Part I. Influence of membrane morphology on ion-exchange and charge propagation in composite polyelectrolyte electrode coatings. Part II. Dynamic surface tension measurements of polarization relaxation at mercury pool electrodes by the method of Wilhelmy.

Part I. Novel composite polyelectrolyte materials were developed that exhibit desirable charge propagation and ion-retention properties. The morphology of electrode coatings cast from these materials was shown to be more important for its electrochemical behavior than its chemical composition.

Part II. The Wilhelmy plate technique for measuring dynamic surface tension was extended to electrified liquid-liquid interphases. The dynamical response of the aqueous NaF-mercury electrified interphase was examined by concomitant measurement of surface tension, current, and applied electrostatic potential. Observations of the surface tension response to linear sweep voltammetry and to step function perturbations in the applied electrostatic potential (e.g., chronotensiometry) provided strong evidence that relaxation processes proceed for time-periods that are at least an order of magnitude longer than the time periods necessary to establish diffusion equilibrium. The dynamical response of the surface tension is analyzed within the context of non-equilibrium thermodynamics and a kinetic model that requires three simultaneous first order processes.

Structural and optical properties of YAG : Ce3+ phosphors by sol-gel combustion method

High-quality Ce3+-doped Y3Al5O12 (YAG:Ce3+) phosphors were synthesized by a facile sol-gel combustion method. In this sol-gel combustion process, citric acid acts as a fuel for combustion, traps the constituent cations and reduces the diffusion length of the precursors. The XRD and FT-IR results show that YAG phase can form through sintering at 900 degrees C for 2 h. This temperature is much lower than that required to synthesize YAG phase via the solid-state reaction method. There were no intermediate phases such as YAlO3 (YAP) and Y4Al2O9 (YAM) observed in the sintering process. The average grain size of the phosphors sintered at 900-1100 degrees C is about 40 nm. With the increasing of sintering temperature, the emission intensity increases due to the improved crystalline and homogeneous distribution of Ce3+ ions. A blue shift has been observed in the Ce3+ emission spectrum of YAG:Ce3+ phosphors with increasing sintering temperatures from 900 to 1200 degrees C. It can be explained that the decrease of lattice constant affects the crystal field around Ce3+ ions. The emission intensity of 0.06Ce-doped YAG phosphors is much higher than that of the 0.04Ce and 0.02Ce ones. The red-shift at higher Ce3+ concentrations may be Ce-Ce interactions or variations in the unit cell parameters between YAG:Ce3+ and YAG. It can be concluded that the sol-gel combustion synthesis method provides a good distribution of Ce3+ activators at the molecular level in YAG matrix. (c) 2005 Elsevier B.V. All rights reserved.

The effect of diffusion and overhangs/vacancies on the microstructure of zig-zag thin film

Basing on some growth models of thin film, we have investigated the growth mechanism of glancing angle deposition (GLAD) film. The simulation verifies that the overhangs/vacancies also contribute to the columnar growth as well as the self-shadowing effect for GLAD thin film. Besides, we have studied the effect of the deposition rate, surface and bulk diffusions on the microstructure of thin film using the time-dependent Monte Carlo method. The results show that the surface and bulk diffusions can significantly enhance the packing density of thin film in GLAD growth, and the increase of the deposition rate induce the moderate decrease of the packing density. (c) 2006 Elsevier B.V. All rights reserved.

Crank-Nicholson method for rate equations in powder random lasers

3rd International Conference on Mathematical Modeling in Physical Sciences (IC-MSQUARE 2014)

Agar from Gracilaria lichenoides and Gracilaria confervoides from Ceylon

"Agar-agar" is a name derived from the jelly obtained from certain red algae in Malaya. In Sri Lanka agar is prepared from the red seaweeds Gracilaria confervoides and Gracilaria lichenoides. They are commonly known as Sri Lanka moss and the local names are "kandha parsi or sanchow parsi". The uses of agar are given together with details of the method of extraction of this substance from Gracilaria lichenoides and Gracilaria confervoides.

Introducing carbon diffusion barriers for uniform, high-quality graphene growth from solid sources.

Carbon diffusion barriers are introduced as a general and simple method to prevent premature carbon dissolution and thereby to significantly improve graphene formation from the catalytic transformation of solid carbon sources. A thin Al2O3 barrier inserted into an amorphous-C/Ni bilayer stack is demonstrated to enable growth of uniform monolayer graphene at 600 °C with domain sizes exceeding 50 μm, and an average Raman D/G ratio of <0.07. A detailed growth rationale is established via in situ measurements, relevant to solid-state growth of a wide range of layered materials, as well as layer-by-layer control in these systems.

