Electrical conductivity of NaF-AlF<Subscript>3</Subscript>-CaF<Subscript>2</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> melts

The electrical conductivity of NaF-AlF₃-Al₂O₃ melts with a CaF₂ concentration of 5 wt % is measured at a continuously varying cell constant when the molar cryolitic ratio CR = [NaF]/[AlF₃] changes from 1.2 to 2.0 [1, 2]. The experimental data are used to obtain a regression equation to describe the dependence of the electrical conductivity of the melts under study on CR, the alumina content, and temperature {χ] = f(CR, [Al₂O₃], T)}.     

Experimental Investigation and Thermodynamic Modeling of the B<Subscript>2</Subscript>O<Subscript>3</Subscript>-FeO-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>-Nd<Subscript>2</Subscript>O<Subscript>3</Subscript> System for Recycling of NdFeB Magnet Scrap

NdFeB magnet scrap is an alternative source of neodymium that could have a significantly lower impact on the environment than current mining and extraction processes. Neodymium can be readily oxidized in the presence of oxygen, which makes it easy to recover neodymium in oxide form. Thermochemical data and phase diagrams for neodymium oxide containing systems is, however, very limited. Thermodynamic modeling of the B₂O₃-FeO-Fe₂O₃-Nd₂O₃ system was hence performed to obtain accurate phase diagrams and thermochemical properties of the system. Key phase diagram experiments were also carried out for the FeO-Nd₂O₃ system in saturation with iron to improve the accuracy of the present modeling. The modified quasichemical model was used to describe the Gibbs energy of the liquid oxide phase. The Gibbs energy functions of the liquid phase and the solids were optimized to reproduce all available and reliable phase diagram data, and thermochemical properties of the system. Finally the optimized database was applied to calculate conditions for selective oxidation of neodymium from NdFeB magnet waste.     

Effect of Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Concentration on Density and Structure of (CaO-SiO<Subscript>2</Subscript>)-xAl<Subscript>2</Subscript>O<Subscript>3</Subscript> Slag

The effect of Al₂O₃ concentration on the density and structure of CaO-SiO₂-Al₂O₃ slag was investigated at multiple Al₂O₃ mole percentages and at a fixed CaO/SiO₂ ratio of 1. The experiments were conducted in the temperature range of 2154 K to 2423 K (1881 °C to 2150 °C) using the aerodynamic levitation technique. In order to understand the relationship between density and structure, structural analysis of the silicate melts was carried out using Raman spectroscopy. The density of each slag sample investigated in this study decreased linearly with increasing temperature. When the Al₂O₃ content was less than 15 mole pct, density decreased with increasing Al₂O₃ content due to the coupling of Si (Al), whereas above 20 mole pct density of the slag increased due to the role of Al³⁺ ion as a network modifier.     

The Ca(SO<Subscript>4</Subscript>)-Na<Subscript>2</Subscript>(SO<Subscript>4</Subscript>)-Ca<Subscript>3</Subscript>(AsO<Subscript>4</Subscript>)<Subscript>2</Subscript>-Na<Subscript>3</Subscript>(AsO<Subscript>4</Subscript>) phase diagram

The phase diagram of the CaSO₄-Na₂SO₄-Ca₃(AsO₄)₂-Na₃(AsO₄) system was measured by differential thermal analysis and by an equilibration and quenching technique. Thermodynamic models were developed giving the Gibbs energies of all phases as functions of temperature and composition. Optimized model parameters were obtained by assessment of all available thermodynamic and phase equilibrium data. The models, which reproduce all the data within experimental error limits, were used to calculate the liquidus surface of the system. The modified quasi-chemical model in the quadruplet approximation was used for the liquid solution. For the various solid solution phases, the modified quasi-chemical model, which accounts simultaneously for short-range-ordering among first-nearest-neighbor (FNN) and second-nearest-neighbor (SNN) pairs, was used for the first time within the framework of the compound energy formalism. The distinction between true model parameters and formalism parameters is made. Implications of the work for the potential use of sulfate fluxes for copper refining are discussed.     

Thermodynamics of MnO-SiO<Subscript>2</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-MnS Liquid Oxysulfide: Experimental and Thermodynamic Modeling

The activities of MnO and MnS in a MnO-SiO₂-Al₂O₃(or AlO_1.5)-MnS liquid oxysulfide solution were investigated by employing the gas/liquid/Pt-Mn alloy chemical equilibration technique under a controlled atmosphere at 1773 K (1500 °C). Also, the sulfide capacity, defined as C _S = (wt pct S)(pO₂/pS₂)^1/2, in MnO-SiO₂-Al₂O₃ slag with a dilute MnS concentration was obtained from the measured experimental data. As X _SiO2/(X _MnO + X _SiO2) in liquid oxysulfide increases, the activity coefficient of MnO decreases, while that of MnS first increases and then decreases. As X(AlO_1.5) in liquid oxysulfide increases, the activity coefficient of MnS increases, while no remarkable change is observed for the activity coefficient of MnO. The behavior of the activity coefficient of MnS was qualitatively analyzed by considering MnO + A _x S _y (SiS₂ or Al₂S₃) = MnS + A _x O _y (SiO₂ or Al₂O₃) reciprocal exchange reactions in the oxysulfide solution. The behavior was shown to be consistent with phase diagram data, namely, the MnS saturation boundary. Quantitative analysis of the activity coefficient of the oxysulfide solution was also carried out by employing the modified quasichemical model in the quadruplet approximation.     

