Thermodynamical modeling of silicon carbide synthesis in thermal plasma

The synthesis process of solid SiC in thermal plasma was investigated theoretically by computing the equilibrium composition of the gas mixtures involving silicon and carbon in the presence of argon and hydrogen at various silicon/carbon amounts and at two different total pressures in the system, in the temperature range between 1000 and 6000 K. Use is made of the fact that a thermal plasma, by definition, is a plasma in (local) thermodynamical equilibrium, which makes possible the theoretical determination of its equilibrium composition at definite temperature by employing Gibbs free energy data for the compounds present in the system. From the calculated compositions of the investigated gas systems the temperature-composition phase diagrams were obtained. Using these data the temperature zones with saturated and/or oversaturated vapour of SiC as well as of Si and C were determined and the possibility of the formation of SiC in the solid state via different reaction routes was analyzed This revised version was published online in July 2006 with corrections to the Cover Date.     

Investigation of organosilicon radicals : I. Methylphenylsilane anion radicals

CNDO/2 calculations with an spd basis set have been carried out on methyl-phenylsilane anion radicals, and the calculated spin density values compared with the experimental hyperfine coupling constants. The CNDO method overestimates the role of d orbitals and the partial charges on hydrogen atoms attached to silicon atom. The partial charge distribution and the carbonsilicon bond order in the anion radicals and the corresponding neutral molecules are discussed. The equilibrium carbonsilicon bond distance in the trimethylphenylsilane molecule and corresponding anion radical have also been investigated.     

Analyzing the phase composition of Si-B and Si-B-Ti alloys based on silicon

An interally consistent analysis of the available data on the conditions of the equilibrium of phases and thermodynamic properties of Si-B alloys based on silicon is performed. Phase equilibria in the Si-B-Ti system in the temperature and concentration regions of the existence of solid solution based on silicon are calculated using the obtained data. Conditions for the precipitation of titanium diboride from Si-B-Ti solid solution at 1523 K are found.     

Comprehension of the S(V)LS mechanism growth of silicon-based nanowires

A comprehensive thermodynamic assessment has been carried out on the Au–Si–O system involved in the growth mechanism of Silicon NanoWires (SiNW) via the solid–liquid–solid process. The driving force needed to trigger the SiNW precipitation is supersaturation of liquid alloy Au–Si. Our model demonstrates, for the first time, how and from where supersaturation is reached. Supersaturation is not due to the migration of silicon from the wafer as claimed by many researchers, but to the existence of SiO volatile species resulting from the metastable equilibrium SiO_{2, amorphous}/Si_wafer. More interesting is that the partial pressure P_SiO does impose an initial minimum radius of the first generation of nanowires in the range of 10 nm. After that, other generations of nanowires will grow due to the new metastable equilibrium SiO_{2, amorphous}/Si_nanowire.     

Thermodynamic Aspects of the Increased Thermal Stability of Silicon by Doping with Transition or Rare-earth Metals

The main reason of the degradation of silicon monocrystals at heating is a structural transformation connected with a partial transition of the diamond-like structure into the structure of white tin. The reason for this transformation being observed under high pressures is the appearance of stress zones at the boundaries of variously oriented crystal microvolumes due to heat expansion anisotropy. The high stress concentration in the microvolumes provides sufficient pressure for the indicated phase transformation which results in the observed degradation of the electrophysical properties of silicon. The prevention of the structural transformation is considered to be possible by doping of Si by transition or rare-earth metals which increases the interatomic energy and decreases the thermal expansion coefficient. The choice of the doping additions is based on the bonding energy and the charge density calculated for a system of non-polarised ionic radii. The technology to increase the thermal stability of silicon has been patented^#.     

