Collective dynamics of supercritical water

Inelastic X-ray scattering experiments on sub- and supercritical water were performed to investigate collective dynamics of this unique solvent. Analysis within a generalized Langevin formalism shows that the positive dispersion of the sound velocity, as compared to the hydrodynamic value, first decreases (1.0<ρ<0.8 g cm⁻³) at all measured momentum transfers (1.3-10.7 nm⁻¹), and then increases (0.7<ρ<0.26 g cm⁻³) again only at higher momentum transfers. We suggest the initial decrease is due to approaching the percolation limit in the number of hydrogen bonds, and the subsequent increase is due to the formation of rigid dimers in sub- and supercritical water.     

Percolation phenomenon in barium samarium titanate-silver composite

Ba₄Sm_9.33Ti₁₈O₅₄-Ag (BST-Ag) composites were prepared by a solid-state ceramic route and its dielectric properties were investigated in the vicinity of percolation threshold. The structure and microstructure of the composites were analyzed by X-ray diffraction along with optical and scanning electron microscopy observations. The effects of silver content and frequency on the dielectric properties of BST-Ag composites were studied using a LCR meter. The relative permittivity (ε_r) of the composite increases with silver content below the percolation limit and is in agreement with power law. A 0.14 volume fraction of silver loading increases the relative permittivity of the composite from 50 to 450 at 10 kHz. Addition of 0.15 volume fraction of silver increases the relative permittivity of the composite in the order of 10⁵. It is found that the giant relative permittivity is almost constant for frequencies from 1 kHz to 1 MHz. This high ε_r composite offers the perspectives for application in electromechanical devices.     

An investigation of structural phase transformation and electrical resistivity in Ta films

In this work, we report the effect of substrate, film thickness and sputter pressure on the phase transformation and electrical resistivity in tantalum (Ta) films. The films were grown on Si(1 0 0) substrates with native oxides in place and glass substrates by varying the film thickness (t) and pressure of the working gas (p_Ar). X-ray diffraction (XRD) analysis showed that the formation of α and β phases in Ta films strongly depend on the choice of substrate, film thickness t and sputter pressure p_Ar. A stable α-phase was observed on Si(1 0 0) substrates for t ≤ 200 nm. Both α and β phases were found to grow on glass substrates at all thicknesses except t = 100 nm. All the films grown on Si(1 0 0) substrates for p_Ar ≤ 6.5 mTorr had α-phase with strong (1 1 0) texture normal to the film plane. The glass substrates promoted the formation of β-phase in all p_Ar except p_Ar = 5.5 mTorr. The resistivity ρ was observed to decrease with t, whereas ρ was increased with p_Ar on Si(1 0 0) substrates. In all films, the measured resistivity ρ was greater than the bulk resistivity. The resistivity ρ was influenced by the effects of surface roughness and grain size.     

Electrical transport of (1−x)La0.7Ca0.3MnO3+xAl2O3 composites

We report the resistivity (ρ)-temperature (T) patterns in (1-x)La_0,7Ca_0,3MnO₃+xAl₂O₃ composites (0≤x≤0.05) over a temperature regime of 50-300 K. Al₂O₃ addition has increased the resistivity of these composites. The Curie temperature (T_C) is almost independent on the Al₂O₃ content and is about 250 K for all the samples, while the metal-insulator transition temperature (T_MI) decreases with increasing Al₂O₃ content. Based on the phenomenological equation for conductivity under a percolation approach, which is dependent on the phase segregation of ferromagnetic metallic clusters and paramagnetic insulating regions, we fitted the experimental data (ρ−T) from 50 to 300 K and find that the activation barrier increases as Al₂O₃ content increases.     

Percolation picture for long wavelength phonons in zinc blende alloys: application to GaInAs

We propose a ‘one bond→two modes’ model for the long wavelength optical phonons in random zinc-blende A_xB_1−xC ternary alloys, based on the percolation site theory. Our model takes into account the ‘fractal→normal’ object transition, which goes with the ‘dispersion→continuum’ topology transition at the percolation thresholds of the A-C and B-C bonds. We first introduce the basics of our model in the case of Zn_1−xBe_x(Se,Te) mixed crystals, whose parent binaries display a high contrast in the bond stiffness, which enhances the percolation effects. We then focus our study on standard systems, which display a much weaker contrast in the bond stiffness. The multi-phonon behavior of GaInAs alloys is re-examined in the light of the percolation model, with much success.     

