Natural As-Sb alloys: texture types, thermal behaviour and mechanism of formation

1987 ◽  
Vol 51 (360) ◽  
pp. 295-304 ◽  
Author(s):  
G. P. Bernardini ◽  
C. Cipriani ◽  
F. Corsini ◽  
G. G. T. Guarini ◽  
G. Mazzetti ◽  
...  

AbstractThe thermal behaviour and mechanism of formation of different texture types of intergrown As-Sb alloys have been studied by DTA and annealing experiments performed on natural samples. The constant composition of the As-rich component and of the stibarsen in the intergrowths, and the large compositional range of the homogeneous solid solution obtained after heating in the DTA cycle, have been established using the linear relationship between cell volume and composition. The high-temperature features detected in the DTA studies of the natural samples confirm previously published phase relations for the synthetic As-Sb system. The low-temperature features can be correlated with the homogenization reaction which leads to the formation of a complete solid solution. Study of TTT plots based on the annealing experiments clearly shows that a diffusion mechanism is involved in the homogenization reaction. This has been further substantiated by fitting the experimental data to kinetic equations for diffusion-controlled processes. The kinetic parameters evaluated from the ending time for the 520, 480, and 420 °C annealing experiments, using both the Arrhenius and the transition state theory formalisms, suggests a rather rigid activated complex for the rate-determining step of the process.

2011 ◽  
Vol 172-174 ◽  
pp. 321-330 ◽  
Author(s):  
Maylise Nastar

A Self-Consistent Mean Field (SCMF) kinetic theory including an explicit description ofthe vacancy diffusion mechanism is developed. The present theory goes beyond the usual local equi-librium hypothesis. It is applied to the study of the early time spinodal decomposition in alloys. Theresulting analytical expression of the structure function highlights the contribution of the vacancydiffusion mechanism. Instead of the single amplification rate of the Cahn-Hillard linear theory, thelinearized SCMF kinetic equations involve three constant rates, first one describing the vacancy re-laxation kinetics, second one related to the kinetic coupling between local concentrations and paircorrelations and the third one representing the spinodal amplification rate. Starting from the same va-cancy diffusion model, we perform kineticMonte Carlo simulations of a Body Centered Cubic (BCC)demixting alloy. The resulting spherically averaged structure function is compared to the SCMF pre-dictions. Both qualitative and quantitative agreements are satisfying.


2017 ◽  
Vol 8 (1) ◽  
Author(s):  
Milesa Ž. Srećković ◽  
Andrei A. Ionin ◽  
Aco J. Janićijević ◽  
Aleksandar R. Bugarinović ◽  
Stanko M. Ostojić ◽  
...  

During six decades of quantum electronics, a vast majority of new types of quantum generators have been developed. Although the principle of population inversion has united different ranges of electromagnetic spectra (and respective quantum generators), the existence of the title laser without the population inversion, makes that the exception had confirmed the rule, i. e. that this title deserves to be discussed further. Developing of formalisms describing the operation of quantum generators, by now have produced several approaches, which must have a quantum mechanics base. For the practical reasons, negative coefficient of absorption is acquired using classic electromagnetics as well, however for the population purposes, quantum representation must be entered. A few levels of formalisms will be set in this paper, linked to quantum generators accenting the optical portion of the spectra. The lowest level descriptions are based on lumped circuits. This could be expanded to equivalents of other physical problems, using program packages developed for the electrical engineering application purposes (Spice, etc.). Schematics are defined at the macro as well as micro equivalent levels (atomic – electronic levels). The kinetic equations with simpler approach will be considered as well as simplified laser equations based on quantum/ semi-quantum approach. The use of Fourier analysis or other appropriate transformations leads to formulating the main five laser equations which serve as the base for various working regimes of quantum generators and amplifiers (free generation regime, Q switch, synchronization, operation with filters, two modes regime, regime with losses, etc.). The Lyapunov stability theorem has to be included here, etc. For some of the chosen types of quantum generator, analytical modeling will be analyzed as well as the results of program packages developed for the lasers dynamics, regimes and parameters. The systems pumped with electronic beams (relativistic) will be considered and the nuclear physics statements discussed which must be included at the beginning, in order to consider further necessary parts of the condensed – solid state theory and laser techniques, after slowing down towards thermal energies. Existing program packages provide fast modeling and visualization of laser energy distribution, temperature, modes, etc. in active material with or without the resonator. A modeling will be performed for the specified geometries and a temperature distribution in active material will be captured during operation of a chosen laser system. Different pump geometries will be compared. Contemporary lasers with the shortest existing pulse durations demand new formalisms. Areas of nonlinear optics and quantum electrody-namics, Glauber states and similar, are areas that have to be included. Two main formalisms thermodynamical and quantum mechanical with transition probabilities using perturbation methods and secondary quantization naturally had to be complemented if the Brillouin, Raman, Compton, soliton, fiber and other lasers are included more generally.


