An AFM, XPS and electrochemical study of molecular electroactive monolayers formed by wet chemistry functionalization of H-terminated Si(1 0 0) with vinylferrocene

Molecular electroactive monolayers have been produced from vinylferrocene (VFC) via light-assisted surface anchoring to H-terminated n- and p-Si(1 0 0) wafers prepared via wet chemistry, in a controlled atmosphere. The resulting Si-C bound hybrids have been characterized by means of XPS and AFM. Their performance as semiconductor functionalized electrodes and their surface composition have been followed by combining electrochemical and XPS measurements on the same samples, before and after use in an electrochemical cell. White-light photoactivated anchoring at short (1 h) exposure times has resulted in a mild route, with a very limited impact on the initial quality of the silicon substrate. In fact, the functionalized Si surface results negligibly oxidized, and the C/Fe atomic ratio is close to the value expected for the pure molecular species. The VFC/Si hybrids can be described as (η⁵-C₅H₅)Fe²⁺(η⁵-C₅H₄)-CH₂-CH₂-Si species, on the basis of XPS results. Electrochemical methods have been applied in order to investigate the role played by a robust, covalent Si-C anchoring mode towards substrate-molecule electronic communication, a crucial issue for a perspective development of molecular electronics devices. The response found from cyclic voltammograms for p-Si(1 0 0) functionalized electrodes, run in the dark and under illumination, has shown that the electron transfer is not limited by the number of charge carriers, confirming the occurrence of electron transfer via the Si valence band. The hybrids have shown a noticeable electrochemical stability and reversibility under cyclic voltammetry (cv), and the trend in peak current intensity vs. the scan rate was linear. The molecule-Si bond is preserved even after thousands of voltammetric cycles, although the surface coverage, evaluated from cv and XPS, decreases in the same sequence. An increasingly larger surface concentration of Fe³⁺ at the expenses of Fe²⁺ redox centers has been found at increasing number of cv’s, experimentally associated with the growth of silicon oxide. Surface SiO⁻ groups from deprotonated silanol termination, induced by the electrochemical treatments, are proposed as the associated counterions for the Fe³⁺ species. They could be responsible for the observed decrease in the electron transfer rate constant with electrode ageing.     

Reciprocating sliding wear behavior of laser-clad small amplitude Mo2Ni3Si/NiSi metal silicide composite coatings

Mo₂Ni₃Si/NiSi metal silicide composite coatings with a fine microstructure consisting of Mo₂Ni₃Si primary dendrites and the interdendritic Mo₂Ni₃Si/NiSi eutectics were fabricated on austenitic stainless steel AISI 321 by laser cladding process. Small amplitude reciprocating sliding wear resistance of the coatings is evaluated as functions of normal load and slip amplitude and the wear mechanisms were discussed based on worn surface morphology observations. Results showed that the Mo₂Ni₃Si/NiSi coatings have excellent small amplitude reciprocating sliding wear resistance.     

Stochastic analysis in life office management: applications to large annuity portfolios

The paper deals with the riskiness analysis for a large portfolio of life annuities. By means of the limiting distribution of the present value of the portfolio, in the first part of the paper a model for evaluating the investment and the projection risks is presented. In the second part, with regard to the investment risk's effects, the insolvency risk is measured considering the cumulative probability distribution function of the discounted average cost per policy. Copyright © 2003 John Wiley & Sons, Ltd.     

Hybrid Electrodes Used in Polymer Electro-Optic Modulator with Ultra-Broadband

Hybrid electrode combined coplanar waveguide (CPW) and microstrip lines in ultra-broadband electro-optic modulators. The characteristics of the modulators with hybrid electrode is like that of the modulator with the microstrip lines, in which the microstrip electrode is loaded above only one arm of Mach-Zehnder (M-Z) optical waveguide, besides the problem of microstrip line to coaxial transition and corona polarization in polymer modulators have been best solved at the same time. By using finite element method (FEM), the characteristic parameters such as half-wave voltage, modulation bandwidth characteristic impedance, effective microwave refractive index of polymer modulators with microstrip line and hybrid electrode are analysed and compared in this paper. The results present that velocity match, impendence match and lower microwave propagating loss is easily realized in modulators with hybrid electrode.     