Short-range order analysis and some physical properties of InxSe1−x glasses

Bulk In_xSe_1−x (with x=5-25 at%) glasses were prepared using the melt-quench technique. Short range order(SRO) was examined by the X-ray diffraction using Cu(k_α) radiation in the wave vector interval 0.28≤k≤6.5 A⁰⁻¹.The SRO parameters have been obtained from the radial distribution function. The inter-atomic distance obtained from the first and second peak are r₁=0.263 and r₂=0.460 nm, which is equivalent In-Se and Se-Se bond length. The fundamental structural unit for the studied glasses is In₂Se₃ pyramid. Using the differential scanning calorimetry (DSC), the crystallization mechanism of In_xSe_1−x chalcogenide glass has been studied. The glass transition activation energy (E_g) is 289±0.3 kj/mol.There is a correlation amongst the glass forming ability, bond strength and the number of lone pair electrons. The utility of the Gibbs-Di Marzio relation was achieved by estimating T_g theoretically.     

Magnetism and magneto-transport studies in sonochemically prepared amorphous Co100−xPtx nano alloys

Bulk amorphous Co_(100−x)Pt_x (0≤x≤50) nano-alloys have been synthesized using high frequency ultrasound, displaying single domain (4-5 nm) behavior wherein weakly exchange-coupled particles lead to a field-dependent resistivity behavior. Magneto-resistivity is correlated to the order-disorder parameter in these powder compacts. The plot of Δρ/ρ₀ as a function of reduced magnetization indicates that all the systems are weakly exchange coupled.     

Bootstrap Percolation and Kinetically Constrained Models on Hyperbolic Lattices

We study bootstrap percolation (BP) on hyperbolic lattices obtained by regular tilings of the hyperbolic plane. Our work is motivated by the connection between the BP transition and the dynamical transition of kinetically constrained models, which are in turn relevant for the study of glass and jamming transitions. We show that for generic tilings there exists a BP transition at a nontrivial critical density, 0<ρ _c <1. Thus, despite the presence of loops on all length scales in hyperbolic lattices, the behavior is very different from that on Euclidean lattices where the critical density is either zero or one. Furthermore, we show that the transition has a mixed character since it is discontinuous but characterized by a diverging correlation length, similarly to what happens on Bethe lattices and random graphs of constant connectivity.     

EPR investigation of a-Si:H aerosol particles formed under silane thermal decomposition

The dangling bond defects were investigated in a-Si:H particles formed under silane thermal decomposition in flow reactor. EPR together with hydrogen evolution method were used. The experimental results allowed us to conclude that there are two kinds of dangling bond defects in a-Si:H aerosol particles. The defects of the first kind are localized on the surface of interconnected microvoids and microchannels (surface dangling bonds) and those of the second kind are embedded in amorphous silicon network (volume dangling bonds). The thermal equilibration of dangling bonds and temperature dependence of equilibrium dangling bond concentration were investigated. It was found that at temperatures > 400 K the dangling bond concentrationNApplied Magnetic Resonance _s reversibly depends on sample temperature. The volume dangling bond concentration increases with temperature increasing (the effective activation energy of dangling bond formationU > 0), and the surface dangling bond concentration decreases with temperature increasing (U < 0). It has been found that EPR line is considerably asymmetric for samples with high hydrogen content and for low hydrogen content the EPR line is weakly asymmetric. A conclusion was drawn that the asymmetry degree depends on amorphous silicon lattice distortions. This conclusion has been confirmed by EPR spectra simulations.     

