Mechanical properties of ZnS nanowires and thin films: Microscopic origin of the dependence on size and growth direction

Mechanical properties of ZnS nanowires and thin films are studied as a function of size and growth direction using all-atom molecular dynamics simulations. Using the stress-strain relationship we extract Young's moduli of nanowires and thin films at room temperature. Our results show that Young's modulus of 0001] nanowires has strong size dependence. On the other hand, 01 (1) over bar0] nanowires do not exhibit a strong size dependence of Young's modulus in the size range we have investigated. We provide a microscopic understanding of this behavior on the basis of bond stretching and contraction due to the rearrangement of atoms in the surface layers. The ultimate tensile strengths of the nanowires do not show much size dependence. To investigate the mechanical behavior of ZnS in two dimensions, we calculate Young's modulus of thin films under tensile strain along the 0001] direction. Young's modulus of thin films converges to the bulk value more rapidly than that of the 0001] nanowire.

Microstructure and dry sliding wear resistance evaluation of plasma nitrided austenitic stainless steel type AISI 316LN against different sliders

In this work, Plasma Nitriding was carried out at a temperature of 570 degrees C on nuclear grade austenitic stainless steel type AISI 316 LN (316LN SS) in a gas mixture of 20% N-2-80% H-2 to improve the surface hardness and thereby sliding wear resistance. The Plasma Nitride (PN) treated surface has been characterized by Vickers microhardness measurements, Scanning Electron Microscopic (SEM) examination, X-ray Diffraction (XRD) and sliding wear assessment. The average thickness of the PN layer was found to be 70 mu m. Microhardness measurements showed a significant increase in the hardness from 210 HV25g (unnitrided sample) to 1040 HV25g (Plasma Nitrided sample). The XRD reveals that PN layer consists of CrN, Fe4N and Fe3N phases along with austenite phase. The tribological parameters such as the friction coefficient and wear mechanism have been evaluated at ambient conditions for PN treated ring (PN ring) vs. ASTM A453 grade 660 pin (ASTM pin), PN ring vs. Nickel based alloy hard faced pin (Colmonoy pin), PN ring vs. 316LN SS pin and 316LN SS ring vs. 316LN SS pin. The wear tracks have been analyzed by SEM, Energy Dispersive X-ray Analysis (EDX) and Optical Profilometry. The untreated 316LN SS ring vs. 316LN SS pin produced severe wear and was characterized by a combination of delamination and adhesion wear mechanism, whereas wear mechanism of the PN rings reveals mild abrasion and a transfer layer from pin materials. (C) 2012 Elsevier B.V. All rights reserved.

Charge-transfer interaction mediated organogels from bile acid appended anthracenes: rheological and microscopic studies

In this article we present dual-component charge-transfer interaction (CT) induced organogel formation with bile acid anthracene conjugates as donors and 2,4,7-trinitrofluorenone (TNF) as the acceptor. The use of TNF (1) as a versatile electron acceptor in the formation of gels is demonstrated through the formation of gels with different steroidal groups on the anthracene moiety in a variety of solvents ranging from aromatic hydrocarbons to long chain alcohols. Thermal stability and variable temperature fluorescence experiments were performed on these CT gels. Dynamic rheological experiments conducted on these gels suggest that these are viscoelastic soft materials and with the gel strength can be modulated by varying the donor/acceptor ratios.

Microscopic dynamics of nanoparticle monolayers at air-water interface

We present results of surface mechanical and particle tracking measurements of nanoparticles trapped at the air-water interface as a function of their areal density. We monitor both the surface pressure (II) and isothermal compression modulus (epsilon) as well as the dynamics of nanoparticle clusters, using fluorescence confocal microscopy while they are compressed to very high density near the two dimensional close packing density Phi similar to 0.82. We observe non-monotonic variation in both epsilon and the dynamic heterogeneity, characterized by the dynamical susceptibility chi(4) with Phi, in such high density monolayers. We provide insight into the underlying nature of such transitions in close packed high density nanoparticle monolayers in terms of the morphology and flexibility of these soft colloidal particles.. We discuss the significance our results in the context of related studies on two dimensional granular or colloidal systems. (C) 2013 Elsevier Inc. All rights reserved.

