An electron spectroscopic study of the surface oxidation of glassy and crystalline Cu-Zr alloys

Surface oxidation of three metglasses in the Cu-Zr system has been investigated by employing X-ray photoelectron spectroscopy and Auger electron spectroscopy with a view to comparing their oxidation behaviour with that of the corresponding crystalline states of the alloys. Surface oxidation of pure Zr metal has also been examined in detail using these techniques. Sub-oxides of Zr are formed during the initial stages of oxidation of Zr (at oxygen exposures <10L), while at higher exposures, ZrO2 is formed together with the highest possible sub-oxide which the authors designate as 'ZrO'. The relative proportion of 'ZrO' goes through a maximum in the range 25-50 L. Both the glassy and the crystalline states of the Cu-Zr alloys exhibit preferential oxidation of Zr. The glassy alloys exhibit a higher rate of oxidation at intermediate exposures compared with the crystalline states of the alloys; the extent of oxidation at higher oxygen exposures is, however, higher for crystalline alloys. Interatomic Auger transitions have been found in the Zr+O2 system as well as in Cu-Zr alloys.

Metal-insulator transition of naxwo3 studied by angle-resolved photoemission spectroscopy

The electronic structure of sodium tungsten bronzes NaxWO3 is investigated by high-resolution angle-resolved photoemission spectroscopy (ARPES). The ARPES spectra measured in both insulating and metallic phases of NaxWO3 reveals the origin of metal-insulator transition (MIT) in sodium tungsten bronze system. It is found that in insulating NaxWO3 the states near the Fermi level (E-F) are localized due to the strong disorder caused by the random distribution of Na+ ions in WO3 lattice. Due to the presence of disorder and long-range Coulomb interaction of conduction electrons, a soft Coulomb gap arises, where the density of states vanishes exactly at E-F. In the metallic regime the states near E-F are populated and the Fermi level shifts upward rigidly with increasing electron doping (x). Volume of electron-like Fermi surface (FS) at the Gamma(X) point of the Brillouin zone gradually increases with increasing Na concentration due to W 5d t(2g) band filling. A rigid shift of the Fermi energy is found to give a qualitatively good description of the Fermi surface evolution. As we move from bulk-sensitive to more surface sensitive photon energy, we found the emergence of Fermi surfaces at X(M) and M(R) point similar to the one at the Gamma(X) point in the metallic regime, suggesting that the reconstruction of surface was due to rotation/deformation of WO6 octahedra.

Effect of metal coating and residual stress on the resonant frequency of MEMS resonators

MEMS resonators are designed for a fixed resonant frequency. Therefore, any shift in the resonant frequency of the final fabricated structure can be a denting factor for its suitability towards a desired application. There are numerous factors which alter the designed resonant frequency of the fabricated resonator such as the metal layer deposited on top of the beam and the residual stresses present in the fabricated structure. While the metal coating, which acts as electrode, increases the stiffness and the effective mass of the composite structure, the residual stress increases or decreases the net stiffness if it is a tensile or compressive type respectively. In this paper, we investigate both these cases by taking two different structures, namely, the micro cantilever beam with gold layer deposited on its top surface and the MEMS gyroscope with residual stresses. First, we carry out experiments to characterize both these structures to find their resonant frequencies. Later, we analytically model those effects and compare them with the experimentally obtained values. Finally, it is found that the analytical models give an error of less than 10% with respect to the experimental results in both the cases.

Implantation Induced Hardening of Nanocrystalline Titanium Thin Films

Formation of nanocrystalline TiN at low temperatures was demonstrated by combining Pulsed Laser Deposition (PLD) and ion implantation techniques. The Ti films of nominal thickness similar to 250 nm were deposited at a substrate temperature of 200 degrees C by ablating a high pure titanium target in UHV conditions using a nanosecond pulsed Nd:YAG laser operating at 1064 nm. These films were implanted with 100 keV N+ ions with fluence ranging from 1.0 x 10(16) ions/cm(2) to 1.0 x 10(17) ions/cm(2). The structural, compositional and morphological evolutions were tracked using Transmission Electron Microscopy (TEM), Secondary Ion Mass Spectrometry (SIMS) and Atomic Force Microscopy (AFM), respectively. TEM analysis revealed that the as-deposited titanium film is an fcc phase. With increasing ion fluence, its structure becomes amorphous phase before precipitation of nanocrystalline fcc TiN phase. Compositional depth profiles obtained from SIMS have shown the extent of nitrogen concentration gradient in the implantation zone. Both as-deposited and ion implanted films showed much higher hardness as compared to the bulk titanium. AFM studies revealed a gradual increase in surface roughness leading to surface patterning with increase in ion fluence.

