Carbon dioxide/propylene oxide coupling reaction catalyzed by chromium salen complexes

A series of chromium/Schiff base complexes N,N'-bis(salicylidene)-1,2-phenylenediamino chromium(III) X were prepared and employed for the alternating copolymerization of carbon dioxide with racemic propylene oxide in the presence of (4-dimethylamino)pyridine. The effect of the complex structure and reaction conditions on the catalytic activity, the poly(propylene carbonate)/cyclic carbonate (PPC/PC) selectivity, and the polymer head-to-tail linkages was examined. The experiments indicated that N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-phenylenediamino chromium(III) (NO3) exhibited the highest PPC/PC selectivity as well as polymer head-to-tail linkages and N,N'-bis(3,5-dichlorosalicylidene)-1,2-phenylenediimino chromiu(III) (NO3) possessed the highest catalytic activity among these chromium/Schiff base complexes. The structure of the produced copolymer was characterized by the IR, H-1 NMR, and C-13 NMR measurements.

Effects of metal catalysts on CO2 gasification reactivity of biomass char

The effects of five metal catalysts (K, Na, Ca, Mg, and Fe) on CO2 gasification reactivity of fir char were studied using thermal gravimetric analysis. The degree of carbonization, crystal structure and morphology of char samples was characterized by X-ray diffractometry (XRD) and scanning electron microscopy (SEM). The CO2 gasification reactivity of fir char was improved through the addition of metal catalysts, in the order K>Na>Ca>Fe>Mg. XRD analysis indicated that Na and Ca improved the formation of crystal structure, and that Mg enhanced the degree of carbon structure ordering. SEM analysis showed that spotted activation centers were distributed on the surface of char samples impregnated with catalysts. Moreover, a loose flake structure was observed on the surface of both K-char and Na-char. Finally, the kinetic parameters of CO2 gasification of char samples were calculated mathematically.

Copolymerization of CO2 and propylene oxide under rare earth ternary catalyst: design of ligand in yttrium complex

Copolymerization of carbon dioxide and propylene oxide was carried out employing (RC6H4COO)(3)Y/glycerin/ZnEt2 (R = -H, -CH3, NO2, -OH) ternary catalyst systems. The feature of yttrium carboxylates (ligand, substituent and its position on the aromatic ring) is of great importance in the final copolymerization. Appropriate design of substituent and position of the ligand in benzoate-based yttrium complex can adjust the microstructure of aliphatic polycarbonate in a moderate degree, where the head-to-tail linkage in the copolymer is adjustable from 68.4 to 75.4%. The steric factor of the ligand in the yttrium complex is crucial for the molecular weight distribution of the copolymer, probably due to the fact that the substituent at 2 and 4-position would disturb the coordination or insertion of the monomer, lead the copolymer with broad molecular distribution. Based on the study of ultraviolet-visible spectra of the ternary catalyst in various solvents, it seems that the absorption band at 240-255 nm be closely related to the active species of the rare earth ternary catalysts.

Study on the Adsorption and Activation of NO and CO over Mixed Oxide Catalysts Containing Cu by Means of TPSR

Adsorption and activation of small molecules NO, CO and CO+ NO on LaSrCuO4, La2CuO4 and La1.7Th0.3CuO4 which are typical samples in the sence of nonstoichiometric oxygen(lambda) anrong the series of La2-x(SrTh)(x)CuO4 +/-lambda mixed oxide catalysts were studied by means of MS- TPD (TPSR ), XRD, chemical analysis and so on. It was shown that the adsorption amount of NO can be correlated with the content of oxygen vacancy while the types and strength of adsorption of NO could be related to the oxidation state of the metallic ion. It was also found that CO molecule was first converted into CO32- and then desorbed in the form of CO2 at high temperature during the adsorption and desorption of CO on the mixed oxide with oxygen vacancy. The fact that the profiles of TPD(TPSR) of NO in co-adsorption of NO+CO and in single NO adsorption are similar shows that the adsorption of NO molecule not only has some priority to that of CO but also is stronger than that of CO. It seems that the adsorption of NO plays a dominate role in the activation and decomposition of NO.

Numerical Study Of Heat Transfer Mechanism In Turbulent Supercritical Co2 Channel Flow

Direct numerical simulation (DNS) of supercritical CO2 turbulent channel flow has been performed to investigate the heat transfer mechanism of supercritical fluid. In the present DNS, full compressible Navier-Stokes equations and Peng-Robison state equation are solved. Due to effects of the mean density variation in the wall normal direction, mean velocity in the cooling region becomes high compared with that in the heating region. The mean width between high-and low-speed streaks near the wall decreases in the cooling region, which means that turbulence in the cooling region is enhanced and lots of fine scale eddies are created due to the local high Reynolds number effects. From the turbulent kinetic energy budget, it is found that compressibility effects related with pressure fluctuation and dilatation of velocity fluctuation can be ignored even for supercritical condition. However, the effect of density fluctuation on turbulent kinetic energy cannot be ignored. In the cooling region, low kinematic viscosity and high thermal conductivity in the low speed streaks modify fine scale structure and turbulent transport of temperature, which results in high Nusselt number in the cooling condition of the supercritical CO2.

