Flame Temperature Effect on the Structure of SiC Nanoparticles Grown by Laser Pyrolysis

Small SiC nanoparticles (10 nm diameter) have been grown in a flow reactor by CO₂ laser pyrolysis from a C₂H₂ and SiH₄ mixture. The laser radiation is strongly absorbed by SiH₄ vibration. The energy is transferred to the reactive medium and leads to the dissociation of molecules and the subsequent growth of the nanoparticles. The reaction happens with a flame. The purpose of the experiments reported in this paper is to limit the size of the growing particles to the nanometric scale for which specific properties are expected to appear. Therefore the effects of experimental parameters on the structure and chemical composition of nanoparticles have been investigated. For a given reactive mixture and gas velocity, the flame temperature is governed by the laser power. In this study, the temperature was varied from 875°C to 1100°C. The chemical analysis of the products indicate that their composition is a function of the temperature. For the same C/Si atomic ratio in the gaseous phase, the C/Si ratio in the powder increases from 0.7 at 875°C up to 1.02 at 1100°C, indicating a growth mechanism limited by C₂H₂ dissociation. As expected, X-ray diffraction has shown an improved crystallisation with increasing temperature. Transmission electron microscopy observations have revealed the formation of 10 nm grains for all values of laser power (or flame temperature). These grains appear amorphous at low temperature, whereas they contain an increasing number of nanocrystals (2 nm diameter) when the temperature increases. These results pave the way to a better control of the structure and chemical composition of laser synthesised SiC nanoparticles in the 10 nm range.     

Crystallization-induced asymmetric transformation. Application to conjugate addition of benzylamine to amides of benzoylacrylic acid

Adducts of the conjugate addition of benzylamine to enantiopure amides of aroylacrylic acid possess high enantiomeric and diastereomeric purity. A high degree of stereoselectivity has been achieved by means of crystallization-induced asymmetric transformation. A practical synthesis leading to dipeptides containing homophenylalanine is depicted.     

Collisional Relaxation of Luminescence Anisotropy in Rarefied Gases in the Condensed Phase

The orientational relaxation of optically induced anisotropy in rarefied gases and at a damped rotation has been investigated. It has been found that the anisotropy relaxation in rarefied gases is described by a reduced kinetic equation depending only on free rotation integrals. The behavior of the integral anisotropy of luminescence for free symmetric and asymmetric top molecules has been elucidated. The law of luminescence depolarization has been obtained for asymmetric top molecules in the Gordon J-diffusion model. It represents the sum of two Stern–Volmer-type dependences, whose relative contribution is determined by the orientation of the dipole moments of transitions with absorption and emission of light in the molecular coordinate system and by the principal moments of inertia of the molecular top. It has been established that in the limit of a strongly damped rotation, kinetic equations of the general form reduce to equations of rotational diffusion. A number of modified diffusion equations correctly describing the contribution of inertial effects to the orientational relaxation of anisotropy have been obtained.     

Interpretive approach to collective effects of electrons in multicenter problems

Interpretive theoretical tools prove valuable in guiding the analysis of experiments in the realm of atomic clusters. Here, we review basic elements of an analytic approach that makes it possible to find and visualize the effective electrostatic potential and Coulomb correlations in multicenter problems. To illustrate the utility of these concepts we apply them to exploring molecular-doped metallic clusters. This study is aiming at a systematic, visual assessment of changes induced in screening, Coulomb correlation and effective potential by varying the charge of the electronegative impurity and its position in the cluster cage.     

Potts model on complex networks

We consider the general p-state Potts model on random networks with a given degree distribution (random Bethe lattices). We find the effect of the suppression of a first order phase transition in this model when the degree distribution of the network is fat-tailed, that is, in more precise terms, when the second moment of the distribution diverges. In this situation the transition is continuous and of infinite order, and size effect is anomalously strong. In particular, in the case of p = 1, we arrive at the exact solution, which coincides with the known solution of the percolation problem on these networks.Received: 3 December 2003, Published online: 17 February 2004PACS: 05.10.-a Computational methods in statistical physics and nonlinear dynamics - 05.40.-a Fluctuation phenomena, random processes, noise, and Brownian motion - 05.50. + q Lattice theory and statistics (Ising, Potts, etc.) - 87.18.Sn Neural networks     

On the evaluation of the nonisothermal kinetic parameters of (GeS2)0.3(Sb2S3)0.7 crystallization using the IKP method

The isoconversional method suggested by Friedman and the invariant kinetic parameters method (IKP) were used in order to examine the kinetics of the nonisothermal crystallization of (GeS₂)_0.3(Sb₂S₃)_0.7. The objective of the paper is to show the usefulness of the IKP method both for determining the activation parameters as well as the model of the investigated process. It was shown that the kinetic triplet [(E, A, f(α), where E is the activation energy, A is the preexponential factor, and f(α) is the differential function of conversion], which results through the application of the IKP method, depends on the set of kinetic models considered. For different sets of kinetic models, proportional values of f(α) are obtained. A criterion for the selection of this set, the use of which lead to the true kinetic triplet corresponding to the analyzed process (E = 163.2 kJ mol^?1; A = 2.47 × 10¹² min^?1 and the Avrami‐Erofeev model, A_m, for m = 2.5–2.6 was suggested. © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 36: 309–315, 2004     

Pervaporation of benzene/cyclohexane mixtures using ion-exchange membrane containing copper ions

The sorption, diffusion, and pervaporation (PV) properties of benzene/cyclohexane (Bz/Cx) mixtures on cation-exchange membranes containing copper ions (Cu(II)) were investigated. The equilibrium sorption isotherms of pure vapors in the membranes and the partial solubility of binary solutions in the membranes were described using the UNIQUAC model. The τ_iM and τ_Mi values were 0.978 and 0.591 for Bz, and 0.922 and 0.475 for Cx. The transient regimes of vapor sorption were employed to calculate the concentration-dependent diffusion coefficients. Long’s model sufficiently explained the diffusivity of Bz and Cx in the membranes. The pre-exponential factors were 3×10⁻¹³ m²/s and the plasticization factors were 3.0 and 3.6 for Bz and Cx, respectively. Excellent agreement was found with the experimental results applying the solubility and diffusivity data to simulate the pervaporation performance (flux and selectivity) using the modified Maxwell–Stefan equation. The membrane containing Cu(II) demonstrates better facilitating capability for Bz transport than that with Na(I), mainly due to its preferential sorption property toward Bz. Replacing Na(I) with Cu(II) into a Neosepta membrane resulted in better separation efficiency and higher Bz flux throughout the entire Bz concentration range.