Self-interrupted regenerative metal cutting in turning

A new approach is used to study the global dynamics of regenerative metal cutting in turning. The cut surface is modeled using a partial differential equation (PDE) coupled, via boundary conditions, to an ordinary differential equation (ODE) modeling the dynamics of the cutting tool. This approach automatically incorporates the multiple-regenerative effects accompanying self-interrupted cutting. Taylor's 3/4 power law model for the cutting force is adopted. Lower dimensional ODE approximations are obtained for the combined tool–workpiece model using Galerkin projections, and a bifurcation diagram computed. The unstable solution branch off the subcritical Hopf bifurcation meets the stable branch involving self-interrupted dynamics in a turning point bifurcation. The tool displacement at that turning point is estimated, which helps identify cutting parameter ranges where loss of stability leads to much larger self-interrupted motions than in some other ranges. Numerical bounds are also obtained on the parameter values which guarantee global stability of steady-state cutting, i.e., parameter values for which there exist neither unstable periodic motions nor self-interrupted motions about the stable equilibrium.

Ring-Opening-Induced Toughening of a Low-Permittivity Polymer-Metal Interface

Integrating low dielectric permittivity (low-k) polymers to metals is an exacting fundamental challenge because poor bonding between low-polarizability moieties and metals precludes good interfacial adhesion. Conventional adhesion-enhancing methods such as using intermediary layers are unsuitable for engineering polymer/metal interfaces for many applications because of the collateral increase in dielectric permittivity. Here, we demonstrate a completely new approach without surface treatments or intermediary layers to obtain an excellent interfacial fracture toughness of > 13 J/m(2) in a model system comprising copper. and a cross-linked polycarbosilane with k similar to 2.7 obtained by curing a cyclolinear polycarbosilane in air.Our results suggest that interfacial oxygen catalyzed molecularring-opening and anchoring of the opened ring moieties of the polymer to copper is the main toughening mechanism. This novel approach of realizing adherent low-k polymer/metal structures without intermediary layers by activating metal-anchoring polymer moieties at the interface could be adapted for applications such as device wiring and packaging, and laminates and composites.

Analysis of multiple crystal forms of Bacillus subtilis BacB suggests a role for a metal ion as a nucleant for crystallization

Bacillus subtilis BacB is an oxidase that is involved in the production of the antibiotic bacilysin. This protein contains two double-stranded beta-helix (cupin) domains fused in a compact arrangement. BacB crystallizes in three crystal forms under similar crystallization conditions. An interesting observation was that a slight perturbation of the crystallization droplet resulted in the nucleation of a different crystal form. An X-ray absorption scan of BacB suggested the presence of cobalt and iron in the crystal. Here, a comparative analysis of the different crystal forms of BacB is presented in an effort to identify the basis for the different lattices. It is noted that metal ions mediating interactions across the asymmetric unit dominate the different packing arrangements. Furthermore, a normalized B-factor analysis of all the crystal structures suggests that the solvent-exposed metal ions decrease the flexibility of a loop segment, perhaps influencing the choice of crystal form. The residues coordinating the surface metal ion are similar in the triclinic and monoclinic crystal forms. The coordinating ligands for the corresponding metal ion in the tetragonal crystal form are different, leading to a tighter packing arrangement. Although BacB is a monomer in solution, a dimer of BacB serves as a template on which higher order symmetrical arrangements are formed. The different crystal forms of BacB thus provide experimental evidence for metal-ion-mediated lattice formation and crystal packing.