1986 ◽  
Vol 51 (11) ◽  
pp. 2473-2480 ◽  
Author(s):  
Jaroslav Nývlt ◽  
Věra Šnoblová ◽  
Miloslav Karel

The three-component system CuSO4-ZnSO4-H2O forms three types of solid solution. Metastable zone widths measured for selected solution compositions at two cooling rates were used to calculate the kinetic parameters of nucleation. The rate of crystal growth was measured by the fluidized bed method. The results show that the addition of Zn2+ to a solution of CuSO4 increases both the nucleation and crystal growth rates, whereas Cu2+ added to a solution of ZnSO4 retards the nucleation rate and slightly increases the rate of crystal growth. The nucleation rate (the metastable zone width) is substantially more sensitive to the addition of a second component than is the rate of crystal growth. The crystal growth rate is controlled by a diffusion mechanism.


2019 ◽  
Vol 20 (21) ◽  
pp. 5420
Author(s):  
Xuan Li ◽  
Yixiang Gao ◽  
Chenpeng Zuo ◽  
Siyuan Zheng ◽  
Fei Xu ◽  
...  

Benzofuran (BF), benzothiophene (BT), indole (IN), dibenzofuran (DBF), dibenzothiophene (DBT), and carbazole (CA) are typical heterocyclic aromatic compounds (NSO-HETs), which can coexist with polycyclic aromatic hydrocarbons (PAHs) in combustion and pyrolysis conditions. In this work, quantum chemical calculations were carried out to investigate the formation of DBF, DBT, and CA from the reactions of BF, BT, and IN with a cyclopentadienyl radical (CPDyl) by using the hybrid density functional theory (DFT) at the MPWB1K/6-311+G(3df,2p)//MPWB1K/6-31+G(d,p) level. The rate constants of crucial elementary steps were deduced over 600−1200 K, using canonical variational transition state theory with a small-curvature tunneling contribution (CVT/SCT). This paper showed that the production of DBF, DBT, and CA from the reactions of BF, BT, and IN with CPDyl involved six elementary steps: the addition reaction, ring closure, the first H shift, C–C cleavage, the second H shift, and elimination of CH3 or H. The cleavage of the C–C bond was regarded as the rate-determining step for each pathway due to the extremely high barrier. The 1-methyl substituted products were more easily formed than the 4-methyl substituted products. The main products were DBF and 1-methyl-DBF, DBT and 1-methyl-DBT, and CA and 1-methyl-CA for reactions of BF, BT, and IN with CPDyl, respectively. The ranking of DBF, DBT, and CA formation potential was as follows: DBT and methyl-DBT formation > DBF and methyl-DBF formation > CA, and methyl-CA formation. Comparison with the reaction of naphthalene with CPDyl indicated that the reactions of CPDyl attacking a benzene ring and a furan/thiophene/pyrrole ring could be inferred to be comparable under high temperature conditions.


1997 ◽  
Vol 481 ◽  
Author(s):  
Y. Le Bouar ◽  
A. G. Khachaturyan

ABSTRACTThe mechanism of formation of a chessboard-like structure observed during coherent decomposition in alloys with several orientation variants of the precipitate phase is considered. It is based on the accommodation of coherency strain achieved by spatial rearrangement of orientation variants of the precipitate phase in an optimal pattern. The computational model of precipitation of the ordered tetragonal phase, based on the continuum stochastic field kinetic equations for the composition and lro parameters profiles, is formulated. Its numerical solution describes the spatial and temporal evolution of the microstructure, from nucleation to coarsening. It is shown that the chessboard-like microstructure is produced by strain-driven, self-assembling of orientation variants of the precipitate phase, faceted by the planes normal to the elastically soft directions. Coarsening of such microstructures occurs by consequent disappearance of entire rows of “tiles” in the pattern.


