Sites of protonation and unimolecular fragmentation of protonated N-hydroxyphthalimide in the gas phase

The low energy collision-induced dissociation, linked scan techniques and isotopic labeling experiment were used to investigate the unimolecular fragmentation of protonated N-hydroxyphthalimide under electron impact and chemical ionization conditions. It was found that this compound shows an unusual reactivity towards protonation. Two possible sites of protonation have been proposed to explain the corresponding fragmentation processes, one is that the protonation takes place on the oxygen atom of hydroxyl group, resulting in the loss of water and the other is the formation of an intermediary proton-bound complex in the fragmentation process, giving rise to the fragment ions of m/z 133 and m/z 135. The results show both cases are coexistence in the fragmentations of protonated N-hydroxyphthalimide, and the unimolecular fragmentation pathways are available.

THERMAL-DECOMPOSITION PROCESSES OF SOME ELECTRICALLY CONDUCTING POLYMERS INVESTIGATED BY DIRECT PYROLYSIS MASS-SPECTROMETRY

Thermal decomposition processes of poly(thio-1,4-phenylene) (PPS), polythiophene (PT) and polyaniline (PAn) were investigated by direct pyrolysis EI or CI mass spectrometry (DPMS). They can provide up to heptemer pyrolynates and give some structure properties. The results indicate that the thermal degradation all undergoes in radical decomposition, PPS pyrolyzes into linear and cyclic oligmers, but PT and PAn pyrolyze only into linear oligmers.

Ethylene polymerization with porous polystyrene spheres supported Cp2ZrCl2 catalyst

A catalyst with porous polystyrene beads supported Cp2ZrCl2 was prepared and tested for ethylene polymerization with methylaluminoxane as a cocatalyst. By comparison, the porous supported catalyst maintained higher activity and produced polyethylene with better morphology than its corresponding solid supported catalyst. The differences between activities of the catalysts and morphologies of the products were reasonably explained by the fragmentation processes of support as frequently observed with the inorganic supported Ziegler-Natta catalysts. Investigation into the distribution of polystyrene in the polyethylene revealed the fact that the porous polystyrene supported catalyst had undergone fragmentation during polymerization.

Structure of [C8H7](+) and intramolecular proton transfer reactions in 3-phenyl-1-butyn-3-ol by MS/MS technique

The electron impact mass spectrum (EIMS) of 3-phenyl-1-butyn-3-ol was reported in this paper. Collision-induced dissociation (CID) was used to study the gas phase ion structure of [C8H7](+) formed by the fragmentation of ionized 3-phenyl-1-butyn-3-ol, and that it has the same structure as m/z 103 ions generated by cinnamic acid and alpha-methylstyrene. Deuterium labelling, metastable ion (MI) and CID experimental results indicate the formation of m/z 103 ion resulting from molecular ion of 3-phenyl-1-butyn-3-ol, which is a stepwise procedure via twice proton transfers, rather than concerted process during the successive elimination of methyl radical and neutral carbon monoxide accompanying hydrogen transfer. Moreover, in order to rationalized these fragmentation processes, the bimolecular proton bound complex between benzyne and acetylene intermediate has been proposed.

Characteristic Dimensionless Numbers in Multi-Scale and Rate-Dependent Processes

For this sake, the macroscopic equations of mechanics and the kinetic equations of the microstructural transformations should form a unified set that be solved simultaneously. As a case study of coupling length and time scales, the trans-scale formulation

Effects of heat-treatment processes on the electroless Ni-B coating and its natural aging mechanism

A Ni-B coating was prepared with EN using potassium borohydride reducing agent. The as-plated micro-structure of the coating was confirmed from XRD to be a mixture of amorphous and supersaturated solid solution. Three kinds of phase transformation were observed from the DSC curve. Different from the previous works, the formation of Ni4B3 and Ni2B was found during some transformation processes. The key factors which influence the variation of micro-hardness and micro-structure in deposits are the formation, the size and amount of Ni3B, Ni4B3 and Ni2B. Aging of the deposits treated under some heat treatment conditions occurred at room temperature. Changes of the micro-hardness indicated aging phenomena evidently. the natural aging phenomena are concerned with various kinds of decomposition of borides, especially with Ni4B3 phase. The extent of natural aging depends on the formation and the quantity of Ni(4)B3 and Ni2B.

Partial-Dislocation-Mediated Processes in Nanocrystalline Ni with Nonequilibrium Grain Boundaries

The partial-dislocation-mediated processes have so far eluded high-resolution transmission electron microscopy studies in nanocrystalline nc Ni with nonequilibrium grain boundaries. It is revealed that the nc Ni deformed largely by twinning instead of extended partials. The underlying mechanisms including dissociated dislocations, high residual stresses, and stress concentrations near stacking faults are demonstrated and discussed.

Predictions for Partial-Dislocation-Mediated Processes in Nanocrystalline Ni by Generalized Planar Fault Energy Curves: An Experimental Evaluation

Generalized planar fault energy (GPFE) curves have been used to predict partial-dislocation-mediated processes in nanocrystalline materials, but their validity has not been evaluated experimentally. We report experimental observations of a large quantity of both stacking faults and twins in nc Ni deformed at relatively low stresses in a tensile test. The experimental findings indicate that the GPFE curves can reasonably explain the formation of stacking faults, but they alone were not able to adequately predict the propensity of deformation twinning.

