Evolutions of Crystal Structure, Stoichiometry and Electrochemical Behavior with Co Substitution in LiNi1-yCoyO2 Positive Electrodes

LiNi1-yCoyO2（0.1 ≤ y ≤ 0.4） positive electrode materials are synthesized by a chemical method with stoichiometric acetates of related cations. Their crystal structure, stoichiometry and electrochemical behaviors versus Co concentration are investigated by x-ray diffraction, synchrotron-based x-ray absorption fine structure and galvanostatic cycling ts. The results reveal that the non-stoiehiometric Ni^2＋, Li/Ni cation mixing and polarization are reduced as the amount of Co substitution increases, clearly indicating that the Co element is a medium for easily oxidizing Ni^2＋ to Ni^3＋ during the synthesis process.     

On the Doppler distortion of the sea-wave spectra

Discussions on a form of a frequency spectrum of wind-driven sea waves just above the spectral maximum have continued for the last three decades. In 1958 Phillips made a conjecture that wave breaking is the main mechanism responsible for the spectrum formation [O.M. Phillips, J. Fluid Mech. 4 (1958) 426]. That leads to the spectrum decay ∼ω⁻⁵, where ω is the frequency of waves. There is a contradiction between the numerous experimental data and this spectrum. Experiments frequently show decay ∼ω⁻⁴ [Y. Toba, J. Oceanogr. Soc. Japan 29 (1973) 209; M.A. Donelan, J. Hamilton, W.H. Hui, Phil. Trans. R. Soc. London A315 (1985) 509; P.A. Hwang, et al., J. Phys. Oceanogr. 30 (1999) 2753]. There are several ways of the explanation of this phenomenon. One of them (proposed by Banner [M.L. Banner, J. Phys. Oceanogr. 20 (1990) 966]) takes into account the Doppler effect due to surface circular currents generated by underlying waves in the Phillips model.In this article the influence of the Doppler effect on an arbitrary averaged spectrum is considered using both analytic and numerical approaches. Although we mostly concentrated on the very important case of Phillips model, the developed technique and general formula can be used for the analysis of other spectra.For the particular case of Phillips spectra we got analytic asymptotics in the vicinity of spectral maximum and for high frequencies. Results were obtained for two most important angular dependences of the spectra: isotropic and strongly anisotropic. Together with the analytic investigation we performed numerical calculations in a wide range of frequencies. Both high and low frequency asymptotics are in very good agreement with the numerical results.It was shown that at least at low frequencies, the correction to the spectrum due to the Doppler shift is negligible. At high frequencies there is an asymptotic with tail ∼ω⁻³.     

Dimensionality-induced effects on transport properties of poly(G)-poly(C)

We consider a ladder model of DNA for addressing the relation between the transport properties and electronic structure and the interbase coupling in poly(G)-poly(C). Based on the negative eigenvalue theorem and transfer matrix method, the density of states and current-voltage characteristics are evaluated, and an expression for the dependence of the band gap on intra- and inter-strand nucleobase couplings is proposed. There exists a semiconducting-metallic transition in poly(G)-poly(C) by modulating the interbase coupling, and the physical nature is traced back to dimensionality-induced effects. Our results provide possibility for interpreting a variety of transport behaviors observed in DNA molecules.     

Growth of fullerene on Ag and hydrogen-passivated Si substrates: Effect of electron beam exposure on growth modes

We have used Auger electron spectroscopy (AES) to investigate the effect of electron beam exposure on growth modes of fullerene (C₆₀) on substrates like Ag and hydrogen-passivated Si(1 1 1). The electron beam comprises of 3.4 keV electrons, which are used in the AES study. To investigate the effect, Auger signal (AS) vs. deposition time (t) measurements were conducted in a sequential mode, i.e., alternating deposition of C₆₀ and analysis using the electron beam. Duration of AES data collection after each deposition was the duration of exposure to electron beam in this experiment. For the growth study of C₆₀ on Ag, three AS-t plots were recorded for three different durations of exposure to electron beam. Changes in the AS-t plot, depending on the duration of exposure to the electron beam, reflect the electron beam-induced damage. Electron beam-induced damages of C₆₀ produce carbon materials of different densities and consequently transmission coefficient (α) of Auger electron through this material changes. In order to fit the AES (AS vs. t) data a model has been used which simultaneously provides the growth mode and the transmission coefficient. Observation of an increasing transmission coefficient with the increasing duration of exposure to the electron beam from α=0.34 to 0.60 indicates the change of the nature of the carbon material due to the partial damage of C₆₀.     

