1,3,6,8-tetrakis (trimethylsilylethynyl) pyrene fluorophore to increasing quantities of 2,4,6-trinitrotoluene in chloroform. Furthermore, thin film of the fluorophores was made by spin coating of a solution of 1.0 x 10(-3) M in chloroform or dichloromethane on a quartz plate and was used for the detection of vapors of nitroaromatics at room temperature. The vapor-phase sensing experiments suggested that the sensing process is reproducible and quite selective for nitroaromatic compounds. Selective fluorescence quenching response including a sharp visual color change for nitroaromatics makes these fluorophores as promising fluorescence sensory materials for nitroaromatic compounds (NAC) with a detection limit of even ppb level as judged with picric acid.

Turbulent near-wake development behind a flat plate

An asymptotic analysis of the two-dimensional turbulent near-wake flow behind a Rat plate with sharp trailing edge has been formulated, The feature that the near-wake, which is dominated by the mixing of the oncoming turbulent boundary layers retains, to a large extent, the memory of the turbulent structure of the upstream boundary layer has been exploited to develop the analysis. This analysis leads to two regions of the near-wake flow (the inner near-wake and the outer near-wake) for which the governing equations are derived. The matching conditions among these regions lead to a logarithmic variation in the normal direction in the overlapping region surrounding the inner near-wake. These features are validated by the available experimental data. Similarity solutions for the velocity distribution (which satisfy the required matching conditions) in the inner near-wake and outer near-wake regions have been obtained by making the appropriate eddy-viscosity assumptions, Uniformly valid solutions for velocity distribution have been constructed for the near-wake. The solutions show good agreement with available experimental data. (C) Elsevier, Paris.

Data rectification and detection of trend shifts in jet engine path measurements using median filters and fuzzy logic

Filtering methods are explored for removing noise from data while preserving sharp edges that many indicate a trend shift in gas turbine measurements. Linear filters are found to be have problems with removing noise while preserving features in the signal. The nonlinear hybrid median filter is found to accurately reproduce the root signal from noisy data. Simulated faulty data and fault-free gas path measurement data are passed through median filters and health residuals for the data set are created. The health residual is a scalar norm of the gas path measurement deltas and is used to partition the faulty engine from the healthy engine using fuzzy sets. The fuzzy detection system is developed and tested with noisy data and with filtered data. It is found from tests with simulated fault-free and faulty data that fuzzy trend shift detection based on filtered data is very accurate with no false alarms and negligible missed alarms.

Effect of the sulfonic acid group on copolymers of aniline and toluidine with m-aminobenzene sulfonic acid

This article describes the results of the preparation and characterization of self-doped conducting copolymers of aniline and toluidine with m-aminobenzene sulfonic acid. The copolymers have an intrinsic acid group that is capable of doping polyaniline. Spectroscopic, morphological, and electrical conductivity studies have provided insight into the structural and electronic properties of the copolymers. The differences in the properties of polyaniline and polytoluidine due to the sulfonic acid ring substituent on the phenyl ring are discussed. The scanning electron micrographs of the copolymers reveal regions of sharp-edged, needle-shaped structures, whereas the X-ray diffraction patterns show that the copolymers are relatively more crystalline in nature. (C) 2002 Wiley Periodicals, Inc.

Mossbauer study of La1-xCaxMn1-y (57)FeyO(3) with x = 0, 0.25; y=0.01

Temperature dependent Mossbauer measurements are done on the samples of La1- xCaxMn1-y (FeyO3)-Fe-57 with x=0 and 0.25, and y=0.01. With decreasing temperature, the specimen with x=0.25 shows a paramagnetic to ferromagnetic transition around 175 K. In the specimen x=0.0, the temperature dependence of both the center shift (delta) and the recoilless fraction (f) can be fitted very well with the Debye theory with a theta(D)=320+/-50 K. But for the specimens with x=0.25, f and delta show distinct deviations from the Debye behavior in the temperature range in which the resistivity shows a sharp decrease. Dips observed in both the f and delta around the transition temperature suggest that the Jahn-Teller distortion observed in these systems is dynamic in nature.

