Air Oxidation of a Ni<Subscript>53</Subscript>Nb<Subscript>20</Subscript>Ti<Subscript>10</Subscript>Zr<Subscript>8</Subscript>Co<Subscript>6</Subscript>Cu<Subscript>3</Subscript> Glassy Alloy at 400–550 °C

Air-oxidation behavior of a Ni₅₃Nb₂₀Ti₁₀Zr₈Co₆Cu₃ amorphous ribbon was studied at 400–550 °C. The oxidation kinetics of the amorphous alloy followed a two-stage parabolic rate law with its oxidation rates steadily increasing with temperature. The steady-state oxidation rate constants of the alloy were faster than those of pure Ni. Triplex scales formed on the glassy alloy, containing an outer layer of NiO. The scales formed in the intermediate layer consisted of Nb₂O₅, NiO, and uncorroded α-Ni, while an additional Nb₂Zr₆O₁₇ phase was also detected in the inner layer. The formation of multilayered scales is responsible for the faster oxidation for the Ni6-AR.     

Mössbauer study of the process of the room-temperature aging of the alloy Cu<Subscript>79</Subscript>Ni<Subscript>14</Subscript>Fe<Subscript>7</Subscript>

Mössbauer spectroscopy was used to investigate the initial stage of the phase separation in the quasi-binary system Cu₇₉Ni₁₄Fe₇ and the subsequent transformation of the alloy structures as a result of prolonged aging at room temperature. For describing the Mössbauer spectra of ferromagnetic particles, which appear upon the spinodal decomposition in a paramagnetic matrix, a model was proposed and approved, which uses particle-size distribution in the approximation of the generalized Lifshitz-Slezov-Wagner (LSW) model and of the linear decrease of the hyperfine field at the ⁵⁷Fe nuclei in the near-surface layers of spherical particles.     

Details on the Formation of Ti<Subscript>2</Subscript>Cu<Subscript>3</Subscript> in the Ag-Cu-Ti System in the Temperature Range 790 to 860 °C

Silver-copper-titanium (Ag-Cu-Ti) ternary alloys are often used as active braze alloys for joining ceramics to metals at temperatures ranging from 780 °C (the melting point of the Ag-Cu eutectic) up to 900 °C. When Ti/Ag-Cu joints are brazed at low temperature (near 800 °C), the intermetallic compound Ti₂Cu₃ (tetragonal, P4/nmm, a = 0.313 nm, c = 1.395 nm) is systematically missing from the interface reaction layer sequence. An experimental investigation based on isothermal diffusion experiments in the Ag-Cu-Ti ternary system has then been undertaken to clarify the issues of thermal stability and formation kinetics of this compound. Evidence has been found for the stability of Ti₂Cu₃ at temperatures ranging from 790 to at least 860 °C. By heat treating Ag-Cu-Ti powder mixtures at 790 °C for increasing times, it has moreover been shown that Ti₂Cu₃ forms at a much slower rate than the two adjacent Ti-Cu compounds: TiCu₄, the first phase to form, and Ti₃Cu₄. This explains why although thermodynamically stable, Ti₂Cu₃ is not obtained when temperature is too low or reaction time too short.     

Activities in the FeTiO<Subscript>3</Subscript>-NiTiO<Subscript>3</Subscript> Solid Solution from Alloy-Oxide Equilibria at 1273 K

Nine tie-lines between Fe-Ni alloys and FeTiO₃-NiTiO₃ solid solutions were determined at 1273 K. Samples were equilibrated in evacuated quartz ampoules for periods up to 10 days. Compositions of the alloy and oxide phases at equilibrium were determined by energy-dispersive x-ray spectroscopy. X-ray powder diffraction was used to confirm the results. Attainment of equilibrium was verified by the conventional tie-line rotation technique and by thermodynamic analysis of the results. The tie-lines are skewed toward the FeTiO₃ corner. From the tie-line data and activities in the Fe-Ni alloy phase available in the literature, activities of FeTiO₃ and NiTiO₃ in the ilmenite solid solution were derived using the modified Gibbs-Duhem technique of Jacob and Jeffes [K.T. Jacob and J.H.E. Jeffes, An Improved Method for Calculating Activities from Distribution Equilibria, High Temp. High Press., 1972, 4, p 177-182]. The components of the oxide solid solution exhibit moderate positive deviations from Raoult’s law. Within experimental error, excess Gibbs energy of mixing for the FeTiO₃-NiTiO₃ solid solution at 1273 K is a symmetric function of composition and can be represented as:

Effect of Si and Y<Subscript>2</Subscript>O<Subscript>3</Subscript> Additions on the Oxidation Behavior of Ni–<Emphasis Type="Italic">x</Emphasis>Al (<Emphasis Type="Italic">x</Emphasis> = 5 or 10 wt%) Alloys at 1150 °C

The effect of Si and Y₂O₃ additions on the oxidation behavior of Ni–xAl (x = 5 or 10 wt%) alloys at 1150 °C was studied. The addition of Y₂O₃ accelerates oxidation rate of alloys, especially growth rate of NiO, but improves adherence of the scale to the substrate. The addition of Si facilitates the selective oxidation of Al, suppresses the formation of NiO and therefore reduces the critical Al content to form continuous layer of alumina scale. Higher Al content decreases the oxidation rate of alloys in binary Ni–Al alloys and increases the oxidation rate of alloys in ternary Ni–Al–Si alloys. The effect of third-element Si is more significant and beneficial than that of Al content in ternary Ni–Al–Si alloys.     

Experimental Investigation of Gas/Matte/Spinel Equilibria in the Cu-Fe-O-S System at 1473 K (1200 °C) and <Emphasis Type="Italic">P</Emphasis>(SO<Subscript>2</Subscript>) = 0.25 atm

The Cu-Fe-O-S system is the key system for the characterisation of the phase chemistry in high-temperature copper making processes. An experimental study was undertaken to investigate the gas/matte/spinel equilibria in the Cu-Fe-O-S system at 1473 K (1200 °C), P(SO₂) = 0.25 atm, and a range of oxygen partial pressures. The experimental methodology involved high temperature equilibration using a primary phase substrate technique in controlled gas atmospheres (CO/CO₂/SO₂/Ar), rapid quenching of the equilibrated phases, followed by direct measurement of phase compositions using electron probe x-ray microanalysis. Particular attention was given to the analysis of reactions during equilibration and confirmation of the achievement of equilibrium in the present study. The new data provide important information for understanding of the gas/matte/spinel interactions at high temperature and provide an essential foundation for the development of the multicomponent thermodynamic database for copper-containing systems.