The plasmon resonance absorption of Ag/SiO2 nanocomposite films

The plasmon resonance absorption of the Ag/SiO2 nanocomposite film is investigated. The measured absorption spectra are compared with those calculated by the Mie theory. The results indicate that the Mie theory on the basis of classical electrodynamics can only partially explain the optical absorption spectra of the Ag/SiO2 nanocomposite film. We believe that the plasmon resonance absorption is mainly an intrinsic quality of the metal particle, and can be explained only with the electronic structure of the metal particle. In the latter, surface resonance state is introduced to systematically discuss the optical absorption spectra of the Ag/SiO2 nanocomposite film. (C) 2003 Elsevier Science B.V. All rights reserved.

Photoluminescence study on coarsening of self-assembled InAlAs quantum dots on GaAs (001)

Red-emission at similar to 640 nm from self-assembled In0.55Al0.45As/Al0.5Ga0.5As quantum dots grown on GaAs substrate by molecular beam epitaxy (MBE) has been demonstrated. We obtained a double-peak structure of photoluminescence (PL) spectra from quantum dots. An atomic force micrograph (AFM) image for uncapped sample also shows a bimodal distribution of dot sizes. From the temperature and excitation intensity dependence of PL spectra, we found that the double-peak structure of PL spectra from quantum dots was strongly correlated to the two predominant quantum dot families. Taking into account quantum-size effect on the peak energy, we propose that the high (low) energy peak results from a smaller (larger) dot family, and this result is identical with the statistical distribution of dot lateral size from the AFM image.

Blue-shift photoluminescence from porous InAlAs

A porous InAlAs structure was first obtained by electrochemical etching. Nano-pore arrays were formed when the In0.52Al0.48As membrane was anodized at constant voltages in an HF aqueous solution. These self-assembled structures showed evident blue-shift photoluminescence emissions. While a quantum size effect alone underestimates the blue-shift energy for a sample with a relatively large average pore wall thickness, a novel effect caused by the asymmetric etching is proposed to account for this phenomenon. The results inferred from the x-ray double crystal diffraction are in good agreement with the experimental data.

Strain gradient theory based on a new framework of non-local model

A new framework of non-local model for the strain energy density is proposed in this paper. The global strain energy density of the representative volume element is treated as a non-local variable and can be obtained through a special integral of the local strain energy density. The local strain energy density is assumed to be dependent on both the strain and the rotation-gradient. As a result of the non-local model, a new strain gradient theory is derived directly, in which the first and second strain gradients, as well as the triadic and tetradic stress, are introduced in the context of work conjugate. For power law hardening materials, size effects in thin metallic wire torsion and ultra-thin cantilever beam bend are investigated. It is found that the result predicted by the theoretical model is well consistent with the experimental data for the thin wire torsion. On the other hand, the calculation result for the micro-cantilever beam bend clearly shows the size effect.

ZnO clusters encapsulated inside micropores of zeolites studied by UV Raman and laser-induced luminescence spectroscopies

Using microporous zeolites as host, sub-nanometric ZnO clusters were prepared in the micropores of the host by the incipient wetness impregnation method. A small amount of sub-nanometric ZnO clusters were introduced into the channels of HZSM-5 zeolite, whereas a large quantity of sub-nanometric ZnO clusters can be accommodated in the supercages of HY zeolite and no macrocrystalline ZnO exists on the extra surface of the HY material. The vibrations of the zeolite framework and ZnO were characterized by UV Raman spectroscopy. The optical properties of these ZnO clusters were studied by UV-visible absorption spectroscopy and laser-induced luminescence spectroscopy. It is found that there are strong host-guest interactions between the framework oxygen atoms of zeolite and ZnO clusters influencing the motions of the framework oxygen atoms. The interaction may be the reason why ZnO clusters are stabilized in the pores of zeolites. Different from bulk ZnO materials, these sub-nanometric ZnO clusters exhibit their absorption onset below 265 nm and show a purple luminescence band (centered at 410-445 nm) that possesses high quantum efficiency and quantum size effect. This purple luminescence band most likely originates from the coordinatively unsaturated Zn sites in sub-nanometric ZnO clusters. On the other hand, the differences in the pore structure between HZSM-5 and HY zeolites cause the absorption edge and the purple luminescence band of ZnO clusters in ZnO/HZSM-5 show a red shift in comparison with those of ZnO clusters in ZnO/HY.