Phase transformation and semiconductor-metal transition in thin films of VO2 deposited by low-pressure metalorganic chemical vapor deposition

Thin films of the semiconducting, monoclinic vanadium dioxide, VO2(M) have been prepared on ordinary glass by two methods: directly by low-pressure metalorganic chemical vapor deposition (MOCVD), and by argon-annealing films of the VO2(B) phase deposited by MOCVD. The composition and microstructure of the films have been examined by x-ray diffraction, scanning electron microscopy, and transmission electron microscopy. Films made predominantly of either the B or the M phase, as deposited, can only be obtained over a narrow range of deposition temperatures. At the lower end of this temperature range, the as-deposited films are strongly oriented, although the substrate is glass. This can be understood from the drive to minimize surface energy. Films of the B phase have a platelet morphology, which leads to an unusual microstructure at the lower-deposition temperatures. Those grown at similar to370 degreesC convert to the metallic, rutile (R) phase when annealed at 550 degreesC, whereas those deposited at 420 degreesC transform to the R phase only at 580 degreesC. (When cooled to room temperature, the annealed films convert reversibly from the R phase to the M phase.) Electron microscopy shows that annealing leads to disintegration of the single crystalline VO2(B) platelets into small crystallites of VO2(R), although the platelet morphology is retained. When the annealing temperature is relatively low, these crystallites are nanometer sized. At a higher-annealing temperature, the transformation leads to well-connected and similarly oriented large grains of VO2(R), enveloped in the original platelet. The semiconductor-metal transition near 68 degreesC leads to a large jump in resistivity in all the VO2(M) films, nearly as large as in epitaxial films on single-crystal substrates. When the annealed films contain well-connected large grains, the transition is very sharp. Even when preferred orientation is present, the transition is not as sharp in as-deposited VO2(M), because the crystallites are not densely packed as in annealed VO2(B). However, the high degree of orientation in these films leads to a narrow temperature hysteresis. (C) 2002 American Institute of Physics.

An assessment of creep deformation and fracture behavior of 2.25Cr-1Mo similar and dissimilar weld joints

The evaluation of the creep deformation and fracture behavior of a 2.25Cr-1Mo steel base metal, a 2.25Cr-1Mo/2.25Cr-1Mo similar weld joint, and a 2.25Cr-1Mo/Alloy 800 dissimilar weld joint at 823 K over a stress range of 90 to WO MPa has been carried out. The specimens for creep testing were taken from single-V weld pads fabricated by a shielded metal arc-welding process using 2.25Cr-1Mo steel (for similar-joint) and INCONEL 182 (for dissimilar-joint) electrodes. The weld pads were subsequently given a postweld hear treatment (PWHT) of 973 K for I hour. The microstructure and microhardness of the weld joints were evaluated in the as-welded, postweld heat-treated, and creep-tested conditions. The heat-affected zone (HAZ) of similar weld joint consisted of bainite in the coarse-prior-austenitic-grain (CPAG) region near the fusion line, followed by bainite in the fine-prior-austenitic-grain (FPAG) and intercritical regions merging with the unaffected base metal. In addition to the HAZ structures in the 2.25Cr-1Mo steel, the dissimilar weld joint displayed a definite INCONEL/2.25Cr-1Mo weld interface structure present either as a sharp line or as a diffuse region. A hardness trough was observed in the intercritical region of the HAZ in both weld joints, while a maxima in hardness was seen at the weld interface of the dissimilar weld joint. Both weld joints exhibited significantly lower rupture lives compared to the 2.25Cr-1Mo base metal. The dissimilar weld joint exhibited poor rupture life compared to the similar weld joint, at applied stresses lower than 130 MPa. In both weld joints, the strain distribution across the specimen gage length during creep testing varied significantly. During creep testing, localization of deformation occurred in the intercritical HAZ. In the similar weld joint, at all stress levels investigated, and in the dissimilar weld joint, at stresses greater than or equal to 150 MPa, the creep failure occulted in the intercritical HAZ. The fracture occurred by transgranular mode with a large number of dimples. At stresses below 150 MPa, the failure in the dissimilar weld joint occurred in the CPAG HAZ near to the weld interface. The failure occurred by extensive intergranular creep cavity formation.

The design and synthesis of redox core-alpha amino acid composites based on thiol-disulfide exchange mechanism and a comparative study of their zinc abstraction potential from [CCXX] boxes in proteins

The design and synthesis of agents that can abstract zinc from their [CCXX] (C=cysteine; X=cysteine/histidine) boxes by thioldisulfide exchange-having as control, the redox parities of the core sulfur ligands of the reagent and the enzyme, has been illustrated, and their efficiency demonstrated by monitoring the inhibition of the transcription of calf thymus DNA by E. coli RNA polymerase, which harbors two zinc atoms in their [CCXX] boxes of which one is exchangeable. Maximum inhibition possible with removal of the exchangeable zinc was seen with redox-sulfanilamide-glutamate composite. In sharp contrast, normal chelating agents (EDTA, phenanthroline) even in a thousand fold excess showed only marginal inhibition, thus supporting an exchange mechanism for the metal removal. (C) 2002 Elsevier Science Ltd. All rights reserved.