Thermodynamic Aspects of the Increased Thermal Stability of Silicon by Doping with Transition or Rare-earth Metals

Summary. The main reason of the degradation of silicon monocrystals at heating is a structural transformation connected with a partial transition of the diamond-like structure into the structure of white tin. The reason for this transformation being observed under high pressures is the appearance of stress zones at the boundaries of variously oriented crystal microvolumes due to heat expansion anisotropy. The high stress concentration in the microvolumes provides sufficient pressure for the indicated phase transformation which results in the observed degradation of the electrophysical properties of silicon. The prevention of the structural transformation is considered to be possible by doping of Si by transition or rare-earth metals which increases the interatomic energy and decreases the thermal expansion coefficient. The choice of the doping additions is based on the bonding energy and the charge density calculated for a system of non-polarised ionic radii. The technology to increase the thermal stability of silicon has been patented^#. Patent of Russia, No 2094904, 13/10/1995     

Nanometer-scale wetting of the silicon surface by its equilibrium oxide

Despite the extremely broad technical applications of the Si/SiO2 structure, the equilibrium wetting properties of silicon oxide on silicon are poorly understood. Here, we produce new results in which a solid-state buffer method is used to systematically titrate oxygen activity about the Si/SiO2 coexistence value. The equilibrium morphology at the Si(001) surface over >8 decades of PO2 about coexistence is revealed to be a uniform sub-stoichiometric SiOx film of sub-nanometer thickness, coexisting with secondary island structures which coarsen with annealing time. A new thermodynamic method using chemical potential to stabilize and control surficial oxides in nanoscale devices is suggested.     

Influence of SiO2 on the Equilibrium in the Cu-Ni-Cu2O-NiO System

The equilibrium between a copper-nickel alloy and an oxide melt in the Cu₂O-NiO-SiO₂ system was studied experimentally. The distribution coefficients of nickel were determined as a function of the content of silicon dioxide, and the ratio of activity coefficients of nickel and copper oxides at 1300°C was found.     

Kinetics and rate-limiting mechanisms of dolomite dissolution at various CO_2 partial pressures

Techniques of rotating-disk and catalyst were used in investigating the kinetics of dolomite dissolution in flowing CO2-H2O system. Experiments run in the solutions equilibrated with various CO2 partial pressures (PCO2) from 30 to 100000 Pa. It shows that dissolution rates of dolomite are related with rotating speeds at conditions far from equilibrium. This was explained by modified diffusion boundary layer (DBL) model. In addition, the dissolution rates increase after addition of carbonic anhydrase (CA) to solutions, where the CA catalyzes CO2 conversion. However, great differences occur among various CO2 partial pressures. The experimental observations give a conclusion that the modified DBL model enables one to predict dissolution rates and their behaviour at various PCO2 with satisfactory precision at least far from equilibrium.     

Melt–Vapor Phase Diagram of the Te–S System

The values of partial pressure of saturated vapor of the constituents of the Те–S system are determined from boiling points. The boundaries of the melt–vapor phase transition at atmospheric pressure and in vacuum of 2000 and 100 Pa are calculated on the basis of partial pressures. A phase diagram that includes vapor–liquid equilibrium fields whose boundaries allow us to assess the behavior of elements upon distillation fractioning is plotted. It is established that the separation of elements is possible at the first evaporation–condensation cycle. Complications can be caused by crystallization of a sulfur solid solution in tellurium.     

A Generalized Formula to Predict the Direction of an Equilibrium Shift

A generalized formula to predict the direction of an equilibrium shift, , is presented, where ξ is the extent of the reaction, t is the characteristic variable to affect an equilibrium and f is the characteristic function whose partial differential with respect to ξ can be used as an equilibrium criterion. When the stable equilibrium of a thermodynamic system is disturbed on condition that f exhibits a minimum with respect to ξ, the equilibrium will shift in the direction to resist the increase of f if the disturbance make f increase; however, the equilibrium will shift in the direction to accelerate the decrease of f if the disturbance make f decrease to minimize f. On condition that f exhibits a maximum with respect to ξ, the equilibrium will shift in the direction to resist the decrease of f if the disturbance make f decrease; however, the equilibrium will shift in the direction to accelerate the increase of f if the disturbance make f increase to maximize f. On the other hand, Le Chatalier’s Principle is not consistent with the real situations under certain circumstances     