1973 ◽  
Vol 26 (9) ◽  
pp. 1935 ◽  
Author(s):  
BI Cruikshank ◽  
NR Davies

No entry of deuterium into olefin could be detected as a result of isomerization of allylbenzene in the presence of palladium(II) catalysts in CH3CO2D or CH3OD. The deuterium isotope effect on the rate of isomerization was found to be high in the case of CH3CO2D, but slight in the case of CH3OD. In the case of catalysis by rhodium complexes, entry of deuterium into olefin occurs in CH3OD but not in CH3CO2D. Isotope effects parallel those observed with palladium(II). The isomerization of PhCD2CH2CH=CH2 catalysed by palladium(II) results in a near-to-random distribution of deuterium throughout the side chain. The results are consistent with a hydrido-π-olefin complex mechanism of isomerization. Differences between catalysis by palladium(II) and rhodium(III) are discussed in terms of possible differences in the mechanism of formation of the active catalyst. In the case of palladium it is concluded that a relatively rapid rate of σ-π interchange and hence of double bond shift occurs within the equilibrium system of catalyst and olefin, and that exchange of olefin with the substrate constitutes the slower, rate-determining step. The behaviour of platinum(II) is generally similar to that of palladium(II) but is only effective at higher temperatures.


1995 ◽  
Vol 308 (1) ◽  
pp. 305-311 ◽  
Author(s):  
S Yagisawa

A comprehensive theory for relating free-energy profiles to kinetic equations of enzyme reactions has been developed. It enables expression of the overall rate and the concentrations of reaction intermediates in terms of the heights of peaks in free-energy profiles for various reactions. The reactions include consecutive reactions with intermittent irreversible steps, those with dead-end side reactions and completely reversible reactions. The usefulness of the theory is shown by analysis of a single-substrate reaction, a reaction with a covalent intermediate, and product inhibition in a two-substrate reaction, in which kinetic parameters such as Vmax and Km are related to the peak heights in free-energy profiles. The paper refers also to the concept of rate-determining step (RDS) and shows the utility of a related concept rate-determining zone (RDZ) which indicates the reaction steps between the main intermediate and the RDS. The concept of RDZ is useful for resolving confusion related to the concept of RDS. It should be emphasized that the present approach is applicable only to linear reactions.


2021 ◽  
Vol 2021 (2) ◽  
pp. 63-71
Author(s):  
G. S. Oleynik ◽  
◽  
A. V. Kotko ◽  

Results of an investigation by scanning electron microscopy methods of the microstructure of self-reinforced aluminum nitride obtained on the basis of aluminum nitride powder and containing 3 mass.% oxygen by plasma-chemical synthesis in the temperature range 1700-2000 °C are presented. Initial aluminum nitride was represented by the wurtzite (2H) phase. Samples were obtained by free sintering in a nitrogen atmosphere. It was established that, during sintering of AlN in the indicated temperature range, three microstructural types of the material and six types of interfaces (three types of intergranular and three types of intragranular ones) formed. The features of the microstructure of the materials are fully determined by the development of intergranular crystal-oriented polytype transitions of 2H AlNmultilayer polytypes (MP) in sintering. The sequence of successive structural transformations that determine the development of polytype transitions was established. 1. Formation of initial 2H AlN grains of the solid solution 2H AlN-O. The substitution of nitrogen by oxygen takes place. 2. The development of isomorphous delamination of the solid solution in every grain with the precipitation of an interlayer enriched in oxygen. 3. In interlayers, polytypes consisting of a series of polytypes with different number of layers (MP) form. Such an interlayer has developed base surfaces and propagates from one boundary to another in the grain, which determines the formation of a special structural state of fragments of boundaries, that border interlayers in the direction <hk0>. 4. The high mobility of the indicated fragments of boundaries determines their break-off from the common boundary and formation of a grain nucleus of anisometric (plate-like) shape. This process begins already at a sintering temperature Tsint. = 1800 °C, and, at Tsint. = 2000 °C, polycrystals practically entirely consist of grains of plate-like shape. In this case, with increase in the sintering temperature, the aspect ratio (the length-to-width ratio) of such grains rises. Keywords: aluminum nitride, polytype transformations, grains, microstructure, boundaries, self-reinforcement.


1990 ◽  
Vol 5 (10) ◽  
pp. 2177-2183 ◽  
Author(s):  
S. Deevi ◽  
Z. A. Munir

The mechanism of formation of titanium nitride by the self-propagating high-temperature synthesis was investigated. Samples were quenched in liquid argon at different stages of the reaction and analyzed by x-ray diffraction and electron microprobe methods. A mechanism is proposed in which the propagation of the reaction wave results in the formation of a thin surface layer of TiN and an unsaturated solid solution. The layer then dissolves to form a solid solution of nitrogen in titanium and then re-forms with continued reaction. On the basis of phase equilibria and diffusion information, an analysis is made in which the feasibility of the proposal mechanism is demonstrated.


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