Interfacial kinetic enhancement of metal ion adsorption on binary mixed self-assembled monolayers

The adsorption of metal ions, a type of surface reaction on binary mixed self-assembled monolayers (SAMs) on a gold surface composed of 1,6-hexanedithiol (HDT) with 11-mercaptoundecanoic acid (MUA), was monitored by in situ surface plasmon resonance (SPR) measurements. The differential SPR reflectance (ΔR) enables the kinetics of adsorption of Pt²⁺ on the mixed SAMs to be investigated. Unlike single HDT SAM, kinetic analyses of the mixed SAMs showed that the rate of adsorption of Pt²⁺ was enhanced and that it was highly dependent on the fraction of MUA present. These SPR measurements suggest that the adsorption rate of metal ions can be readily manipulated simply by using mixed SAMs.     

Nonextensive treatment of nucleation and growth in a thin layer

In this study, a generalized method based upon nonextensive statistics is presented for nucleation and growth processes in a thin layer between two interfaces. It is shown that the presented mathematical model, which uses an index called the entropic index that measures the nonextensivity of the physical system, successfully deals with the nucleation and growth processes, and works better than Johnson–Mehl–Avrami–Kolmogorov model. The presented model also contains Austin–Rickett model as a special case.     

Magnetic characterization of dual phase FeZrB soft magnetic alloy

The magnetic properties and the annealing process of Fe₇₈Zr₇B₁₅ amorphous ribbons are investigated by X-ray diffraction (XRD), differential scanning calorimetry, and vibrating sample magnetometer. The fully amorphous structure of the as-quenched ribbons is confirmed by the XRD pattern. The Curie temperature and the saturation magnetization M_s of the ribbons are 305 °C and 124.3 emu/g, respectively. Annealing at 550 °C can result in an increase in M_s with annealing time due to the increasing crystallized volume fraction of α-Fe phase. The optimized annealing process is established at 550 °C for 20-30 min with maximum M_s of 146.6 emu/g. The morphology of the ribbons annealed at 550 °C is observed by scanning electron microscopy, showing that nanocrystalline α-Fe grains are dispersed in an amorphous matrix.     

Crystallization and grain growth characteristics of yttria-stabilized zirconia thin films grown by pulsed laser deposition

Knowledge about the crystallization and grain growth characteristics of metal oxide thin films is essential for effective microstructural engineering by thermal post-annealing and the integration to Si-based miniaturized electroceramic devices. Finite size and interface effects may cause fundamentally different behavior compared to three dimensional macroscopic systems. This work presents a comprehensive investigation of the crystallization kinetics and microstructural evolution upon thermal post-annealing of amorphous 200 nm and 1.2 μm thin films of 8 mol% yttria-stabilized zirconia grown by pulsed laser deposition (PLD) using ex- and in-situ X-ray diffraction, Raman spectroscopy, and electron microscopy techniques. The layers exhibit a remarkably low crystallization temperature of 200-250 °C while exposure to energetic electrons induces the formation of randomly dispersed ~ 20 nm sized crystallites already at ambient temperature. The isothermal amorphous to crystalline phase transformation kinetics can be described quantitatively by the Johnson-Mehl-Avrami-Kolmogorov model. They reveal characteristics of a three dimensional growth under cation bulk diffusion control with heterogeneous nucleation that changes from continuous to instantaneous initial seeding at temperatures above 300 °C. Large (> 100 nm) equiaxed grains are formed rapidly without a stabilization of transient nanocrystals during the thermally induced phase transformation. A stagnation of normal grain growth resulting in a logarithmic normal size distribution is observed once the average grain dimensions approach the film thickness. The results on the crystallization and grain growth of the PLD-grown YSZ films are evaluated with regards to the fabrication of YSZ solid electrolyte membranes for Si-supported micro solid oxide fuel cells and gas sensors.     

Directional crystallization and self-assembling initiated by mechanical shock or electron beam in nanocrystalline Co-C and Fe-C films

We investigated iron and cobalt films with 20% carbon concentration with nanocrystalline structure. One of the aims of this work is to analyze the physical nature of high-speed structural self-assembling as often happens in explosive crystallization processes in these films.     

Self-assembly of nanoparticles on the surface of ionic crystals: Structural properties

With a suitable combination of ligand-stabilised nanoparticle suspension and ionic salt solutions, it is possible to produce microcrystals that are coated with nanoparticles. The self-assembly process of coating microcrystals by gold nanoparticles (NP) is mediated by the crystal lattice. This is the so-called CLAMS process - a generic process for self-organisation of nanoparticles on the surface of crystals [M. Murugeshan, D. Cunningham, J.-L. Martnez-Albertos, R. Vrcelj, B.D. Moore, Chem. Commun. (2005) 2677]. We are exploring here the structural properties of these self-assembled structures by using different imaging techniques.     