Structural and photo-luminescence properties of nanocrystalline silicon films deposited at low temperature by plasma-enhanced chemical vapor deposition

Nanocrystalline silicon (nc-Si) films were prepared by a plasma-enhanced chemical vapor deposition method at a deposition temperature below 220 °C with different dynamic pressures (P_g), hydrogen flow rates ([H₂]), and RF powers, using SiH₄/H₂/SiF₄ mixtures. We examined the photo-luminescence (PL) spectra and the structural properties. We observed two stronger and weaker PL spectra with a peak energies around E_PL = 1.8 and 2.2-2.3 eV, respectively, suggesting that the first band was related to nanostructure in the films, and another band was associated with SiO-related bonds. The nc-Si films with rather large PL intensity was obtained for high [H₂] and/or low pressure values, However, effects of [H₂] are likely to be different from those of P_g. The average grain size (δ) and the crystalline volume fraction (ρ) at first rapidly increase, and then slowly increase, with increasing P_g. Other parameters exhibited opposite behaviors from those of δ or ρ. These results were discussed in connection with the changes in the PL properties with varying the deposition conditions.     

Microwave spectra of HPO and DPO: molecular structure

Microwave spectra of the unstable phosphorus containing molecule, HPO, and its deuterated species were measured in the frequency range of 70-380 GHz. The molecule was produced by a DC-glow discharge of a gas mixture of PH₃, CO₂, and H₂(D₂). Rotational constants and centrifugal distortion constants for HPO and DPO were determined accurately. Harmonic force constants were evaluated from the centrifugal distortion constants determined in the present study, and with vibrational frequencies reported previously. The zero-point average structure for HPO was obtained by taking the isotopic difference of the PH bond length into consideration: r_z(PH)=1.473(7) Å, r_z(PO)=1.4843(9) Å, and θ_z=104.57(16)°. The errors were estimated from the residual inertial defect. Equilibrium bond lengths for the PH and PO bonds were derived as 1.455(7) and 1.4800(9) Å, respectively, by assuming anharmonic constants of the corresponding diatomic molecules.     

Reactivity of 3-hexyne on oxygen modified Ru(0 0 1) surfaces: Observation of oxametallacycles by RAIRS

The chemical behaviour of 3-hexyne on oxygen modified Ru(0 0 1) surfaces has been analysed under ultrahigh-vacuum, using reflection-absorption infrared spectroscopy (RAIRS). The effects of oxygen coverage, 3-hexyne exposure and adsorption temperature were studied. Two modified Ru(0 0 1) surfaces were prepared: Ru(0 0 1)-(2 × 2)-O and Ru(0 0 1)-(2 × 1)-O that correspond to oxygen coverages (θ_O) of 0.25 and 0.5 ML, respectively. The striking result is the direct bonding to an O atom when the modified surfaces are exposed to a very low dose (0.2 L) of 3-hexyne at low temperature (100 K). For θ_O = 0.25 ML, an unsaturated oxametallacycle [Ru-O-C(C₂H₅)C(C₂H₅)-Ru] is proposed, identified by RAIRS for the first time, through the νCC and νCO modes. Further decomposition at 110 K yields smaller oxygenated intermediates, such as acetyl [μ₃-η²(C,O)-CH₃CO], co-adsorbed with a small amount of carbon monoxide and non-dissociated species. The temperature at which a fraction of molecules undergoes complete C-C and C-H bond breaking is thus much lower than on clean Ru(0 0 1). The ultimate decomposition product observed by RAIRS at 220 K is methylidyne [CH]. Another key observation was that the adsorption temperature is not determinant of the reaction route, contrarily to what occurs on clean Ru(0 0 1): even when 3- hexyne strikes the surface at a rather high temperature (220 K), the multiple bond does not break completely. For θ_O = 0.5 ML, a saturated oxametallacycle [Ru-O-CH(C₂H₅)-CH(C₂H₅)-Ru] is also proposed at 100 K, identified by the ν_asO-C-C (at 1043 cm⁻¹) and ν_sO-C-C (at 897 cm⁻¹) modes, showing that some decomposition with C-H bond breaking occurs. For this oxygen coverage, the reaction temperatures are lower, and the intermediate surface species are less stable.     