NO--CO--O2 Reaction on a Metal Catalytic Surface using Eley--Rideal Mechanism

Interactions among the reacting species NO, CO and O2 on metal catalytic surfaces are studied by means of Monte Carlo simulation using the Eley-Rideal （ER） mechanism. The study of this three-component system is important for understanding of the reaction kinetics by varying the relative ratios of the reactants. It is found that contrary to the conventional Langmuir-Hinshelwood （LFI） thermal mechanism in which two irreversible phase transitions are obtained between active states and poisoned states, a single phase transition is observed when the ER mechanism is combined with the LH mechanism. The phase diagrams of the surface coverage and the steady state production of CO2, N2 and N2O are evaluated as a function of the partial pressures of the reactants in the gas phase. The continuous production of CO2 starts as soon as the CO pressure is switched on and the second order phase transition at the first critical point is eliminated, which is in agreement with the experimental findings.     

Time-resolved fluorescence intensity issued from a heterogeneous slab: Sensitivity characterization

Optical imaging using fluorescent contrast agents has become an interesting tool to differentiate diseased lesions from normal tissue. However, several sensitivity characterizations may strongly influence the time-dependent fluorescence measurements. Herein, we present a numerical model based on the finite element method that allows the simulation of time-resolved reflectance and transmittance signals from heterogeneous media mimicking breast tissues with an embedded fluorescent object (tumor). The influence, on the computed signals, of several tumor depths, as well as various fluorophore concentrations and several fluorescent markers targeting are analyzed. The results show the possibility of uncoupling location depth from the shape of the target. Therefore, the analysis of the time to reach half the maximum intensity is validated as a good localization scheme. Then, the transmitted data show that the maximal detected intensity at the bottom of the medium is very sensitive to the dye concentration but not to the tumor shape. Moreover, the strong competition between concentration determination and fluorophore distribution is presented. These results will lead to a better detection and localization of tumors.     

Growth instabilities of vapor deposited films: atomic size versus deflection effect

Two previously suggested, physically distinct mechanisms for a growth instability of vapor deposited films, the finite atomic size effect and the particle deflection effect due to interatomic attraction, are reconsidered, further analyzed, and compared. We substantiate why the instability caused by interatomic attraction must be considered as the truly underlying instability mechanism. We demonstrate that aspects of the structure zone model of Movchan and Demchishin can also be consistently explained using the growth instability induced by particle deflection instead of the instability arising from the atomic size effect. Most significantly we show that, for vapor deposited amorphous Zr₆₅Al_7.5Cu_27.5-films, the growth instability due to the atomic size effect cannot be present. Received 12 December 2001 Published online 6 June 2002     

Ionic effects on overstretching transition of B-DNA

A three-dimensional model is proposed herein to study the ionic effects of a NaCl solution on the overstretching transition of long B-DNA molecules. In this model, the bending deformations of DNA backbones, cooperativity of base-stacking interactions, electrostatic interactions, and spatial effects of the DNA double-helix structure are taken into account. The energy of electrostatic interactions is given as a function of the ionic strength and of the folding angle based on the Poisson-Boltzmann equation. An expression is derived, which shows that the overstretching force is linear with the natural logarithm of the ionic strength. The analytical results of this model are in good agreement with recently reported experimental results.     

Characterization of SBA-15 doped (PEO + LiClO4) polymer electrolytes for electrochemical applications

SBA-15 mesoporous material was prepared by the simple hydrothermal process and added to poly(ethylene oxide) (PEO) and lithium percholorate (LiClO₄) as a filler. X-ray Diffractometry (XRD), Differential Scanning Calorimetry (DSC) and Scanning Electron Microscopy (SEM) were used to determine the characteristics of the composite polymer electrolyte. The SEM of the electrolyte containing 10 wt% of SBA-15 confirms the highest miscibility and amorphous nature. SBA-15 doped (PEO + LiClO₄) polymer electrolytes have shown improved conductivity over the pure PEO and (PEO + LiClO₄) electrolyte. The mesoporous SBA-15 acted as crystal cores and fined the crystallites thus decreasing the crystallinity, which provided a much more continuous amorphous domain for Li⁺ ions to move easily in the (PEO + LiClO₄) electrolyte.