Comparative thermodynamic analysis of the binary system Bi−Sb

Results of the comparative thermodynamic analysis of the binary system Bi?Sb obtained by DTA measurements and predicting are presented in this paper. Activities, activity coefficients, partial and integral molar quantities for Bi and Sb at temperatures 973, 1073 and 1173 K in the investigated binary system Bi?Sb determined by DTA measurements and thermodynamic predicting are given. An excellent agreement between the experimental and predicted results is reached. Also, a phase diagram of the investigated system Bi?Sb obtained by DTA shows good agreement with literature and it can be concluded that DTA could be satisfactorily used for quantitative thermodynamic analysis of any binary system containing equilibrium between solid and liquid solutions. It was also determined that conclusion about linear dependence ofgKs constant for binary eutectic systems and systems with phase transformation is valid for binary system containing equilibrium between solid and liquid solutions too.     

Stabilization of methane hydrate by pressurization with He or N2 gas

The behavior of methane hydrate was investigated after it was pressurized with helium or nitrogen gas in a test system by monitoring the gas compositions. The results obtained indicate that even when the partial pressure of methane gas in such a system is lower than the equilibrium pressure at a certain temperature, the dissociation rate of methane hydrate is greatly depressed by pressurization with helium or nitrogen gas. This phenomenon is only observed when the total pressure of methane and helium (or nitrogen) gas in the system is greater than the equilibrium pressure required to stabilize methane hydrate with just methane gas. The following model has been proposed to explain the observed phenomenon: (1) Gas bubbles develop at the hydrate surface during hydrate dissociation, and there is a pressure balance between the methane gas inside the gas bubbles and the external pressurizing gas (methane and helium or nitrogen), as transmitted through the water film; as a result the methane gas in the gas bubbles stabilizes the hydrate surface covered with bubbles when the total gas pressure is greater than the equilibrium pressure of the methane hydrate at that temperature; this situation persists until the gas in the bubbles becomes sufficiently dilute in methane or until the surface becomes bubble-free. (2) In case of direct contact of methane hydrate with water, the water surrounding the hydrate is supersaturated with methane released upon hydrate dissociation; consequently, methane hydrate is stabilized when the hydrostatic pressure is above the equilibrium pressure of methane hydrate at a certain temperature, again until the dissolved gas at the surface becomes sufficiently dilute in methane. In essence, the phenomenon is due to the presence of a nonequilibrium state where there is a chemical potential gradient from the solid hydrate particles to the bulk solution that exists as long as solid hydrate remains.     

Thermodynamic model of solubility for CO2 in dimethyl sulfoxide

The solubility of CO₂ in dimethyl sulfoxide has been determined from 293.15 K to 313.15 K and partial pressure of CO₂ from 5.56 kPa to 18.2 kPa. Based on the data obtained from the CO₂ solubility experiments, a gas–liquid phase equilibrium model for CO₂–DMSO system was proposed. The average relative deviation between the experimental data of equilibrium partial pressure of CO₂ in DMSO and the corresponding data predicted by the model proposed is 4.85%, it shows that the agreement is satisfactory.     

A general method of calculating phase equilibria in a multicomponent system by means of a hill-climbing minimization procedure

A generalization of the method of calculating the state of equilibrium of a multicomponent system, using a hill-climbing minimization procedure, is proposed. Moreover, an original method of calculating values for partial free energies from the state of equilibrium has been made an essential part of the general schedule.     

