Intermetallic compound layer growth at the interface of solid refractory metals molybdenum and niobium with molten aluminum

The growth mechanisms and growth kinetics of intermetallic phases formed between the solid refractory metals Mo and Nb and molten aluminum have been studied for contact times ranging from 1 to 180 minutes at various temperatures in the range from 700 to 1100°C. The growth of the layers of the resulting intermetallic phases has been investigated under static conditions in a saturated melt and under dynamic conditions using forced convection in unsatured aluminum melts. The Nb/Al interfacial microstructure consisted of a single intermetallic phase layer, Al₃Nb, whereas two to four different phase layers were observed in the Mo/Al interface region, depending upon the operating temperature. It was found that, in a satured melt, the intermetallic phase growth process was diffusion-controlled. The parabolic growth constants of the first and second kind and integral values of the chemical diffusion coefficients over the widths of the phases were calculated for both Mo/Al and Nb/Al systems. It also was found that the AlNb₂ phase grew between the Nb and Al₃Nb phases after consumption of the saturated Al phase. Similarly, the AlMo₃ phase grew between the Mo and Al₈Mo₃ phases with diminishing of all the other existing compound phases. In an unsaturated melt, the intermetallic phase layer grows at the solid surface while, simultaneously, dissolution occurs at the solid/liquid interface. This behavior is compared to the growth mechanisms proposed in existing theories, taking into consideration that interaction occurs between neighboring phases. It was found that the intermetallic phase, Al₈Mo₃, adjoining the base metal, was not bonded strongly to the base metal Mo and was brittle; its hardness also was larger than that of the layer near the adhering aluminum and the adjacent phases.     

Interaction of niobium and tungsten monocarbides in molten copper

The chemical interaction of uncompacted monocarbide NbC and WC powders, which were taken at mass carbide ratios NbC: WC = 10: 1, 3: 1, 1: 1, and 1: 3 and a total carbide content of 20 wt %, in molten copper is studied at 1300°C. The primary and secondary phase transformations that result in the appearance and decomposition of an (Nb,W)C solid solution are analyzed. The activating role of low-frequency vibration is shown.     

Kinetics of oxide formation in liquid copper and silver

The process of formation of oxide phases in liquid copper and liquid silver has been studied by pumping oxygen into the liquid alloy with the use of a solid-electrolyte electrochemical cell. The oxygen potential at the electrolyte-metal interface is monitored simultaneously by the electrochemical cell. A wide range of effects were observed ranging from the very rapid formation of a layer of oxide at the electrolyte-metal interface to what appears to be homogeneous nucleation of the oxide in the metal. The results may help to explain some of the difficulties that sometimes have been observed in using this type of cell to measure the oxygen potential of a liquid metal. The results indicate that a supersaturation ratio of about 9 is necessary for homogeneous nucleation of iron oxide (most probably Fe₃O₄(s)) in liquid copper containing 0.01 to 0.07 pct iron. The interfacial tensionσ _{Cu-Fe 3}O₄ is calculated to be 0.74 J/m². In experiments with higher concentrations of deoxidant (0.2 pct Fe in Cu and 0.2 to 0.4 pct Ni in Ag) equilibrium precipitation of oxides apparently predominates over homogeneous nucleation for the experimental conditions employed. A mathematical model which partly explains the different effects observed is presented.     

Kinetics of interaction of tantalum disilicide with tantalum and other metals

The rate of growth of Ta₅Si₃ in the Ta?TaSi₂ system has been measured with good accuracy in the temperature range of 1150° to 1370°C (2100° to 2500°F) using couples consisting of dense wafers of the components. The isothermal growth is shown to be parabolic and the temperature dependence of the growth constant is given byk=5 exp (?77,000/RT) It has been shown that tantalum diffusion is negligible by comparison with silicon diffusion. The Ta₅Si₃ was found to exist in both tetragonal and hexagonal forms. A more limited investigation of silicon loss from TaSi₂ to W, Mo, Nb, Zr, Ti, and Re indicates that none of these is superior to tantalum in limiting the degradation of the tantalum disilicide. In most instances a layer of composition M₅Si₃ forms on the metal side of the couple.     

Reaction of a molten mixture of titanium,aluminum, and silicon oxides with hot-pressed silicon nitride

The formation temperature of a liquid phase and the solidification temperature of a molten mixture of Al₂O₃-TiO₂-SiO₂ oxides on a silicon nitride substrate are determined. Data are obtained for the change in kinetics. It is established that the intensity of interaction of molten Al₂O₃-TiO₂-SiO₂ with silicon nitride depends on the oxide mixture composition. With heating there are two possibilities: improvement and worsening of Si₃N₄ crystallite wetting with a liquid phase as well as solidification of the melt. The temperature range where a liquid phase exists for actual materials is about 15°C, which markedly worsens the process of structure formation with Si₃N₄ during sintering.Translated from Poroshkovaya M etallurgiya, No. 5, pp. 39–44, May, 1993.     

Interaction of copper sulfides with copper oxides in the molten state

Reactions of Cu₂S with Cu₂O, CuS with Cu₂O and CuS with CuO in the molten state were examined in the presence of one atmosphere of argon at 1200°C. A rate law of the form,r _SO2 =kN_SN_O was applicable for each reaction system studied. Comparison of the rate constants for the systems, under conditions of similar initial mole fraction of sulfur to mole fraction of oxygen ratios, showed that Cu₂O was much more reactive than CuO in its reaction with copper sulfides. These results are incorporated in a mechanism in which Cu₂O reacts with the sulfide in the rate determining step. Experiments carried out in the presence of oxygen indicated the importance of a CuO-Cu₂O equilibrium in the overall reaction mechanism.     