Studies on friction and transfer layer: role of surface texture

Friction influences the nature of transfer layer formed at the interface between tool and metal during sliding. In the present investigation, experiments were conducted using “Inclined Scratch Tester” to understand the effect of surface texture of hard surfaces on coefficient of friction and transfer layer formation. EN8 steel flats were ground to attain surfaces of different textures with different roughness. Then super purity aluminium pins were scratched against the prepared steel flats. Scanning electron micrographs of the contact surfaces of pins and flats were used to reveal the morphology of transfer layer. It was observed that the coefficient of friction and the formation of transfer layer depend primarily on the texture of hard surfaces, but independent of surface roughness of hard surfaces. It was observed that on surfaces that promote plane strain conditions near the surface, the transfer of material takes place due to the plowing action of the asperities. But, on a surface that promotes plane stress conditions the transfer layer was more due to the adhesion component of friction. It was observed that the adhesion component increases for surfaces that have random texture but was constant for the other surfaces

Photocatalytic degradation of phenol by base metal-substituted orthovanadates

Base metal (Cr, Mn, Fe, Ni, Cu) substituted CeVO4 compounds were synthesized by the solution combustion technique. These compounds were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, UV-vis spectroscopy, transmission electron microscopy and BET surface area analyzer. The characterization indicated that the base metals were substituted in the ionic state in all the compounds. These compounds were used for the photocatalytic degradation of phenol and the degradation rates obtained in the presence of these compounds werecompared against that obtained with the commercial Degussa P-25 TiO2 catalyst. Fe and Cr substituted CeVO4 showed photocatalytic activity that was comparable with that of Degussa P-25 TiO2. The concentration of toxic intermediates was high when the reaction was carried out in presence of Degussa P-25 TiO2 but it was found to be insignificant when the reaction was carried out in presence of base metal-substituted CeVO4. The effect of % Fe-substitution (varied from 1 to 5 at%) in CeVO4 on the photocatalytic activity was also investigated and it was observed that 1 at% Fe-substituted compound showed the highest activity. A mathematical model describing the kinetics of the photocatalytic degradation of phenol was developed on the basis of the catalyst structure and taking into account the formation of all the possible intermediates. The variation of the concentration of phenol and the intermediates was described by the model and the reaction rateconstants were determined. (C) 2010 Elsevier B.V. All rights reserved.

Magnetotransport of Dirac fermions on the surface of a topological insulator

We study the properties of Dirac fermions on the surface of a topological insulator in the presence of crossed electric and magnetic fields. We provide an exact solution to this problem and demonstrate that, in contrast to their counterparts in graphene, these Dirac fermions allow relative tuning of the orbital and Zeeman effects of an applied magnetic field by a crossed electric field along the surface. We also elaborate and extend our earlier results on normal-metal-magnetic film-normal metal (NMN) and normal-metal-barrier-magnetic film (NBM) junctions of topological insulators [S. Mondal, D. Sen, K. Sengupta, and R. Shankar, Phys. Rev. Lett. 104, 046403 (2010)]. For NMN junctions, we show that for Dirac fermions with Fermi velocity vF, the transport can be controlled using the exchange field J of a ferromagnetic film over a region of width d. The conductance of such a junction changes from oscillatory to a monotonically decreasing function of d beyond a critical J which leads to the possible realization of magnetic switches using these junctions. For NBM junctions with a potential barrier of width d and potential V-0, we find that beyond a critical J, the criteria of conductance maxima changes from chi=eV(0)d/h upsilon(F)=n pi to chi=(n+1/2)pi for integer n. Finally, we compute the subgap tunneling conductance of a normal-metal-magnetic film-superconductor junctions on the surface of a topological insulator and show that the position of the peaks of the zero-bias tunneling conductance can be tuned using the magnetization of the ferromagnetic film. We point out that these phenomena have no analogs in either conventional two-dimensional materials or Dirac electrons in graphene and suggest experiments to test our theory.

