Electron spectroscopies and their use for materials characterization

We present here a general overview of electron spectroscopies from a practical point of view. The most frequently used ones are described and the type of structural information they can provide on materials is explained in relation to the physical processes on which they are based. Furthermore, we explore critically and in detail various tools that have been developed to allow a systematic solving of structures by these spectroscopies.     

Reversible changes of the fill factor in the ZnO/CdS/Cu(In,Ga)Se2 solar cells

The reversible persistent changes of the fill factor (FF) induced by the illumination and voltage bias along with changes in the electronic properties of the ZnO/CdS/Cu(In,Ga)Se₂ photovoltaic devices have been studied. Admittance spectroscopy and capacitance–voltage characterization reveal a correlation between the FF and the space charge distribution within the absorber. Our experiments provide evidence that a major source of FF loss in efficient devices is caused by excess negative charge close to the interface. We explain the persistent changes in the net acceptor concentration in the interface region by the relaxation effects due to compensating donors—the same mechanism, which leads to metastable changes of the doping level in the bulk of the absorber.     

Oxidation of oleuropein studied by EPR and spectrophotometry

The autoxidation at alkaline pH and enzymatic oxidation by mushroom tyrosinase of oleuropein, the dominant biophenol present in the fruits and leaves of Olea europea, was followed by both electron paramagnetic resonance (EPR) and absorption spectroscopy. For comparison, the same oxidation processes were applied to 4‐methylcatechol, a simple polyphenol present in olive mill wastewaters. EPR spectra of stable o‐semiquinone radicals produced during autoxidation at pH 12 and short‐lived o‐semiquinone free radicals produced during autoxidation at pH 9.0 or tyrosinase action and stabilized by chelation with a diamagnetic metal ion (Mg²⁺) were recorded for both polyphenols, and the corresponding hyperfine splitting constants were determined. The UV‐Vis spectral characteristics of the oxidation of polyphenols were highly dependent on the type of polyphenol, oxidant type and the pH of the reaction. The kinetic behavior of tyrosinase in the presence of oleuropein and 4‐methylcatechol was followed by recording spectral changes at 400 nm (absorption maximum) over time. The tysosinase activity with oleuropein showed a pronounced pH optimum at pH 6.5 and a minor one around pH 8. From the data analysis of the initial rate at pH 6.5, the kinetic parameters K_m = 0.34 ± 0.03 mM and V_max = 0.029 ± 0.002 ΔA₄₀₀ min^–1 were determined for oleuropein.     

反应温度对聚苯胺薄膜生长的影响

在不同反应温度条件下采用原位聚合法在石英基片上制备了聚苯胺薄膜．对薄膜样品进行了紫外光谱、SEM、电性能表征。实验结果表明，过高的合成温度会加速聚合反应过程，抑制膜厚的增长，引起薄膜的热降解，进而对样品的导电性产生不良影响。根据生长速率与合成温度的依赖关系，估算了聚合反应的活化能Ea=34.4kJ/mol。     

Nonaqueous Phase Liquid Pool Dissolution as a Function of Average Pore Water Velocity

Bench-scale reactor experiments were performed to study the dissolution of a binary naphthalene-in-nonane mixture nonaqueous phase liquid (NAPL) pool over a wide range of average pore water velocities, vx (≈0.1–60 m/day). Experimental NAPL pool dissolution flux values were determined using a steady-state mass balance approach. The experimental flux data were compared to model predictions made assuming either local equilibrium or mass-transfer limited conditions. The local equilibrium model could describe the trends in the average effluent concentration and dissolution flux with 0.110?m/day. Data determined to be under mass-transfer limited conditions were fit to the nonequilibrium model to estimate values for an overall mass-transfer coefficient. The calculated overall mass-transfer coefficients had an average value of 0.407 m/day and showed no correlation with vx, probably due to mass-transfer resistance becoming dominated by the diffusional resistance in the NAPL. These results suggest that the nonequilibrium approach is better suited for describing high velocity (vx>10?m/day) dissolution of multicomponent NAPL pools, and that flushing of groundwater at very high velocities may not be an effective approach for enhancing NAPL-pool dissolution flux.     

Influence of the surface conditions on permeation in the deuterium–MANET system

The condition of the surfaces is of crucial importance for the deuterium permeation through materials. In this work a study of the surface constants for the adsorption (σk₁) and release (σk₂) of deuterium under different surface conditions on the martensitic steel DIN 1.4914 (MANET) has been carried out. The growth of an oxide surface layer (Cr₂O₃) of about 25–30 nm in a MANET sample, heat treated in an oxidizing environment, compared to the bare MANET that have a ‘natural' oxide of about 5 nm has provoked a reduction of both the permeation rate and the recombination coefficient (about 3 orders of magnitude). In addition, the permeation governing process has changed from diffusion-limited to surface-limited. The measurements of the permeation rate of deuterium were performed by a gas-phase permeation technique over the temperature range 574–746 K and for deuterium driving pressures in the range from 3 to 10⁵ Pa.     

Artificial Neural Network Modeling of Osmotic Dehydration Mass Transfer Kinetics of Fruits

Artificial neural network (ANN) models were developed for the prediction of transient moisture loss (ML) and solid gain (SG) in osmotic dehydration of fruits using process kinetics data from the literature. ANN models for ML and SG were developed based on data over a broad range of operating conditions and ten common processing variables: temperature and concentration of osmotic solution, immersion time, initial water and solid content of the fruit, porosity, surface area, characteristic length, solution-to-fruit mass ratio, and agitation level. The trained models were able to accurately predict the outputs with associated regression coefficients (r) of 0.96 and 0.93, respectively, for ML and SG. These ANN models performed much better than those obtained from linear multivariate regression analysis. The large number of process variables and their wide ranges considered along with their easy implementation in a spreadsheet make them very useful and practical for process design and control.     

DX centers in AlxGa1-xAs bulk alloy,AlAs/GaAs ordered,and disordered superlattices

Properties of theDX centers in Al_0.5Ga_0.5As bulk alloy (b-AL), (AlAs)₂ (GaSa)₂ ordered superlattice (o-SL) and (AlAs) _m (GaAs) _n disordered superlattice (d-SL) (m = 1, 2, 3,n = 1, 2, 3) with the same macroscopic composition were measured and compared. By deconvolution of deep level transient spectroscopy (DLTS) spectrum due to theDX center, we have found a decrease in the number of separate peaks in DLTS spectrum in an intentionally atomic ordered arrangement. Visiting Scholar of the Japan Society for the Promotion of Science. On leave from Department of Electrical Engineering, San Jose State University, San Jose, California 95192-0084, USA.     

Modeling the Absorption of Acidic Gases by Alkanolamine Solutions Incorporating Several Reactions

A general model, based on double film theory, is developed to study absorption with chemical reactions. In the liquid film region, the model is a set of differential equations that describe the mass transfer accompanying several chemical reactions; the resolution of the system is achieved by the finite difference method using an implicit scheme combined with Newton's method. Continuity equations and equilibrium coefficients are exploited in the treatment of the bulk region, which is based on the Newton‐Raphson method; the results are used directly as boundary conditions in the liquid film equations. Maxwell‐Stefan equations have been used as a rigorous approach in this model.