Effects of antimony on the surface tension of molten silicon

The effect of antimony concentration (C(Sb)/mass%) on the surface tension of molten silicon has been determined with the sessile drop method in the temperature range from 1693 to 1773 K and in the range of the oxygen partial pressure, Po(2), in an Ar atmosphere from 10(-23) to 10(-21) MPa. The results show that the surface tension of molten silicon decreases with increasing Sb concentration in the range of C(Sb)<0.9 mass%, which indicates positive adsorption of Sb in molten silicon and can be fairly described with the Szyszkowski's equation. The maximum decrease rate of surface tension is about 65 mN m(-1) (mass% C(Sb))(-1), and the temperature coefficient of surface tension, (partial differential sigma/ partial differential T)C(Sb), increases with increasing C(Sb). The evaporation of the systems was only observed between the melting points of antimony (904 K) and silicon (1683 K), and the surface tension presents no dependence on measuring time above the melting point of silicon.     

Temperature and density measurements in a recombining argon plasma with diluent

Spectroscopic and callorimetric measurements of temperature arid number density have been made using a 50-kW radio-frequency inductively coupled plasma (RFICP) torch operated at atmospheric pressure with maximum temperatures and electron densities near 8,1000 K and 2 x 10²¹ m³, respectively These measurements enabled the determination o/ the stale o/ equilibrium and of the corresponding applicability of rarious diagnostic techniques in hoth a recombining argon plasma and a recombining plasma with hydrogen or nitrogen. Results indicate that the Pure argon plasma is well described by u partial equilibrium model in which the free and bound-excited electrons are in mutual equilibrium irespective of possible departures from equilibrium with the ground state. The addition of just tenths of a percent of either atomic Hydrogen or nitrogen, however, disturbs this partial equilibrium hr argon plasmas with electron densities roughly less than 10²¹ m³ such that only diagnostic techniques which are independent o/ partial equilibrium assumptions can be reliably implemented.     

Hydrolytic polymerization of caprolactam. II. Vapor–liquid equilibria

The system water–caprolactam–polymer at equilibrium is regarded as a solution consisting of two solvents (water and caprolactam) and one solute (polymer). The activities of water and caprolactam in equilibrium at 270°C in the range of 2–10 wt-% total water content have been determined by vapor-pressure measurements. Water shows large negative deviations from Raoult's law, as a consequence of the different size of water and polymer molecules. The partial molar free energies of mixing are compared with the expressions derived from the Flory-Huggins theory of polymer solutions; the results are not conclusive, but seem to indicate a qualitative agreement with the theory. The increase in vapor pressure during polymerization in sealed systems and the water dependence of the polycondensation equilibrium are discussed and explained in terms of water activity changes.     

Determination of polybutylene terephthalate polycondensation equilibrium constant using a batch reactor

The PBT polycondensation equilibrium constant at 255°C was determined using a batch reactor. Starting from a Polybutylene terephthalate (PBT) prepolymer having a degree of polymerisation of 12.7, equilibrium experiments were performed in the range of 1 to 50 mbar. The equilibrium degree of polymerisation (i) was determined indirectly using dilute solution viscometry of a solution of 1 weight % PBT in m - cresol. The degree of polymerisation of PBT obtained at equilibrium in the range of 1 to 50 mbar at 255°C as a function of the BDO partial pressure (mbar) could be expressed by: i = 111.47 − 86.18 exp(−1.14 equation/tex2gif-stack-1.gif). The equilibrium solubility of 1,4 butanediol (BDO) in the PBT melt was derived form the BDO partial pressure using the Flory - Huggins theory. The PBT polycondensation reaction equilibrium constant was related to the degree of polymerisation by the equation: in the range i = 26 − 100. The PBT polycondensation equilibrium constant at high degrees of polymerisation is in line with literature data and thermodynamics.     

Determination of the Three-dimensional Network Parameters of Radiation-Cured Siloxane Rubber Vulcanizates

The dependence of the concentration of network junction points, as determined by equilibrium swelling ratio, in an SKTV-shch siloxane rubber and siloxane rubber–silicon dioxide formulations on the dose of ionizing radiation was investigated. The radiation-chemical yield of crosslinking was shown to increase with increasing the filler content. This result was tentatively explained by reducing the molecular mobility of the rubber chains adsorbed at the surface of silicon dioxide particles.