Support-Dependent Activity of Noble Metal Substituted Oxide Catalysts for the Water Gas Shift Reaction

The water gas shift reaction was carried out over noble metal ion substituted nanocrystalline oxide catalysts with different supports. Spectroscopic studies of the catalysts before and after the reaction showed different surface phenomena occurring over the catalysts. Reaction mechanisms were proposed based upon the surface processes and intermediates formed. The dual site mechanism utilizing the oxide ion vacancies for water dissociation and metal ions for CO adsorption was proposed to describe the kinetics of the reaction over the reducible oxides like CeO2. A mechanism based on the interaction of adsorbed CO and the hydroxyl group was proposed for the reaction over ZrO2. A hybrid mechanism based on oxide ion vacancies and surface hydroxyl groups was proposed for the reaction over TiO2. The deactivation of the catalysts was also found to be support dependent. Kinetic models for both activation and deactivation were proposed. (C) 2010 American Institute of Chemical Engineers AIChE J, 56: 2662-2676, 2010

Metal-Insulator Transition in the Hubbard Model on a Triangular Lattice

We discuss the results of an extensive mean-field investigation of the half-filled Hubbard model on a triangular lattice at zero temperature. At intermediate U we find a first-order metal-insulator transition from an incommensurate spiral magnetic metal to a semiconducting state with a commensurate linear spin density wave ordering stabilized by the competition between the kinetic energy and the frustrated nature of the magnetic interaction. At large U the ground state is that of a classical triangular antiferromagnet within our approximation. In the incommensurate spiral metallic phase the Fermi surface has parts in which the wave function renormalization Z is extremely small. The evolution of the Fermi surface and the broadening of the quasi-particle band along with the variation of the plasma frequency and a charge stiffness constant with U/t are discussed.

Nature of nitrogen adsorbed on transition metal surfaces as revealed by electron spectroscopy and cognate techniques

The nature of the chemisorbed states of nitrogen on various transition metal surfaces is discussed comprehensively on the basis of the results of electron spectroscopic investigations augmented by those from other techniques such as LEED and thermal desorption. A brief discussion of the photoemission spectra of free N2, a comparison of adsorbed N2 and CO as well as of physisorption of N2 on metal surfaces is also presented. We discuss the chemisorption of N2 on the surfaces of certain metals (e.g. Ni, Fe, Ru and W) in some detail, paying considerable attention to the effect of electropositive and electronegative surface modifiers. Features of the various chemisorbed states (one or more weakly chemisorbed gamma-states, strongly chemisorbed alpha-states with bond orders between 1 and 2. and dissociative chemisorbed beta-states) on different surfaces are described and relations between them indicated. While the gamma-state could be a precursor of the alpha-state, the alpha-state could be the precursor of the beta-state and this kind of information is of direct relevance to ammonia synthesis. The nature of adsorption of N2 on the surfaces of some metals (e.g. Cr, Co) deserves further study and such investigations might as well suggest alternative catalysts for ammonia synthesis.

Nucleation and growth of Al2O3/metal composites by oxidation of aluminum alloys

The nucleation and growth mechanisms during high temperature oxidation of liquid Al-3% Mg and Al-3% Mg-3% Si alloys were studied with the aim of enhancing our understanding of a new composite fabrication process. The typical oxidation sequence consists of an initial event of rapid but brief oxidation, followed by an incubation period of limited oxide growth after which bulk Al2O3/Al composite forms. A duplex oxide layer, MgO (upper) and MgAl2O4 (lower), forms on the alloy surface during initial oxidation and incubation. The spinel layer remains next to the liquid alloy during bulk oxide growth and is the eventual repository for most of the magnesium in the original alloy. Metal microchannels developed during incubation continuously supply alloy through the composite to the reaction interface. During the growth process, a layered structure exists at the upper extremity of the composite, consisting of MgO at the top surface, MgAl2O4 (probably discontinuous), Al alloy, and finally the bulk Al2O3 composite containing microchannels of the alloy. The bulk oxide growth mechanism appears to involve continuous formation and dissolution of the Mg-rich oxides at the surface, diffusion of oxygen through the underlying liquid metal, and epitaxial growth of Al2O3 on the existing composite body. The roles of Mg and Si in the composite growth process are discussed.

An electron spectroscopic study of the adsorption of nitrogen on a Ni/TiO2 catalyst prepared in situ in the spectrometer: evidence for dissociative adsorption in the strong-metal-support-interaction (SMSI) state

Nitrogen is dissociatively adsorbed on an annealed Ni/TiO2 surface just as on a Ti–Ni alloy surface while it is molecularly adsorbed on a Ni/Al2O3 surface.