Calculation of the surface energy of fcc-metals with the empirical electron surface model

The empirical electron surface model (EESM) based on the empirical electron theory and the dangling bond analysis method has been used to establish a database of surface energy for low-index surfaces of fcc-metals such as Al, Mn, Co, Ni, Cu, Pd, Ag, Pt, Au, and Pb. A brief introduction of EESM will be presented in this paper. The calculated results are in agreement with experimental and other theoretical values. Comparison of the experimental results and calculation values shows that the average relative error is less than 10% and these values show a strong anisotropy. As we predicted, the surface energy of the close-packed plane (1 1 1) is the lowest one of all index surfaces. For low-index planes, the order of the surface energies is γ_(1 1 1) < γ_(1 0 0) < γ_(1 1 0) < γ_(2 1 0). It is also found that the dangling bond electron density and the spatial distribution of covalent bonds have a great influence on surface energy of various index surfaces.     

Synthesis and surface modified hard magnetic properties in Co0.5Pt0.5 nanocrystallites from a rheological liquid precursor

Small crystallites of a metastable phase Co_0.5Pt_0.5 are precipitated by heating a rheological liquid precursor of cobalt–hydrazine complex and platinum chloride H₂PtCl₆·xH₂O in polymer molecules of poly(vinylpyrrolidone) (PVP) in ethylene glycol. The hydrazine co-reduces nascent atoms from the Co²⁺ and Pt⁴⁺ that recombine and grow as Co_0.5Pt_0.5. The PVP molecules cap a growing Co_0.5Pt_0.5 as it achieves a critical size so that it stops growing further in given conditions. X-ray diffraction pattern of a recovered powder reveals a crystalline Co_0.5Pt_0.5 phase (average crystallite size D∼8 nm) of a well-known Fm3m-fcc crystal structure with the lattice parameter a=0.3916 nm (density ρ=14.09 g/cm³). A more ordered L1₀ phase (ρ=15.91 g/cm³) transforms (D≥25 nm) upon annealing the powder at temperature lesser than 700 °C (in vacuum). At room temperature, the virgin crystallites bear only a small saturation magnetization M_s=5.54 emu/g (D=8 nm) of a soft magnet and it hardly grows on bigger sizes (D≤31 nm) in a canted ferromagnetic structure. A rectangular hysteresis loop is markedly expanded on an optimally annealed L1₀ phase at 800 °C for 60 min, showing a surface modified coercivity H_c=7.781 kOe with remnant ratio M_r/M_s=0.5564, and M_s=39.75 emu/g. Crystallites self-assembled in an acicular shape tailor large H_c from ideal single domains and high magnetocrystalline anisotropy of a hard magnet L1₀ phase.     

Theoretical study of cisplatin adsorption on silica

The adsorption of cisplatin and its complexes, cis-[PtCl(NH₃)₂]⁺ and cis-[Pt(NH₃)₂]²⁺, on a SiO₂(1 1 1) hydrated surface has been studied by the Atom Superposition and Electron Delocalization method. The adiabatic energy curves for the adsorption of the drug and its products on the delivery system were considered. The electronic structure and bonding analysis were also performed. The molecule-surface interactions are formed at expenses of the OH surface bonds. The more important interactions are the Cl-H bond for cis-[PtCl₂(NH₃)₂] and cis-[PtCl(NH₃)₂]⁺ adsorptions, and the Pt-O interaction for cis-[Pt(NH₃)₂]²⁺ adsorption. The Cl p orbitals and Pt s, p y d orbitals of the molecule and its complexes, and the s H orbital and, the s and p orbitals of the O atoms of the hydrated surface are the main contribution to the surface bonds.     

CF4 radio frequency plasma surface modification of silicone rubber for use as outdoor insulations

For further prolonging the serve life of silicone rubber (SIR) for outdoor insulation and increasing its resistance of pollution flashover, surface modifications of SIR were carried out via CF₄ capacitively coupled plasma at radio frequency (RF) power of 60, 100 and 200 W for a treatment time up to 20 min under CF₄ flow rate of 20 sccm. Static contact angle measurement was employed to estimate the change of hydrophobicity of the modified SIR. The variation of the surface functional groups of the modified SIR was observed by attenuated total reflection Fourier transform infrared (ATR-FTIR) spectrum and X-ray photoelectron spectroscopy (XPS). The surface topography was observed by atom force microscopy (AFM). The results indicate that the static contact angle of SIR surface is improved from 100.7° to 150.2° via the CF₄ plasma modification, and the super-hydrophobic surface of modified SIR, which corresponds to a static contact angle of 150.2°, appears at RF power of 200 W for a 5-min treatment time. According to the results, it is suggested that the formation of super-hydrophobic surface is ascribed to the co-action of the increase of roughness created by the ablation reaction of CF₄ plasma and the formation of [SiF_x(CH₃)_2−xO]_n (x = 1, 2) structure produced by the direct attachment of F atoms to Si.     

