Hydroxylation of oxygen-covered Cu(110) and Zn(0001) surfaces by interaction with CH3OH, (CH3)2NH, H2S, HCl and other proton donor molecules

EELS studies provide definitive evidence for the hydroxylation of oxygen-covered Cu(110) and Zn(0001) surfaces on interaction with proton donor molecules such as H2O, CH3OH, HCOOH, NH3 and (CH3)2NH. The occurrence of surface hydroxylation is unambigouusly shown by a study of the interaction of H2S and HCl with an oxygen covered Cu(110) surface.

Effect of HCl on the adsorption of oxygen on Cu(110) surface: An eels study

Oxygen is shown to adsorb molecularly on a clean Cu(110) surface at 80 K and dissociate around 150 K forming atomic oxygen. Adsorption of oxygen on an HCl covered surface at low temperatures results in the formation of adsorbed hydroxyl groups and water in addition to adsorbed molecular oxygen. The molecular oxygen species is stable up to 190 K on the HCl covered surface.

Coherent phonons in pyrochlore titanates A(2)Ti(2)O(7) (A = Dy, Gd, Tb): A phase transition in Dy2Ti2O7 at 110 K

We study the generation of coherent optical phonons in spin-frustrated pyrochlore single crystals Dy2Ti2O7, Gd2Ti2O7, and Tb2Ti2O7 using femtosecond laser pulses (65 fs, 1.57 eV) in degenerate time-resolved transmission experiments as a function of temperature from 4 to 296 K. At 4 K, two coherent phonons are observed at similar to 5.3 THz (5.0 THz) and similar to 9.3 THz (9.4 THz) for Dy2Ti2O7 (Gd2Ti2O7), whereas three coherent phonons are generated at similar to 5.0, 8.6, and 9.7 THz for Tb2Ti2O7. In the case of spin-ice Dy2Ti2O7, a clear discontinuity is observed in the linewidths of both the coherent phonons as well as in the phase of lower-energy coherent phonon mode, indicating a subtle structural change at 110 K. Another important observation is a phase difference of pi between the modes in all the samples, thus suggesting that the driving forces behind the generation of these modes could be different in nature, unlike a purely impulsive or displacive mechanism.

Coadsorption of Dioxygen and Water on the Ni(110) Surface: Role of O1--Type Species in the Dissociation of Water

While the adsorption of dioxygen at a clean Ni(110) surface gives rise to two O(1s) features at 531 and 530 eV assigned to O-(a) and O2-(a) type species respectively, coadsorption of dioxygen and water mixtures result in the additional formation of hydroxyl species characterized by an O(1s) peak at 532.3 eV. The latter is attributed to the oxygen induced dissociation of water via a low energy pathway involving the O-(a)-type species. The proportions of the O-(a) and the hydroxyl species are greater for small O-2/H2O ratios and lower temperatures (120 K). With increase in temperature, the relative surface concentrations of the O-(a) and the hydroxyl species decrease while there is an increase in the concentration of the oxidic O2-(a) species. Thus, the surface concentrations of both the hydroxyl and the O2-(a) species depend critically on the presence of O- type species. Above 300K the surface chemistry in the main involves the conversion of O- to O2- species via the hydroxyl species.

Nature of the Oxygen Species at Ni(110) and Ni(100) Surfaces Revealed by Exposure to Oxygen and Oxygen-Ammonia Mixtures: Evidence for the Surface Reactivity of O- Type Species

Adsorption of dioxygen at clean Ni(110) and Ni(100) surfaces gives rise to two prominent features in the O(1s) spectra at 530 and 531 eV due to O2- and O- type species, respectively. Interaction of ammonia with a Ni(100)-O surface where theta(oxygen) < 0.1 ML favors the dissociation of NH3 giving NHn, (n = 1, 2) and N(a) species. This is accompanied by a decrease in the intensity of the 531 eV feature. On the other hand. a Ni(100)-O surface where the oxygen species are mainly of the O2- type is unreactive, Coadsorption studies of NH3-O-2 mixtures show that at Ni(110) surfaces the uptake of both oxygen and ammonia increase with the proportion of oxygen in the NH3-O-2 mixture. The surface concentrations of the O- species and the NHn species also increase with the increase in the O-2/NH3 ratio while the slope of the plot of sigma(N) versus sigma(O-) is around unity. The results demonstrate the high surface reactivity of the O- species and its role in the dissociation of ammonia. Based on these observations, the possibility of the formation of a surface complex between ammonia and oxygen (specifically O-) is suggested. Results from vibrational spectroscopic studies of the coadsorption of NH3-O-2 mixtures are consistent with those from core-level spectroscopic studies.