As-doped p-type ZnO films by sputtering and thermal diffusion process

As-doped p-type ZnO films were grown on GaAs by sputtering and thermal diffusion process. Hall effect measurements showed that the as-grown films were of n-type conductivity and they were converted to p-type behavior after thermal annealing. Moreover, the hole concentration of As-doped p-type ZnO was very impressible to the oxygen ambient applied during the annealing process. In addition, the bonding state of As in the films was investigated by x-ray photoelectron spectroscopy. This study not only demonstrated an effective method for reliable and reproducible p-type ZnO fabrication but also helped to understand the doping mechanism of As-doped ZnO. (c) 2006 American Institute of Physics.

A novel method of determining semiconductor parameters in EBIC and SEBIV modes of SEM

We present a novel method for determining semiconductor parameters such as diffusion length L, lifetime tau and surface recombination velocity S of minority carriers by employing scanning electron microscopy (SEM). This new method is applicable to both electron beam induced current (EBIC and surface electron beam induced voltage (SEBIV) modes in SEM. The quantitative descriptions for EBIC and SEBIV signals are derived. The parameters L, S and tau can be directly extracted from the expressions for EBIC or SEBIV signals and their relaxation characteristics in experiment. As an example, the values of L, S and tau for n-p junction and p-Si crystal are determined by using the novel method in EBIC or SEBIV mode. The carrier diffusion length of a p-Si crystal is determined to be 8.74 mum in SEBIV mode. It is very close to the normal diffusion length of 7.41 mum of this sample. The novel method is proved to be very helpful for the quantitative characterization of semiconductor materials and devices. Especially, the SEBIV mode in SEM shows great potential for investigating semiconductor structures nondestructively.

Effects of convection and solid wall on the diffusion in microscale convection flows

The diffusive transport properties in microscale convection flows are studied by using the direct simulation Monte Carlo method. The effective diffusion coefficient D is computed from the mean square displacements of simulated molecules based on the Einstein diffusion equation D = x2 t /2t. Two typical convection flows, namely, thermal creep convection and Rayleigh– Bénard convection, are investigated. The thermal creep convection in our simulation is in the noncontinuum regime, with the characteristic scale of the vortex varying from 1 to 100 molecular mean free paths. The diffusion is shown to be enhanced only when the vortex scale exceeds a certain critical value, while the diffusion is reduced when the vortex scale is less than the critical value. The reason for phenomenon of diffusion reduction in the noncontinuum regime is that the reduction effect due to solid wall is dominant while the enhancement effect due to convection is negligible. A molecule will lose its memory of macroscopic velocity when it collides with the walls, and thus molecules are hard to diffuse away if they are confined between very close walls. The Rayleigh– Bénard convection in our simulation is in the continuum regime, with the characteristic length of 1000 molecular mean free paths. Under such condition, the effect of solid wall on diffusion is negligible. The diffusion enhancement due to convection is shown to scale as the square root of the Péclet number in the steady convection regime, which is in agreement with previous theoretical and experimental results. In the oscillation convection regime, the diffusion is more strongly enhanced because the molecules can easily advect from one roll to its neighbor due to an oscillation mechanism. © 2010 American Institute of Physics. doi:10.1063/1.3528310

A new method of measuring alcohol clusters in polyimide membrane: combination of inverse gas chromatography with equilibrium swelling

A new method of measuring the mean size of solvent clusters in swollen polymer membrane is presented in this paper. This method is based on a combination of inverse gas chromatography (IGC) and equilibrium swelling. The mechanism is that weight fraction activity coefficient of solvent in swollen polymer is influenced by its clusters size. The mean clusters size of solvent in swollen polymer can be calculated as the quotient of the weight fraction activity coefficient of clustering system dividing the weigh fraction activity coefficient of non-clustering system. In this experiment, the weigh fraction activity coefficient of non-clustering system was measured with IGC. Methanol, ethanol and polyimide systems were tested with the new method at three temperatures, 20, 40, and 60degreesC. The mean clusters size of methanol in polyimide was five, four, and three at each temperature condition, respectively. Ethanol did not form clusters (the mean clusters size was one). In contrast to the inherent narrow temperature range in DSC, XRD, and FTIR methods, the temperature range in IGC and equilibrium swelling is broad. Compared with DSC. XRD. and FTIR, this new method can detect the clusters of solvent-polymer system at higher temperature.

