Electrochemically driven organic monolayer formation on silicon surfaces using alkylammonium and alkylphosphonium reagents

The functionalization of silicon surfaces with organic monolayers, bound through Si–C bonds, is an area of wide interest due to the technological promise of organosilicon hybrid devices, but also to investigate fundamental surface reactivity. In this paper, the use of alkylammonium and alkylphosphonium cations as sources of organic moieties to bind to hydrogen-terminated flat and porous silicon is demonstrated. Tetraalkylammonium, tetraalkyl/arylphosphonium reagents, and alkyl pyridinium salts can be utilized, but trialkylammonium salts cannot as they yield substantial surface oxidation. Under electrochemical conditions, either potentiostatic or galvanostatic modes, alkyl groups derived from the ammonium or phosphonium salts are grafted to the silicon surface and are bound through Si–C bonds. Covalent attachment of the organic monolayers to the surface was demonstrated by XPS, AFM scribing, and FTIR. The mechanism may proceed via reduction of the ammonium salt yielding alkyl radicals, R, which may be reduced to R⁻ and attack surface Si–Si bonds, leading to Si–C bonds, or the formation of silyl anions (≡Si⁻) under the cathodic conditions followed by nucleophilic attack on the trialkylammonium cation.     

Restructuring of force networks

The compaction of granular packings or soils is a collective process which for higher densities becomes increasingly slower reaching glassy behaviour. We present a study of this problem from various points of view, in particular we will represent the evolving force network that percolates through the system by an inverse fiber rupture model. Received 15 March 2002 and Received in final form 29 July 2002     

Study of photoconductivity and photoluminescence of organic/porous silicon complexes

In this paper, time-varying photoconductivity (PC) and the photoluminescence (PL) of different complexes were studied. Due to thick polymer layer hindering light penetrating into porous silicon (PS) layer, intrinsic PS luminescence in polymer/PS system disappeared. The physical origin of PL may be related to the recombination mechanisms involving surface defect states such as silicon oxide, siloxene. Due to carrier transfer controlled by different energy barrier, different devices prepared from different doped Si wafer showed opposite current-voltage characteristic.     

Corona-induced graft polymerization for surface modification of porous polyethersulfone membranes

Graft polymerization of acrylic acid (AA) onto porous polyethersulfone (PES) membrane surfaces was developed using corona discharge in atmospheric ambience as an activation process followed by polymerization of AA in aqueous solution. The effects of the corona parameters and graft polymerization conditions on grafting yield (GY) of AA were investigated. The grafting of AA on the PES membranes was confirmed by ATR-FTIR and X-ray photoelectron spectroscopy (XPS) analysis. Porosimetry measurements indicate the average pore diameters and porosities of the modified membranes decrease with the increase of the GY. The hydrophilicity and surface wetting properties of the original and modified membranes were evaluated by observing the dynamic changes of water contact angles. It is found that the grafting of AA occurs not only on the membrane surfaces, but also on the pore walls of the cells inside the membrane. The permeability experiments of protein solution reveal that the grafting of PAA endows the modified membranes with enhanced fluxes and anti-fouling properties. The optimized GY of AA is in the range of 150-200 μg/cm². In addition, the tensile experiments show the corona discharge treatment with the power lower than 150 W yields little damage to the mechanical strength of the membranes.     

Strongly nonlinear luminescence in oxidized porous silicon films

Partially oxidized free-standing porous silicon films show a strongly superlinear increase in photoluminescence (PL) intensity above a threshold cw excitation intensity of 10 W/cm². The PL-intensity increase can be expressed by a power law with n9 as a function of the excitation intensity. The PL-peak wavelength of this emission is slightly redshifted from that at low-excitation levels. These changes are fully reversible and reproducible, but not observed in samples on substrate. We attribute this behavior to thermal reexcitation of carriers trapped at the dangling bond states in initially nonluminescent Si nanocrystallites.     

Adsorption of molecular gases on porous materials in the SAFT-VR approximation

A simple molecular thermodynamic approach is applied to the study of the adsorption of gases of chain molecules on solid surfaces. We use a model based on the Statistical Associating Fluid Theory for Variable Range (SAFT-VR) potentials [A. Gil-Villegas, A. Galindo, P.J. Whitehead, S.J. Mills, G. Jackson, A.N. Burgess, J. Chem. Phys. 106 (1997) 4168] that we extend by including quasi-two-dimensional approximation to describe the adsorption properties of these types of real gas [A. Martínez, M. Castro, C. McCabe, A. Gil-Villegas, J. Chem. Phys. 126 (2007) 074707]. The model is applied to ethane, ethylene, propane, and carbon dioxide adsorbed on activated carbon and silica gel, which are porous media of significant industrial interest. We show that the adsorption isotherms obtained by means of the present SAFT-VR modeling are in fair agreement with the experimental results provided in the literature.     

完全可压缩渗流驱动问题的特征线有限元方法及其误差分析

多孔介质中渗流驱动问题数值方法的研究，对合理经济地开发油田，了解地下油水运动规律有一定意义。特征线法结合差分或有限元法解渗流问题，在理论和应用上获得了成功３－５，但还有很多问题需进一步研究２．前人研究多是假定流体不可压或微可压，本文研究一类完全可压缩两相驱动问题。采用特征线法与有限元法相结合，构造并分析了全离散数值格式，基于周期性假设，证明了最优Ｌ２模误差估计。     

Optical inter- and intra-band transitions in silicon nanocrystals: The role of surface vibrations

Silicon nanocrystals (ncs) belong to an interesting class of semiconductor nanostructures that manifest size dependent electronic properties. This well known effect of quantum confinement can explain many properties of silicon ncs. However, with decreasing size and dimension of the ncs, the role of surface phenomena becomes substantial. For example, we have shown recently that the strong luminescence from these ncs should be assigned to the exclusion of nonradiative channels rather than to the enhancement of radiative inter-band transitions. In addition, using infrared intra-band transitions spectroscopy, we were able to resolve the quantized electronic sublevels of small silicon ncs. We have found that under appropriate conditions, these electronic sublevels are resonantly coupled to surface vibrations. We suggest that this coupling mechanism is responsible for the exclusion of nonradiative channels in silicon ncs.     

Stability analysis using multiple scales homotopy approach of coupled cylindrical interfaces under the influence of periodic electrostatic fields

The influence of axial periodic electric fields on streaming flows through three coaxial infinitely vertical cylinders is considered. The three fluid layers are assumed to be incompressible, dielectric, viscous and saturated through porous media. To relax the mathematical manipulation of the problem, the viscous potential theory is considered. Through the current work, the stability analysis of the coupled Mathieu equations is developed in the analogy of the multiple scales homotopy technique. Away from the symmetric and anti-symmetric modes, the present study investigates a general case of the surface waves deflections. To overcome the lengthy of the algebraic calculations, the matrices concept is utilized. The stability analysis reveals the resonance as well as non-resonance cases. A set of graphs are depicted to indicate some resonance cases for a chosen sample through a dimensionless system. Therefore, the influence of some physical parameters on the stability picture is indicated. In addition, the perturbed solutions of the governed Mathieu equations are graphed.