The effect of thermal-activation on dislocation processes at an atomistic crack-tip

The effects of thermal activation on the dislocation emission from an atomistic crack tip are discussed, Molecular dynamics simulations at different constant temperatures are carried out to investigate the thermal effects. The simulated results show that the processes of the partial dislocation generation and emission are temperature dependent. As the temperature increases, the incipient duration of the partial dislocation nucleation becomes longer, the critical stress intensity factor for partial dislocation emission is reduced and, at the same loading level, more dislocations are emitted. The dislocation velocity moving away from the crack tip and the separations of partial dislocations are apparently not temperature dependent. The simulated results also show that, as the temperature increases, the stress distribution along the crack increases slightly. Therefore stress softening at the crack tip induced by thermal activation does not exist in the present simulation. A simple model is proposed to evaluate the relation of the critical stress intensity factor versus temperature. The obtained relation is in good agreement with our molecular dynamics results.

Numerical Study of Heat Transfer Mechanism in Turbulent Supercritical CO2 Channel Flow

Direct numerical simulation (DNS) of supercritical CO2 turbulent channel flow has been performed to investigate the heat transfer mechanism of supercritical fluid. In the present DNS, full compressible Navier-Stokes equations and Peng-Robison state equation are solved. Due to effects of the mean density variation in the wall normal direction, mean velocity in the cooling region becomes high compared with that in the heating region. The mean width between high-and low-speed streaks near the wall decreases in the cooling region, which means that turbulence in the cooling region is enhanced and lots of fine scale eddies are created due to the local high Reynolds number effects. From the turbulent kinetic energy budget, it is found that compressibility effects related with pressure fluctuation and dilatation of velocity fluctuation can be ignored even for supercritical condition. However, the effect of density fluctuation on turbulent kinetic energy cannot be ignored. In the cooling region, low kinematic viscosity and high thermal conductivity in the low speed streaks modify fine scale structure and turbulent transport of temperature, which results in high Nusselt number in the cooling condition of the supercritical CO2.

Microscopic Model Of Nano-Scale Particles Removal In High Pressure Co2-Based Solvents

A physical model is presented to describe the kinds of static forces responsible for adhesion of nano-scale copper metal particles to silicon surface with a fluid layer. To demonstrate the extent of particle cleaning, Received in revised form equilibrium separation distance (ESD) and net adhesion force (NAF) of a regulated metal particle with different radii (10-300 nm) on the silicon surface in CO2-based cleaning systems under different pressures were simulated. Generally, increasing the pressure of the cleaning system decreased the net adhesion force between spherical copper particle and silicon surface entrapped with medium. For CO2 + isopropanol cleaning system, the equilibrium separation distance exhibited a maximum at temperature 313.15 K in the Equilibrium separation distance regions of pressure space (1.84-8.02 MPa). When the dimension of copper particle was given, for example, High pressure 50 nm radius particles, the net adhesion force decreased and equilibrium separation distance increased with increased pressure in the CO2 + H2O cleaning system at temperature 348.15 K under 2.50-12.67 MPa pressure range. However, the net adhesion force and equilibrium separation distance both decreased with an increase in surfactant concentration at given pressure (27.6 or 27.5 MPa) and temperature (318 or 298 K) for CO2 + H2O with surfactant PFPE COO-NH4+ or DiF(8)-PO4-Na+. (C) 2008 Elsevier B.V. All rights reserved.

Laser intensity dependence of high-order harmonic generation from aligned CO2 molecules

We investigate experimentally the high-order harmonic generation from aligned CO2 molecules and demonstrate that the modulation inversion of the harmonic yield with respect to molecular alignment can be altered dramatically by fine-tuning the intensity of the driving laser pulse for harmonic generation. The results can be modeled by employing the strong field approximation including a ground state depletion factor. The laser intensity is thus proved to be a parameter that can control the high-harmonic emission from aligned molecules.

Local thermal fixing of a photorefractive LiNbO3 hologram by use of a CO2 laser

A real-time, in situ fixing method by use of heating with a CO2 laser beam is suggested for thermal fixing of a small local hologram in the bulk of a Fe:LiNbO3 photorefractive crystal. For heating up to 100 degrees C-200 degrees C a volume with a shape similar to that of the laser beam a heat-guiding technique is developed. On the basis of the heat-transfer equations, different heating modes with or without metal absorbers for heat guiding-obtained by use of a continuous or pulsed laser beam are analyzed. The optimal mode may be pulsed heating with absorbers. On this basis experiments have been designed and demonstrated. It is seen that the fixing process with CO2 laser beam is short compared with the process by use of an oven, and the fixing efficiency is quite high. (C) 1998 Optical Society of America.

Welding of Al alloy plates using a novel high-average-power pulsed CO2 laser

A novel high-average-power pulsed CO2 laser with a unique electrode structure is presented. The operation of a 5-kW transverse-flow CO2 laser with the preionized pulse-train switched technique results in pulsation of the laser power, and the average laser power is about 5 kW. The characteristic of this technique is switching the preionized pulses into pulse trains so as to use the small preionized power (hundreds of watts) to control the large main-discharge power (tens of kilowatts). By this means, the cost and the complexity of the power supply are greatly reduced. The welding of LF2, LF21, LD2, and LY12 aluminum alloy plates has been successfully achieved using this laser. (c) 2005 Society of Photo-Optical Instrumentation Engineers.