A density functional study of atomic oxygen and water molecule adsorption on Ni(1 1 1) and chromium-substituted Ni(1 1 1) surfaces

Density functional theory (DFT) for generalized gradient approximation calculations has been used to study the adsorption of atomic oxygen and water molecules on Ni(1 1 1) and different kind of Ni-Cr(1 1 1) surfaces. The fcc hollow site is energetically the most favorable for atomic oxygen adsorption and on top site is favorable for water adsorption. The Ni-Cr surface has the highest absorption energy for oxygen at 6.86 eV, followed by the hcp site, whereas the absorption energy is 5.56 eV for the Ni surface. The Ni-O bond distance is 1.85 Å for the Ni surface. On the other hand, the result concerning the Ni-Cr surface implies that the bond distances are 1.93-1.95 Å and 1.75 Å for Ni-O and Cr-O, respectively. The surface adsorption energy for water on top site for two Cr atom substituted Ni-Cr surface is 0.85 eV. Oxygen atoms prefer to bond with Cr rather than Ni atoms. Atomic charge analysis demonstrates that charge transfer increases due to the addition of Cr. Moreover, a local density of states (LDOS) study examines the hybridization occurring between the metal d orbital and the oxygen p orbital; the bonding is mainly ionic, and water bonds weakly in both cases.     

Interaction of amines with native aluminium oxide layers in non-aqueous environment: Application to the understanding of the formation of epoxy-amine/metal interphases

Interaction of propylamine (PA), 1,2-diaminoethane (DAE) or 3-aminomethyl-3,5,5-trimethylcyclohexylamine (isophorone diamine, IPDA) with native aluminium oxide layers in non-aqueous environment has been studied using time-resolved inductively coupled plasma optical emission spectroscopy (ICP-OES) and X-ray photoelectron spectroscopy (XPS). The formation of several surface complexes has been evidenced. Monodentate and bidentate metal-bond surface complexes (MBSC) result from interactions between the amine terminations of the molecule and aluminium cations by donation of the N lone electron pair to the metal ion (Lewis-like mechanism leading to OAl?N bonds). Monodentate and bidentate hydrogen-bond surface complexes (HBSC) are due to interaction of the amino group with surface hydroxyl groups by protonation of the amine termination (Brønsted-like mechanism leading to the formation of AlOH?N bonds) or interaction with carbonaceous contamination (C_xO_yH_z?N bonds). Diamines can also form mixed complexes with one amino group forming an O-Al?N bond and the other group forming an AlOH…N or C_xO_yH_z?N bond. AlOH?N and C_xO_yH_z…N bonds are less stable under vacuum than OAl?N bonds, leading to partial desorption of the DAE molecules in vacuum and modification of the interaction modes. Only DAE and IPDA can lead to partial dissolution of the aluminium native (hydr)oxide films. A detailed mechanism of dissolution has been proposed based on the formation of mononuclear bidentate (chelate) MBSC by ligand exchange between the terminal η¹-OH and bridged μ₂-OH surface sites and the amino terminations of the molecule. The detachment of this complex from the surface is likely to be the precursor step to the formation of the interphase in epoxy-amine/metal systems.     

Study of the adsorption, electronic structure and bonding of C2H4 on the FeNi(1 1 1) surface

The adsorption of C₂H₄ on the FeNi(1 1 1) alloy surface has been studied by ASED-MO tight binding calculations. The C₂H₄ molecule presents its most stable geometry with the CC bond axis parallel to the surface along the [1, −1, 0] direction, bonded on top Fe atom and bonded along a Fe-Fe bridge site. As a consequence, the strength of the local Fe-Fe bond decreases between 37 and 62% of its original bulk value. This bond weakening is mainly due to the new C-Fe interactions however no Fe₃C carbide formation is evidenced on surface. The Fe-Ni and Ni-Ni superficial bonds are only slightly modified.