Wave dynamic processes induced by a supersonic projectile discharging from a shock tube

A numerical study on wave dynamic processes occurring in muzzle blast flows, which are created by a supersonic projectile released from the open-end of a shock tube into ambient air, is described in this paper. The Euler equations, assuming axisymmetric flows, are solved by using a dispersion-controlled scheme implemented with moving boundary conditions. Three test cases are simulated for examining friction effects on the muzzle flow. From numerical simulations, the wave dynamic processes, including two blast waves, two jet flows, the bow shock wave and their interactions in the muzzle blasts, are demonstrated and discussed in detail. The study shows that the major wave dynamic processes developing in the muzzle flow remain similar when the friction varies, but some wave processes, such as shock-shock interactions, shock-jet interactions and the contact surface instability, get more intensive, which result in more complex muzzle blast flows.

Wave Dynamic Processes in Cellular Detonation Reflection from Wedges

When the cell width of the incident detonation wave (IDW) is comparable to or larger than the Mach stem height, self-similarity will fail during IDW reflection from a wedge surface. In this paper, the detonation reflection from wedges is investigated for the wave dynamic processes occurring in the wave front, including transverse shock motion and detonation cell variations behind the Mach stem. A detailed reaction model is implemented to simulate two-dimensional cellular detonations in stoichiometric mixtures of H (2)/O (2) diluted by Argon. The numerical results show that the transverse waves, which cross the triple point trajectory of Mach reflection, travel along the Mach stem and reflect back from the wedge surface, control the size of the cells in the region swept by the Mach stem. It is the energy carried by these transverse waves that sustains the triple-wave-collision with a higher frequency within the over-driven Mach stem. In some cases, local wave dynamic processes and wave structures play a dominant role in determining the pattern of cellular record, leading to the fact that the cellular patterns after the Mach stem exhibit some peculiar modes.

A coupling model for terrestrial processes in arid areas and its application

In this paper, the importance of investigation on terrestrical processes in arid areas for mankind's living environment protection and local economy development as well as its present state of the art are elucidated. A coupling model, which evaluates heat, mass, momentum and radiative fluxes in the SPAC system, is developed for simulating microclimate over plant and bare soil. Especially, it is focussed on the details of turbulence transfer. For illustration, numerical simulation of the water-heat exchange processes at Shapotou Observatory, GAS, Ninxia Province are conducted, and the computational results show that the laws of land-surface processes are rather typical in the arid areas.

Cross-relaxation dynamics on anomalous saturation processes in low pressure supersonic cw HF chemical laser amplifier

It is assumed that both translational and rotational nonequilibrium cross-relaxations play a role simultaneoulsy in low pressure supersonic cw HF chemical laser amplifier. For two-type models of gas flow medium with laminar and turbulent flow diffusion mixing, the expressions of saturated gain spectrum are derived respectively, and the numerical calculations are performed as well. The numerical results show that turbulent flow diffusion mixing model is in the best agreement with the experimental result.

Two Bifurcation Transition Processes in Floating Half Zone Convection of Larger Prandtl Number Fluid

Processes of the onset oscillation in the thermocapillaxy convection under the Earth's gravity are investigated by the numerical simulation and experiments in a floating half zone of large Prandtl number with different volume ratio. Both computational and experimental results show that the steady and axisymmetric convection turns to the oscillatory convection of m=1 for the slender liquid bridge, and to the oscillatory convection before a steady and 3D asymmetric state for the case of a fat liquid bridge. It implies that, there are two critical Marangoni numbers related, respectively, to these two bifurcation transitions for the fat liquid bridge. The computational results agree with the results of ground-based experiments.

Progress In Modeling Of Fluid Flows In Crystal Growth Processes

Modeling of fluid flows in crystal growth processes has become an important research area in theoretical and applied mechanics. Most crystal growth processes involve fluid flows, such as flows in the melt, solution or vapor. Theoretical modeling has played an important role in developing technologies used for growing semiconductor crystals for high performance electronic and optoelectronic devices. The application of devices requires large diameter crystals with a high degree of crystallographic perfection, low defect density and uniform dopant distribution. In this article, the flow models developed in modeling of the crystal growth processes such as Czochralski, ammonothermal and physical vapor transport methods are reviewed. In the Czochralski growth modeling, the flow models for thermocapillary flow, turbulent flow and MHD flow have been developed. In the ammonothermal growth modeling, the buoyancy and porous media flow models have been developed based on a single-domain and continuum approach for the composite fluid-porous layer systems. In the physical vapor transport growth modeling, the Stefan flow model has been proposed based on the flow-kinetics theory for the vapor growth. In addition, perspectives for future studies on crystal growth modeling are proposed. (c) 2008 National Natural Science Foundation of China and Chinese Academy of Sciences. Published by Elsevier Limited and Science in China Press. All rights reserved.

Comparison Of The Quasi-Static Method And The Dynamic Method For Simulating Fracture Processes In Concrete

Concrete is heterogeneous and usually described as a three-phase material, where matrix, aggregate and interface are distinguished. To take this heterogeneity into consideration, the Generalized Beam (GB) lattice model is adopted. The GB lattice model is much more computationally efficient than the beam lattice model. Numerical procedures of both quasi-static method and dynamic method are developed to simulate fracture processes in uniaxial tensile tests conducted on a concrete panel. Cases of different loading rates are compared with the quasi-static case. It is found that the inertia effect due to load increasing becomes less important and can be ignored with the loading rate decreasing, but the inertia effect due to unstable crack propagation remains considerable no matter how low the loading rate is. Therefore, an unrealistic result will be obtained if a fracture process including unstable cracking is simulated by the quasi-static procedure.