Topology Optimization of Micromachined Structures with the Manufacturing Constraints of KOH Etching of (110) Silicon

The focus of this paper is on designing useful compliant micro-mechanisms of high-aspect-ratio which can be microfabricated by the cost-effective wet etching of (110) orientation silicon (Si) wafers. Wet etching of (110) Si imposes constraints on the geometry of the realized mechanisms because it allows only etch-through in the form of slots parallel to the wafer's flat with a certain minimum length. In this paper, we incorporate this constraint in the topology optimization and obtain compliant designs that meet the specifications on the desired motion for given input forces. Using this design technique and wet etching, we show that we can realize high-aspect-ratio compliant micro-mechanisms. For a (110) Si wafer of 250 µm thickness, the minimum length of the etch opening to get a slot is found to be 866 µm. The minimum achievable width of the slot is limited by the resolution of the lithography process and this can be a very small value. This is studied by conducting trials with different mask layouts on a (110) Si wafer. These constraints are taken care of by using a suitable design parameterization rather than by imposing the constraints explicitly. Topology optimization, as is well known, gives designs using only the essential design specifications. In this work, we show that our technique also gives manufacturable mechanism designs along with lithography mask layouts. Some designs obtained are transferred to lithography masks and mechanisms are fabricated on (110) Si wafers.

Dielectric properties of (110) oriented PbZrO3 and La-modified PbZrO3 thin films grown by sol-gel process on Pt(111)/Ti/SiO2/Si substrate

Highly (110) preferred orientated antiferroelectric PbZrO3 (PZ) and La-modified PZ thin films have been fabricated on Pt/Ti/SiO2/Si substrates using sol-gel process. Dielectric properties, electric field induced ferroelectric polarization, and the temperature dependence of the dielectric response have been explored as a function of composition. The Tc has been observed to decrease by ∼ 17 °C per 1 mol % of La doping. Double hysteresis loops were seen with zero remnant polarization and with coercive fields in between 176 and 193 kV/cm at 80 °C for antiferroelectric to ferroelectric phase transformation. These slim loops have been explained by the high orientation of the films along the polar direction of the antiparallel dipoles of a tetragonal primitive cell and by the strong electrostatic interaction between La ions and oxygen ions in an ABO3 perovskite unit cell. High quality films exhibited very low loss factor less than 0.015 at room temperature and pure PZ; 1 and 2 mol % La doped PZs have shown the room temperature dielectric constant of 135, 219, and 142 at the frequency of 10 kHz. The passive layer effects in these films have been explained by Curie constants and Curie temperatures. The ac conductivity and the corresponding Arrhenius plots have been shown and explained in terms of doping effect and electrode resistance.

Temperature-pressure-induced solid-solid < 100 > to < 110 > reorientation in FCC metallic nanowire: a molecular dynamic study

Atomistic simulation of initial < 100 > oriented FCC Cu nanowires shows a novel coupled temperature-pressure dependent reorientation from < 100 > to < 110 > phase. A temperature-pressure-induced solid-solid < 100 > to < 110 > reorientation diagram is generated for Cu nanowire with varying cross-sectional sizes. A critical pressure is reported for Cu nanowires with varying cross-sectional sizes, above which an initial < 100 > oriented nanowire shows temperature independent reorientation into the < 110 > phase. The effect of surface stresses on the < 100 > to < 110 > reorientation is also studied. The results indicate that above a critical cross-sectional size for a given temperature-pressure, < 100 > to < 110 > reorientation is not possible. It is also reported here that for a given applied pressure, an increase in temperature is required for the < 100 > to < 110 > reorientation with increasing cross-sectional size of the nanowire. The temperature-pressure-induced solid-solid < 100 > to < 110 > reorientation diagram reported in the present paper could further be used as guidelines for controlling the reorientations/shape memory in nano-scale applications of FCC metallic nanowires.