Förster energy transfer from poly(arylene–ethynylene)s to an erbium–porphyrin complex

We study the infrared emission at 1.54 μm of an organolanthanide complex, Er(III)-tetraphenylporphyrin [Er(TPP)acac], both as a result of direct optical excitation and via energy transfer from host π-conjugate polymers of type poly(arylene–ethynylene) [PAE]. In the first case, the emission of the neat complex is characterized in inert transparent materials and a value of the quantum yield at 1.54 μm φ_IR=4×10⁻⁴ is measured. Then, fluorescence resonance transfer is investigated in blends of Er(TPP)acac with PAEs by monitoring the quenching of the polymer fluorescence along with the enhancement of both the visible emission of the ligand and the near-infrared band of Er³⁺. These different procedures allow a detailed analysis of the transfer efficiency within a specific implementation of the Förster model for polymeric donors. The experimental values of the critical radius R₀, ranging from 1.3 to 2.5 nm for the different blends, are in good agreement with theory for a wide interval of the physical and spectroscopic parameters. This suggests that other mechanisms for excitation transfer do not play a significant role in these materials.     

Evidences of phase separation in moisture‐cured poly(urethane urea)s by means of temperature modulated differential scanning calorimetry

The degree of phase separation in several moisture‐cured poly(urethane urea)s (PUUs) was studied by FTIR spectroscopy, wide angle X‐ray diffraction (WAXD), and temperature‐modulated differential scanning calorimetry (TMDSC). This latter technique was shown to be particularly useful in analysing the degree of phase separation in PUU polymers. Both phase mixing and phase segregation coexisted in the PUUs and the degree of phase separation increased as the urea hard segment (HS) content in the PUU increased. The maximum solubility of urea HSs into the polyol soft segments (SSs) was achieved for 50 wt % urea HS content in diol‐based PUUs, whereas for triol‐based PUUs the highest solubility between HS and SS was reached for lower urea HS amount. Finally, the higher the urea HS content the higher the extent of phase separation in the PUU. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 3034–3045, 2007     

环境对MgB_2氧化过程中MgO晶须生长形状的影响

用扫描电镜研究了在 Mg B2 氧化过程中环境对 Mg O晶须生长形状的影响。仅有 Mg B2 时 ,在 80 0℃左右空气气氛中 ,可生长出纳米尺寸的 Mg O晶须。若把 Mg B2 添加到氧化铝陶瓷基体中 ,则生长成竹节状晶须。Mg O晶须生长形状的差别可能是由于氧浓度以及位错等因素造成的。     

2,9-disubstituted 1,10-phenanthroline nickel complexes: Syntheses,characterization, and their ethylene oligomerization

Nickel complexes 1–4 ligated with 2,9-disubstituted-1,10-phenanthroline were synthesized and characterized by FT-IR spectra and elemental analysis. The molecular structure of complex 2 was confirmed by X-ray crystal diffraction analysis. Activated with methylaluminoxane (MAO), those complexes showed moderate activities for ethylene oligomerization. Published in Kinetika i Kataliz, 2007, Vol. 48, No. 5, pp. 710–714. This article was submitted by the authors in English.     

A method to collect an infrared spectrum in solution.

Herein we report a new method to collect a qualified infrared spectrum of a solute in solution by two solvent cells with different thickness during background single-beam spectrum scanning. By collecting the background spectrum with two cells (two stages), we successfully achieved accurate solvent compensation between a sample and a reference, namely, the solvent amounts in the sample and background measurements could become congruent. Therefore, the solvent bands were thoroughly suppressed in the infrared spectrum and a qualified spectrum of the solute was obtained.