Highly Active Carbon-supported PdSn Catalysts for Formic Acid Electrooxidation

PdSn/C catalysts with different atomic ratios of Pd to Sn were synthesised by a NaBH4 reduction method. Electrochemical tests show that the alloy catalysts exhibit significantly higher catalytic activity and stability for formic acid electrooxidation (FAEO) than the Pd/C catalyst prepared with the same method. XRD and TEM indicate that a particle-size effect is not the main cause for the high performance. XPS confirms that Pd is modified by Sn through an electronic effect which can decrease the adsorption strength of poisonous intermediates on Pd and thus promote the FAEO greatly.

Preparation of a carbon supported Pt catalyst using an improved organic sol method and its electrocatalytic activity for methanol oxidation

The organic sol method for preparing ultrafine transition metal colloid particles reported for the first time by Bonnemann et al. [H. Bonnemann, W Brijoux, R. Brinkmann, E. Dinjus, T. Jou beta en, B. Korall, Angew. Chem. Int. Ed. Engl., 30 (1991) 1312] has been improved in this paper. The improved organic sol method uses SnCl2 as the reductant and methanol as the organic solvent. Thus, this method is very simple and inexpensive. It was found that the average size of the Pt particles in the Pt/C catalysts can be controlled by adjusting the evaporating temperature of the solvent. Therefore, the Pt/C catalysts prepared by the same method are suitable for evaluating the size effect of the Pt particles on electrocatalytic performance for methanol oxidation. The results of the X-ray diffraction (XRD) and transmission electron microscopy (TEM) showed that when the evaporating temperatures of the solvent are 65, 60, 50, 40, and 30 degrees C, the average sizes of the Pt particles in the Pt/C catalysts prepared are: 2.2, 3.2, 3.8, 4.3, and 4.8 nm, respectively. The X-ray photoelectron spectroscopic (XPS) results demonstrated that the small Pt particles are easily oxidized and the decomposition/adsorption of methanol cannot proceed on the surfaces of Pt oxides.

小湾坝基卸荷岩体参数研究

The Xiao-wan Power Station is the second highest arch dam in the world under construction. The height of the dam is about 292m. Large-scale excavation in the dam foundation of Xiao-wan Power Station has brought intensive unloading phenomenon. We collected a large number of firsthand data on unloaded rock mass in dam foundation, which supplies a natural testing ground for researching unloaded rock mass after excavation. Detailed study was carried out on the parameters of unloaded rock mass in the dam foundation of Xiao-wan Power Station. The study is not only importance for the Xiao-wan Power Station, but also has important instruction significance to similar projects in the Southwest of China. In order to study the mechanical parameters of unloaded rock mass, large field and laboratory tests were carried out. The test results showed the size effect of the sample is obvious. The change of deformation modulus of rock is not obvious. However, the Poisson's ratio of rock is increased under unloaded condition, its value is even more than 0.5. The theoretical forecasted results is accordance to the field tests including sound wave data and deformation monitoring data, which shows the forecasted results were reasonable. The soften yield criterion was adopted in the thesis to study the characteristics of the brittle rock mass in order to simulate their brittle failures. Based on the study results above, the transform of the structural plane network model to the numerical one was carried out, which made it feasible to consider the influence of large amount joints on the mechanical characteristic of rock mass in the numerical analyses. Using a factor, the degree of the damage or strengthen of rock mass can be determined rapidly, which proposed a rapid and feasible method for the determination of the parameters of rock mass.