Spatiotemporal chaos in a model for CO oxidation on Pt(110)

We present numerical studies of a model for CO oxidation on the surface of Pt(110) proposed in Ref. 1. The model shows several interesting regimes, some of which exhibit spatiotemporal chaos. The time series of the CO concentration at a given point consists of a sequence of pulses. We concentrate on interpulse intervals theta and show that their distribution P(theta) approaches a delta function continuously as the system goes from a state M, with meandering spirals, to a state S, with spatially frozen spiral cores. This should be verifiable experimentally.

k.p based closed form energy band gap and transport electron effective mass model for 100] and 110] relaxed and strained Silicon nanowire

In this paper, we address a physics based closed form model for the energy band gap (E-g) and the transport electron effective mass in relaxed and strained 100] and 110] oriented rectangular Silicon Nanowire (SiNW). Our proposed analytical model along 100] and 110] directions are based on the k.p formalism of the conduction band energy dispersion relation through an appropriate rotation of the Hamiltonian of the electrons in the bulk crystal along 001] direction followed by the inclusion of a 4 x 4 Luttinger Hamiltonian for the description of the valance band structure. Using this, we demonstrate the variation in Eg and the transport electron effective mass as function of the cross-sectional dimensions in a relaxed 100] and 110] oriented SiNW. The behaviour of these two parameters in 100] oriented SiNW has further been studied with the inclusion of a uniaxial strain along the transport direction and a biaxial strain, which is assumed to be decomposed from a hydrostatic deformation along 001] with the former one. In addition, the energy band gap and the effective mass of a strained 110] oriented SiNW has also been formulated. Using this, we compare our analytical model with that of the extracted data using the nearest neighbour empirical tight binding sp(3)d(5)s* method based simulations and has been found to agree well over a wide range of device dimensions and applied strain. (C) 2012 Elsevier Ltd. All rights reserved.

A queuing approach for inventory planning with batch ordering in multi-echelon supply chains

This paper presents stylized models for conducting performance analysis of the manufacturing supply chain network (SCN) in a stochastic setting for batch ordering. We use queueing models to capture the behavior of SCN. The analysis is clubbed with an inventory optimization model, which can be used for designing inventory policies . In the first case, we model one manufacturer with one warehouse, which supplies to various retailers. We determine the optimal inventory level at the warehouse that minimizes total expected cost of carrying inventory, back order cost associated with serving orders in the backlog queue, and ordering cost. In the second model we impose service level constraint in terms of fill rate (probability an order is filled from stock at warehouse), assuming that customers do not balk from the system. We present several numerical examples to illustrate the model and to illustrate its various features. In the third case, we extend the model to a three-echelon inventory model which explicitly considers the logistics process.

Beta-Turn Conformations In Crystal-Structures Of Model Peptides Containing Alpha,Alpha-Di-N-Propylglycine And Alpha,Alpha-Di-N-Butylglycine

The crystal state conformations of three peptides containing the alpha, alpha-dialkylated residues, alpha,alpha-di-n-propylglycine (Dpg) and alpha,alpha-di-n-butylglycine (Dbg), have been established by x-ray diffraction. Boc-Ala-Dpg-Ala-OMe (I) and Boc-Ala-Dbg-Ala-OMe (III) adopt distorted type II beta-turn conformations with Ala (1) and Dpg/Dbg (2) as the corner residues. In both peptides the conformational angles at the Dxg residue (I: phi = 66.2 degrees, psi = 19.3 degrees; III: phi = 66.5 degrees, psi = 21.1 degrees) deviate appreciably from ideal values for the i + 2 residue in a type II beta-turn. In both peptides the observed (N...O) distances between the Boc CO and Ala(3) NH groups are far too long (I: 3.44 Angstrom; III: 3.63 Angstrom) for an intramolecular 4 --> 1 hydrogen bond. Boc-Ala-Dpg-Ala-NHMe (II) crystallizes with two independent molecules in the asymmetric unit. Both molecules IIA and IIB adopt consecutive beta-turn (type III-III in IIA and type III-I in IIB) or incipient 3(10)-helical structures, stabilized by two intramolecular 4 --> 1 hydrogen bonds. In all four molecules the bond angle N-C-alpha-C' (tau) at the Dxg residues are greater than or equal to 110 degrees. The observation of conformational angles in the helical region of phi,psi space at these residues is consistent with theoretical predictions.

Electron spin resonance absorption in organic metal polyaniline and its blend with PMMA

The electron spin resonance absorption in the synthetic metal polyaniline (PANI) doped with PTSA and its blend with poly(methylmethacrylate) (PMMA) is investigated in the temperature range between 4.2 and 300 K. The observed line shape follows Dyson's theory for a thick metallic plate with slowly diffusing magnetic dipoles. At low temperatures the line shape become symmetric and Lorentzian when the sample dimensions are small in comparison with the skin depth. The temperature dependence of electron spin relaxation time is discussed. (C) 1999 Elsevier Science Ltd. All rights reserved.