Kinetics of removal of bismuth and lead from molten copper alloys in vacuum induction melting

An investigation was made of the rates of removal of bismuth and lead from molten copper alloys stirred differently under vacuum at 1403 K. The heating conditions, which corresponded to highest, intermediate, and lowest stirring, were referred to as HC-A, HC-B, and HC-C, respectively. The rates of removal were described by a first-order rate equation involving the final concentration of the impurity. The overall mass-transfer coefficient for bismuth or lead (i),K _i, was determined, and it was found that K_i(HC-A) > K_i(HC-B) but K_i(HC-B) < K_i(HC-C) in Cu-Bi, Cu-Pb, and Cu-Bi-Pb alloys. In general, it was found that K_i(Cu-Bi-Pb) > K_i(Cu-Bi) or K_i(Cu-Pb). Oxygen reducedK _i more than sulfur. The reducing effect of oxygen and sulfur was weakened when stirring rate increased. In vacuum melting of Cu-Bi-Pb-O and Cu-Bi-Pb-S alloys under HC-C,K _i tended to decrease with increasing oxygen and sulfur concentrations. The loss of copper indicated that the rates were determined by liquid-phase mass-transfer and evaporation. The liquid-phase mass-transfer coefficient,K _L, was calculated, and it was found thatK _L(UC- A) > K_L(HC-B) but K_L(HC-B) < K_L(HC-C). The last relation was contrary to current theoretical prediction. A new model was assumed to account for this fact. The observed relative volatility coefficients of bismuth and lead were much smaller than their respective theoretical coefficients. Oxygen and sulfur adsorbed on the surface of the melt were considered to be close to equilibrium with their respective bulk concentrations, and their effects on the evaporation mass-transfer coefficients for bismuth and lead were estimated to be fairly small. This result means that the observed reduction ofK _i is due mostly to the decrease inK _L and made possible the calculation ofK _L. Oxygen decreasedK _L more than sulfur. In vacuum melting of Cu-Bi-Pb-O and Cu-Bi-Pb-S alloys under HC-C,K _L decreased linearly with increasing oxygen or sulfur concentration. The final concentrations of bismuth and lead in these alloys under HC-C tended to increase with increasing oxygen and sulfur concentrations and tended to decrease with increasingK _i andK _L.     

The effect of silicon on the formation and properties o f tungsten - nickel - copper contacts

Powder Metallurgy and Metal Ceramics -     

China''''s imports and exports of tungsten,molybdenum,tin and antimony by category

~~China's imports and exports of tungsten,molybdenum,tin and antimony by category~~     

Formation of the structure and properties of molybdenum disilicide films during solidification on silicon

Physical metallography is used to study the phase composition, structure, and physical properties of thin (100–600 m) molybdenum disilicide films formed on silicon. The main factors which affect film properties are the chemical composition of the starting material, sputtering conditions, heat treatment, the phase state of the substrate, and impurities. It is established that solidification kinetics depend on the orientation of the silicon single-crystal substrate.Institute of Materials Science Problems, Ukrainian National Academy of Sciences, Kiev. Translated from Poroshkovaya Metallurgiya, Nos. 3/4(384), pp. 50–54, March–April, 1966. Original article submitted April 25, 1994.     

Thermodynamic properties of aluminum, magnesium, and calcium in molten silicon

The thermodynamic properties of aluminum, magnesium, and calcium in molten silicon were investigated using a chemical equilibration technique at 1723 to 1848 K, 1698 to 1798 K, and 1723 to 1823 K, respectively. The activity coefficient of aluminum in molten silicon was determined by equilibrating molten silicon-aluminum alloys with solid Al₂O₃ and Al₆Si₂O₁₃, that of magnesium was determined by equilibrating molten silicon-magnesium alloys and MgO-SiO₂-Al₂O₃ melts doubly saturated with MgSiO₃ and SiO₂, and that of calcium was determined by equilibrating molten silicon-calcium alloys with SiO₂-saturated CaO-SiO₂ melts. The activity coefficients at infinite dilution relative to the pure liquid state were determined as follows:

Kinetics of layer growth and multiphase diffusion in ion- nitrided titanium

Pure titanium specimens were ion nitrided in a nitrogen plasma in the temperature range of 800 ‡C to 1080 ‡C at various nitrogen partial pressures. During ion nitriding, titanium nitrides TiN and Tiin2N and nitrogen solid solution layers (α and Β) were formed consistent with the equilibrium phase diagram. The kinetics of growth of these layers were studied as a function temperature and ion-nitriding parameters. An analytical diffusion model for multiphase diffusion was used to calculate the diffusion coefficients of nitrogen in the phases of the Ti-TiN system from layer growth experiments. Using the layer growth data, the temperature dependence of nitrogen diffusion in TiN (δ), Ti₂N (ε), and α titanium was found to obey the following relations: Dinδ=4.4±1.62 × 10su-5 exp-36,500±1400/RT Dinε=2.7±1.05 ×10su-3 exp-35,760±2500/RT Dinα=0.96±0.08 × exp-51,280-505/RT Concentration profiles of nitrogen were measured in specimens ion nitrided at 900 ‡C. The profiles were in good agreement with the predicted ones at high nitrogen concentrations. How-ever, at low nitrogen concentrations, a deviation was observed, assumed to be due to a con-centration dependence of nitrogen diffusion in a titanium. Formerly Graduate Student, New Mexico Institute of Mining and Technology