非均匀性对岩石破裂过程影响的研究

Rock heterogeneity plays an important role in rock fracturing processes. However, because fracturing is a dynamic process and it is very difficult to quantify materials' heterogeneity, most of the theories dealing with local failure were based on the homogeneity assumption, very few involving stress distribution heterogeneity and successive local failure due to rock heterogeneity. Therefore, based on various references, the author studied the laws and mechanism of influences of heterogeneity on rock fracturing processes, under the frame of the project "Study on Associate Mechanism between Rock Mass Fracture and Strength Failure", funded by Nation Natural Science Fund. the research consists of such aspects as size effect correction to rock fracture parameters, SEM (Scanning Electron Microscope) real-time observation on rock samples under different loads, micro-hardness testing, and numerical simulating based on microstructure. There are some important research results as followed: 1. Unifying formula for nonlinear and non-singularity correction, simplifying the complex process of correcting size effect on rock fracture toughness. 2. Using the methods of micro-hardness testing mineral grain and random jointing micrograph digitizing mineral slice, preliminarily solving the problems of numerical simulating and quantitatively describing the heterogeneous strength and its distribution rules, which has certain innovation and better practicability. 3. Based on SEM real-time observation, studying the micro-process of fracturing in marble, sandstone, granite, and mushroom stone samples with premanufactured cracks under tension, pure-shear and compression-shear conditions. Strength Failure was observed: there was some kind failure occurred before Fracture Failure in marble and sandstone samples with double cracks under pure-shearing. It is believed that the reason of strength failure developing is that stress concentrations is some locations are larger than that near the end of pre-manufactured cracks. 4. Based on the idea that rock macro-constitute is composed of complex microstructure, the promising method used to handle heterogeneity considers not only the heterogeneity of the rock medium, but also the heterogeneity of the rock structure. 5. Putting forward two types of rock strength failure: medium strength failure induced by heterogeneity of rock medium and structure strength failure induced by heterogeneity rock structure. 6. By evaluating potential fracture cell with proper failure priority, the numerical simulating method solved the problem of simulating the coextensive strength failure and fracture failure with convention strength failure rules. The result of numerical analysis shows that the influence of heterogeneity on rock fracturing processes is evident. The sinuosity of the rock fracture-propagation path, and the irregular fluctuation of loading displacement curve, is mainly controlled by the heterogeneity of rock medium.

花岗岩风化土微观结构及其工程地质特性研究

Saprolite is the residual soil resulted from completely weathered or highly weathered granite and with corestones of parent rock. It is widely distributed in Hong Kong. Slope instability usually happens in this layer of residual soil and thus it is very important to study the engineering geological properties of Saprolite. Due to the relic granitic texture, the deformation and strength characteristics of Saprolite are very different from normal residual soils. In order to investigate the effects of the special microstructure on soil deformation and strength, a series of physical, chemical and mechanical tests were conducted on Saprolite at Kowloon, Hong Kong. The tests include chemical analysis, particle size analysis, mineral composition analysis, mercury injection, consolidation test, direct shear test, triaxial shear test, optical analysis, SEM & TEM analysis, and triaxial shear tests under real-time CT monitoring.Based on the testing results, intensity and degree of weathering were classified, factors affecting and controlling the deformation and strength of Saprolite were identified, and the interaction between those factors were analyzed.The major parameters describing soil microstructure were introduced mainly based on optical thin section analysis results. These parameters are of importance and physical meaning to describe particle shape, particle size distribution (PSD), and for numerical modeling of soil microstructure. A few parameters to depict particle geometry were proposed or improved. These parameters can be used to regenerate the particle shape and its distribution. Fractal dimension of particle shape was proposed to describe irregularity of particle shapes and capacity of space filling quantitatively. And the effect of fractal dimension of particle shape on soil strength was analyzed. At the same time, structural coefficient - a combined parameter which can quantify the overall microstructure of rock or soil was introduced to study Saprolite and the results are very positive. The study emphasized on the fractal characteristics of PSD and pore structure by applying fractal theory and method. With the results from thin section analysis and mercury injection, it was shown that at least two fractal dimensions Dfl(DB) and Df2 (Dw), exist for both PSD and pore structure. The reasons and physical meanings behind multi-fractal dimensions were analyzed. The fractal dimensions were used to calculate the formation depth and weathering rate of granite at Kowloon. As practical applications, correlations and mathematical models for fractal dimensions and engineering properties of soil were established. The correlation between fractal dimensions and mechanical properties of soil shows that the internal friction angle is mainly governed by Dfl 9 corresponding to coarse grain components, while the cohesion depends on Df2 , corresponding to fine grain components. The correlations between the fractal dimension, friction angle and cohesion are positive linear.Fractal models of PSD and pore size distribution were derived theoretically. Fragmentation mechanism of grains was also analyzed from the viewpoint of fractal. A simple function was derived to define the theoretical relationship between the water characteristic curve (WCC) and fractal dimension, based on a number of classical WCC models. This relationship provides a new analytical tool and research method for hydraulic properties in porous media and solute transportation. It also endues fractal dimensions with new physical meanings and facilitates applications of fractal dimensions in water retention characteristics, ground water movement, and environmental engineering.Based on the conclusions from the fractal characteristics of Saprolite, size effect on strength was expressed by fractal dimension. This function is in complete agreement with classical Weibull model and a simple function was derived to represent the relationship between them.In this thesis, the phenomenon of multi-fractal dimensions was theoretically analyzed and verified with WCC and saprolite PSD results, it was then concluded that multi-fractal can describe the characteristics of one object more accurately, compared to single fractal dimension. The multi-fractal of saprolite reflects its structural heterogeneity and changeable stress environment during the evolution history.