Branched crystal morphology of linear polyethylene crystallized in a two-dimensional diffusion-controlled growth field

The branched crystal morphology of linear polyethylene formed at various temperatures from thin films has been studied by atomic-force microscopy (AFM), transmission electron microscopy (TEM), electron diffraction (ED) pattern and polymer decoration technique. Two types of branched patterns, i.e. dendrite and seaweed patterns, have been visualized. The fractal dimension d(f) = 1.65 of both dendrite and some of seaweed patterns was obtained by using the box-counting method, although most of the seaweed patterns are compact. Selected-area ED patterns indicate that the fold stems tilt about 34.5degrees around the b-axis and polymer decoration patterns show that the chain folding direction and regularity in two (200). regions are quite different from each other. Because of chain tilting, branched crystals show three striking features: 1) the lamella-like branches show two (200) regions with different thickness; 2) the crystals usually bend towards the thin region; 3) the thick region grows faster by developing branches, thus branches usually occur outside the thick region. The branched patterns show a characteristic width w, which gives a linear relationship with the crystallization temperature on a semilogarithmic plot.

Digital simulation in a thin layer spectroelectrochemical cell with minigrid platinum electrode by microregion approximation explicit finite difference method

The microregion approximation explicit finite difference method is used to simulate cyclic voltammetry of an electrochemical reversible system in a three-dimensional thin layer cell with minigrid platinum electrode. The simulated CV curve and potential scan-absorbance curve were in very good accordance with the experimental results, which differed from those at a plate electrode. The influences of sweep rate, thickness of the thin layer, and mesh size on the peak current and peak separation were also studied by numerical analysis, which give some instruction for choosing experimental conditions or designing a thin layer cell. The critical ratio (1.33) of the diffusion path inside the mesh hole and across the thin layer was also obtained. If the ratio is greater than 1.33 by means of reducing the thickness of a thin layer, the electrochemical property will be far away from the thin layer property.

Study on diffusion of electroactive species in polyelectrolyte polyethylene glycol lithium perchlorate by chronoamperometry at a microdisk electrode

The mass transport dynamics of Ferrocene in polyelectrolyte polyethylene glycol lithium perchlorate (PEG . LiClO4) was studied by using chronoamperometry at a microdisk electrode. Chronoamperometry is a powerful method for the study of mass transport in polyelectrolyte, it has many advantages over the conventional methods at a microelectrode and the steady-state method at an ultramicroelectrode. By using this method the apparent diffusion coefficient D-app and concentration C-a of the electroactive species, can be estimated from a single experiment without previous knowledge of either one. We have estimated D-app and C-a of ferrocene in PEG . LiClO4 polyelectrolyte from 25 degrees C to 75 degrees C. The dependence on the concentration of electroactive species was observed. The diffusion coefficients decrease with increasing ferrocene concentration and decreasing temperature. The mass transport mechanism is explained, by using a free volume model.

INFLUENCE ON THE THIN-LAYER SPECTROELECTROCHEMISTRY - DIFFUSION WITHIN A THIN-LAYER CELL

The potential step and cyclic voltammetric experiments in the thin layer cell were studied by the digital simulation method in this work. A relationship between the time needed for exhaustive electrolysis of the electroactive species and the thickness of the thin layer cell was obtained. On the basis of this formula, the lower time limit for a kinetic plot of the following chemical reaction can be estimated. For the cyclic voltammetry, a semiempirical formula was derived for the peak-peak potential difference (Delta Ep) in terms of the sweep rate (v), thickness of the cell (d), diffusion coefficient (D) and electron transfer number (n) 59 - n Delta Ep/n Delta Ep = 0.328(RT D/nF vd(2))(1.20).

UNSTEADY DIFFUSION KINETICS OF ZIEGLER-NATTA HETEROGENEOUS CATALYST POLYMERIZATION .4. PREDICTION OF EXPERIMENTAL RESULTS OF PROPYLENE ETHYLENE 1-HEXADECENE TERPOLYMERIZATION

The prediction, based on unsteady diffusion kinetics, of the enhancement of reactivity and incorporation of 1-hexadecene in its copolymerization with propylene on adding a small amount of ethylene (increase from 5,2 mol-% to 10,8 mol-% when 2% of ethylene was added, and to 16,1 mol-% when 5% was added) was verified in the terpolymerization of propylene/1-hexadecene/ethylene on a commercial Solvay-type delta-TiCl3 catalyst. The catalyst efficiency was thus also increased. These augmentations originate from the increase in diffusion coefficient of 1-hexadecene at the catalyst surface when the PP crystallinity decreases on introduction of ethylene. Calculation based on unsteady diffusion kinetics showed that the order of diffusion coefficients ethylene > propylene > 1-hexadecene is reversed as the monomer concentration increases when the monomers are not at their equilibrium concentration. Sequence distribution as determined by means of C-13 NMR revealed a tendency of blocky structure rather than a Bernoullian one. The terpolymer compositions obtained by means of an IR method developed in this work conform rather well with the NMR results. Results in this work not only support the unsteady diffusion kinetics but also provide a new route to prepare olefinic copolymer rubbers with heterogeneous titanium catalysts.