Evidence of collective relaxation behavior in the reentrant phase of oxygen-rich LaMnO3

The reentrant low temperature phase of the perovskite manganite LaMnO3+delta (delta=0.22) has been investigated with ac susceptibility and dc magnetization studies. A critical examination of the memory effects in ac susceptibility leads us to the conclusion that the slow dynamics in the system is a consequence of collective relaxation processes resulting from interactions between ferromagnetic clusters, whose presence was indicated in earlier studies. Here, we postulate that the collective behavior is due to the existence of long-range (dipolar) interactions between the large ferromagnetic `superspins'. This is also confirmed by an abnormally large microscopic spin-flip time (similar to 10(-9) s) compared to a canonical spin glass. (C) 2013 Elsevier B.V. All rights reserved.

Chemical unfolding of chicken villin headpiece in aqueous dimethyl sulfoxide solution: cosolvent concentration dependence, pathway, and microscopic mechanism

Unfolding of a protein often proceeds through partial unfolded intermediate states (PUIS). PUIS have been detected in several experimental and simulation studies. However, complete analyses of transitions between different PUIS and the unfolding trajectory are sparse. To understand such dynamical processes, we study chemical unfolding of a small protein, chicken villin head piece (HP-36), in aqueous dimethyl sulfoxide (DMSO) solution. We carry out molecular dynamics simulations at various solution compositions under ambient conditions. In each concentration, the initial step of unfolding involves separation of two adjacent native contacts, between phenyl alanine residues (11-18 and 7-18). This first step induces, under appropriate conditions, subsequent separation among other hydrophobic contacts, signifying a high degree of cooperativity in the unfolding process. The observed sequence of structural changes in HP-36 on increasing DMSO concentration and the observed sequence of PUIS, are in approximate agreement with earlier simulation results (in pure water) and experimental observations on unfolding of HP-36. Peculiar to water-DMSO mixture, an intervening structural transformation (around 15% of DMSO) in the binary mixture solvent retards the progression of unfolding as composition is increased. This is reflected in a remarkable nonmonotonic composition dependence of RMSD, radius of gyration and the fraction of native contacts. At 30% mole fraction of DMSO, we find the extended randomly coiled structure of the unfolded protein. The molecular mechanism of DMSO induced unfolding process is attributed to the initial preferential solvation of the hydrophobic side chain atoms through the methyl groups of DMSO, followed by the hydrogen bonding of the oxygen atom of DMSO to the exposed backbone NH groups of HP-36.

Microscopic and dielectric studies of ZnO nanoparticles loaded in ortho-chloropolyaniline nanocomposites

We have studied the preparation of zinc oxide nanoparticles loaded in various weight percentages in ortho-chloropolyaniline by in situ polymerization method. The length of the O-chloropolyaniline tube is found to be 200 nm and diameter is about 150 nm wherein the embedded ZnO nanoparticles is of 13 nm as confirmed from scanning electron microscopy as well as transmission electron microscopy characterizations. The presence of the vibration band of the metal oxide and other characteristic bands confirms that the polymer nanocomposites are characterized by their Fourier transmission infrared spectroscopy. The X-ray diffraction pattern of nanocomposites reveals their polycrystalline nature. Electrical property of nanocomposites is a function of the filler as well as the matrix. Cole-Cole plots reveal the presence of well-defined semicircular arcs at high frequencies which are attributed to the bulk resistance of the material. Among all nanocomposites, 30 wt% shows the low relaxation time of 151 s, and hence it has high conductivity.

Current rectification by a single ZnS nanorod probed using a scanning tunneling microscopic technique

We report on the rectification properties from a single ZnS nanorod measured using the UHV-SPM technique. The rectification behavior is evidenced from the current-voltage characteristics measured on a single ZnS nanorod. We propose a tunneling mechanism where the direct tunneling mechanism is dominant at lower applied bias voltages followed by resonant tunneling through discrete energy levels of the nanorod. A further increase in the bias voltage changes the tunneling mechanism to the Fowler-Nordheim tunneling regime enabling rectification behavior. Realizing rectification from a single ZnS nanorod may provide a means of realizing a single nanorod based miniaturized device.