Reversible regeneration of molybdenum carbonyl species on an alumina thin film

The thin alumina film-supported metallic molybdenum model catalyst was prepared by thermal decomposition of MO(CO)6, and CO chemisorption on the catalyst was investigated in-situ by thermal desorption spectroscopy (TDS) and X-ray photoelectron spectroscopy (XPS). The results showed that a molybdenum-carbonyl-like species was formed on the alumina surface at low temperature by high coordination of CO with the surface metallic molybdenum nanoparticles, indicating a reversible regeneration of molybdenum carbonyl on the alumina surface. CO chemisorption on the model catalyst surface caused the Mo 3d XPS peak to shift toward higher binding energy. The formed molybdenum carbonyl species appeared at about 240 K in the TDS. The supported metallic molybdenum nanoparticles were quite different from the bulk molybdenum in chemical properties, which indicated a prominent particle-size effect of the clusters.

Effect of Rock Mass Structure and Block Size on the Slope Stability-Physical Modeling and Discrete Element Simulation

This paper studies the stability of jointed rock slopes by using our improved three-dimensional discrete element methods (DEM) and physical modeling. Results show that the DEM can simulate all failure modes of rock slopes with different joint configurations. The stress in each rock block is not homogeneous and blocks rotate in failure development. Failure modes depend on the configuration of joints. Toppling failure is observed for the slope with straight joints and sliding failure is observed for the slope with staged joints. The DEM results are also compared with those of limit equilibrium method (LEM). Without considering the joints in rock masses, the LEM predicts much higher factor of safety than physical modeling and DEM. The failure mode and factor of safety predicted by the DEM are in good agreement with laboratory tests for any jointed rock slope.

Effect of Particle Size on the Formation of Adiabatic Shear Band In Particle Reinforced Metal Matrix Composites

In this paper, the effect of particle size on the formation of adiabatic shear band in 2024 All matrix composites reinforced with 15% volume fraction of 3.5, 10 and 20 mum SiC particles was investigated by making use of split Hopkinson pressure bar (SHPB). The results have demonstrated that the onset of adiabatic shear banding in the composites strongly depends on the particle size and adiabatic shear banding is more readily observed in the composite reinforced with small particles than that in the composite with large particles. This size dependency phenomenon can be characterized by the strain gradient effect. Instability analysis reveals that high strain gradient is a strong driving force for the formation of adiabatic shear banding in particle reinforced metal matrix composites (MMCp).