Analysis of excimer laser annealing of amorphous SiGe on La2O3//Si structures

The reduction of complementary metal oxide semiconductor dimensions through transistor scaling is in part limited by the SiO₂ dielectric layer thickness. Among the materials evaluated as alternative gate dielectrics one of the leading candidate is La₂O₃ due to its high permittivity and thermodynamic stability. However, during device processing, thermal annealing can promote deleterious interactions between the silicon substrate and the high-k dielectric degrading the desired oxide insulating properties.The possibility to grow poly-SiGe on top of La₂O₃//Si by laser assisted techniques therefore seems to be very attractive. Low thermal budget techniques such as pulsed laser deposition and crystallization can be a good choice to reduce possible interface modifications due to their localized and limited thermal effect.In this work the laser annealing by ArF excimer laser irradiation of amorphous SiGe grown on La₂O₃//Si has been analysed theoretically by a numerical model based on the heat conduction differential equation with the aim to control possible modifications at the La₂O₃//Si interface. Simulations have been carried out using different laser energy densities (0.26-0.58 J/cm²), different La₂O₃ film thickness (5-20 nm) and a 50 nm, 30 nm thick amorphous SiGe layer. The temperature distributions have been studied in both the two films and substrate, the melting depth and interfaces temperature have been evaluated. The fluences ranges for which the interfaces start to melt have been calculated for the different configurations.Thermal profiles and interfaces melting point have shown to be sensitive to the thickness of the La₂O₃ film, the thicker the film the lower the temperature at Si interface.Good agreement between theoretical and preliminary experimental data has been found.According to our results the oxide degradation is not expected during the laser crystallization of amorphous Si_0.7Ge_0.3 for the examined ranges of film thickness and fluences.     

红辉沸石合成A型分子筛的红外光谱研究

以天然红辉沸石合成了A型分子筛，通过XRD、IR光谱研究了其晶化过程。发现在1000-950cm^-1、750一600cm^-1、560cm^-1、460cm^-1处的红外吸收峰随结晶度有规律的变化，初步探讨其反应机理。     

Structure-dependent activities of Cu2O cubes in thermal decomposition of ammonium perchlorate

Catalytic activity of three kinds of Cu₂O cubes with different structures for thermal decomposition of ammonium perchlorate (AP) has been investigated in this paper. Cu₂O crystals in the form of cubic aggregate, mono-dispersed cube and {100} planes etched cube have been synthesized through a microwave-assisted solvothermal method by adjusting the composition of solvent. The decomposition of AP in the presence or absence of Cu₂O cubes has been investigated non-isothermally through thermogravimetry and differential scanning calorimetry (DSC). The data obtained from DSC have been applied for the calculation and comparison of the kinetic parameters of AP decomposition process through a model-free approach. The obtained kinetic parameters have been used to predict the reaction rate and progress of AP with Cu₂O cubes under isothermal conditions or at temperature mode corresponding to real climate changes.     

Ultrasound assisted two-stage biodiesel synthesis from non-edible Schleichera triguga oil using heterogeneous catalyst: Kinetics and thermodynamic analysis

Present work deals with the ultrasound-assisted biodiesel production from low cost, substantial acid value kusum (Schleichera triguga) oil using a two-step method of esterification in presence of acid (H₂SO₄) catalyst followed by transesterification using a basic heterogeneous barium hydroxide (Ba(OH)₂) catalyst. The initial acid value of kusum oil was reduced from 21.65 to 0.84 mg of KOH/g of oil, by acid catalyzed esterification with 4:1 methanol to oil molar ratio, catalyst concentration 1% (v/v), ultrasonic irradiation time 20 min at 40 °C. Then, Ba(OH)₂ concentration of 3% (w/w), methanol to oil molar ratio of 9:1, ultrasonic irradiation time of 80 min, and temperature of 50 °C was found to be the optimum conditions for transesterification step and triglyceride conversion of 96.8% (wt) was achieved. This paper also examined the kinetics as well as the evaluation of thermodynamic parameters for both esterification and transesterification reactions. The lower value of activation energy and higher values of kinetic constants indicated a fast rate of reaction, which could be attributed to the physical effect of emulsification, in which the microturbulence generated due to radial motion of bubbles, creates an intimate mixing of the immiscible reactants causing the increase in the interfacial area, giving faster reaction kinetics. The positive values of Gibbs-free energy (ΔG), enthalpy (ΔH) and negative value of entropy (ΔS) revealed that both the esterification and transesterification were non-spontaneous, endothermic and endergonic reactions. Therefore, the present work has not only established the escalation obtained due to ultrasonication but also exemplified the two-step approach for synthesis of biodiesel from non-edible kusum oil based on the use of heterogeneous catalyst for the transesterification step.