Structural characterization of electrodeposited boron

Structural characterization of electrodeposited boron was carried out by using transmission electron microscopy and Raman spectroscopy. Electron diffraction and phase contrast imaging were carried out by using transmission electron microscopy. Phase identification was done based on the analysis of electron diffraction patterns and the power spectrum calculated from the lattice images from thin regions of the sample. Raman spectroscopic examination was carried out to study the nature of bonding and the allotropic form of boron obtained after electrodeposition. The results obtained from transmission electron microscopy showed the presence of nanocrystallites embedded in an amorphous mass of boron. Raman microscopic studies showed that amorphous boron could be converted to its crystalline form at high temperatures.

Studies on microscopic structure of diesel sprays under atmospheric and high gas pressures

In the present work, the spray structure of diesel from a 200-mu m, single-hole solenoid injector is studied using microscopic imaging at injection pressures of 700, 1000 and 1400 bar for various gas pressures. A long-distance microscope with a high resolution camera is used for spray visualization with a direct imaging technique. This study shows that even at very high injection pressures, the spray structure in an ambient environment of atmospheric pressure reveals presence of entangled ligaments and non-spherical droplets during the injection period. With increase in the injection pressure, the ligaments tend to get smaller and spread radially. The spray structure studies are also conducted at high gas pressures in a specially designed high pressure chamber with optical access. The near nozzle spray structure at the end of the injection shows that the liquid jet breakup is improved with increase in gas density. The droplet size measurement is possible only late in the injection duration when the breakup appears to be complete and mostly spherical droplets are observed. Hence, droplet size measurements are performed after 1.3 ms from start of the injection pulse. Spatial and temporal variation in Sauter Mean `Diameter (SMD) is observed and reported for the case corresponding to an injection pressure of 700 bar. Overall, this study has highlighted the importance of verifying the extentof atomization and droplet shape even in dense sprays before using conventional dropsizing methods such as PDPA.

Microscopic description of the evolution of the local structure and an evaluation of the chemical pressure concept in a solid solution

Extended x-ray absorption fine-structure studies have been performed at the Zn K and Cd K edges for a series of solid solutions of wurtzite Zn1-xCdxS samples with x = 0.0, 0.1, 0.25, 0.5, 0.75, and 1.0, where the lattice parameter as a function of x evolves according to the well-known Vegard's law. In conjunction with extensive, large-scale first-principles electronic structure calculations with full geometry optimizations, these results establish that the percentage variation in the nearest-neighbor bond distances are lower by nearly an order of magnitude compared to what would be expected on the basis of lattice parameter variation, seriously undermining the chemical pressure concept. With experimental results that allow us to probe up to the third coordination shell distances, we provide a direct description of how the local structure, apparently inconsistent with the global structure, evolves very rapidly with interatomic distances to become consistent with it. We show that the basic features of this structural evolution with the composition can be visualized with nearly invariant Zn-S-4 and Cd-S-4 tetrahedral units retaining their structural integrity, while the tilts between these tetrahedral building blocks change with composition to conform to the changing lattice parameters according to the Vegard's law within a relatively short length scale. These results underline the limits of applicability of the chemical pressure concept that has been a favored tool of experimentalists to control physical properties of a large variety of condensed matter systems.

Finite size scaling in crossover among different random matrix ensembles in microscopic lattice models

Using numerical diagonalization we study the crossover among different random matrix ensembles (Poissonian, Gaussian orthogonal ensemble (GOE), Gaussian unitary ensemble (GUE) and Gaussian symplectic ensemble (GSE)) realized in two different microscopic models. The specific diagnostic tool used to study the crossovers is the level spacing distribution. The first model is a one-dimensional lattice model of interacting hard-core bosons (or equivalently spin 1/2 objects) and the other a higher dimensional model of non-interacting particles with disorder and spin-orbit coupling. We find that the perturbation causing the crossover among the different ensembles scales to zero with system size as a power law with an exponent that depends on the ensembles between which the crossover takes place. This exponent is independent of microscopic details of the perturbation. We also find that the crossover from the Poissonian ensemble to the other three is dominated by the Poissonian to GOE crossover which introduces level repulsion while the crossover from GOE to GUE or GOE to GSE associated with symmetry breaking introduces a subdominant contribution. We also conjecture that the exponent is dependent on whether the system contains interactions among the elementary degrees of freedom or not and is independent of the dimensionality of the system.