Non-equilibrium transformations involving L1<Subscript>2</Subscript>-Al<Subscript>3</Subscript>Zr in ternary Al-X-Zr alloys

The metastable L1₂-Al₃Zr phase has been obtained as a solidification product on melt-spinning ternary Al-X-Zr (X = Cu, Ni) alloys. Different non-equilibrium effects of the metastable Al₃Zr phase (L1₂) have been observed in the as-solidified and heat-treated alloys. The solidification sequence begins with the formation of the L1₂-Al₃Zr (cubic) phase as a primary phase, followed by heterogeneous nucleation of α-Al. Morphological changes in the primary phase result in a shape transformation from a faceted cube to one with concave interfaces and protrusions along the corners, having a preferential growth along the 〈111〉 direction. This is brought about by a kinetic effect taking place during the growth of the L1₂-Al₃Zr phase into the surrounding liquid, as the alloy is quenched. In another instance, the primary L1₂-Al₃Zr phase nucleates as solid-state precipitates of the same L1₂-Al₃Zr phase on annealing, by dissolution and reprecipitation of solute, under the influence of moving grain boundaries. A third case shows the metastable L1₂ phase nucleating on the equilibrium DO₂₃-Al₃Zr phase, upon solidification. This is attributed to the sluggish growth kinetics of the latter.     

The Viscous Behavior of FeO<Subscript>t</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> Copper Smelting Slags

Understanding the viscous behavior of copper smelting slags is essential in increasing the process efficiency and obtaining the discrete separation between the matte and the slag. The viscosity of the FeO_t-SiO₂-Al₂O₃ copper smelting slags was measured in the current study using the rotating spindle method. The viscosity at a fixed Al₂O₃ concentration decreased with increasing Fe/SiO₂ ratio because of the depolymerization of the molten slag by the network-modifying free oxygen ions (O²⁻) supplied by FeO. The Fourier transform infrared (FTIR) analyses of the slag samples with increasing Fe/SiO₂ ratio revealed that the amount of large silicate sheets decreased, whereas the amount of simpler silicate structures increased. Al₂O₃ additions to the ternary FeO_t-SiO₂-Al₂O₃ slag system at a fixed Fe/SiO₂ ratio showed a characteristic V-shaped pattern, where initial additions decreased the viscosity, reached a minimum, and increased subsequently with higher Al₂O₃ content. The effect of Al₂O₃ was considered to be related to the amphoteric behavior of Al₂O₃, where Al₂O₃ initially behaves as a basic oxide and changes to an acidic oxide with variation in slag composition. Furthermore, Al₂O₃ additions also resulted in the high temperature phase change between fayalite/hercynite and the modification of the liquidus temperature with Al₂O₃ additions affecting the viscosity of the copper smelting slag.     

Thermal diffusivity measurements of some synthetic CaO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> slags

In an attempt to systematize the knowledge of the heat conduction of liquid silicates, the effective thermal diffusivities of some synthetic slags containing CaO, Al₂O₃, and SiO₂ have been measured, using the three-layer laser-flash method on a differential scheme in the temperature range of 1625 to 1825 K. The effective thermal diffusivities measured, which are a combination of the phononic and photonic heat-transfer mechanisms, were found to increase with increasing temperature for all the presently investigated slags. The slag compositions were chosen in such a way that the changes in the effective thermal diffusivities would reflect the changes in the structure of the slags. It was observed that, at a CaO/Al₂O₃ molar ratio of 4.42, an increase of the SiO₂ content had very little effect on the effective thermal diffusivity values. On the other hand, addition of SiO₂ to a slag with the CaO/Al₂O₃ molar ratio of 2.59 resulted in a significant increase in the effective thermal diffusivity. The addition of Al₂O₃ to slags with a constant CaO/SiO₂ molar ratio resulted in a marked increase in the effective thermal diffusivity. Both these trends indicate that there might be an influence of the network formation in silicate melts on the effective thermal diffusivity.     

Density Measurements of Low Silica CaO-SiO<Subscript>2</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Slags

Density measurements of a low-silica CaO-SiO₂-Al₂O₃ system were carried out using the Archimedes principle. A Pt 30 pct Rh bob and wire arrangement was used for this purpose. The results obtained were in good agreement with those obtained from the model developed in the current group as well as with other results reported earlier. The density for the CaO-SiO₂ and the CaO-Al₂O₃ binary slag systems also was estimated from the ternary values. The extrapolation of density values for high-silica systems also showed good agreement with previous works. An estimation for the density value of CaO was made from the current experimental data. The density decrease at high temperatures was interpreted based on the silicate structure. As the mole percent of SiO₂ was below the 33 pct required for the orthosilicate composition, discrete \textSiO₄^{4 -} {\text{SiO}}_{4}^{4 - } tetrahedral units in the silicate melt would exist along with O^2– ions. The change in melt expansivity may be attributed to the ionic expansions in the order of

Thermodynamic evaluation and optimization of the MnO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and MnO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> systems and applications to inclusion engineering

All available thermodynamic and phase-diagram data have been critically evaluated and optimized for the liquid-slag phase and for all solid phases at 1 bar pressure from 298 K to above the liquidus temperatures for the systems MnO-Al₂O₃ and MnO-Al₂O₃-SiO₂, and a database of model parameters has been prepared. The modified quasichemical model was employed for the molten-slag phase. Calculations using the database were performed with applications to inclusion engineering for Mn/Si killed steel.     

Effects of an α-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> thin film on the oxidation behavior of a single-crystal Ni-based superalloy

A ∼150-nm-thick coating layer consisting of α-Al₂O₃ as the major phase with a minute amount of Φ-Al₂O₃ was deposited on the surface of a single-crystal Ni-based superalloy by chemical vapor deposition (CVD). Within 0.5 hours of oxidation at 1150°C, the resulting thermally grown oxide (TGO) formed on the coated alloy surface underwent significant lateral grain growth. Consequently, within this time scale, the columnar nature of the TGO became established. After 50 hours, a network of ridges was clearly observed on the TGO surface instead of equiaxed grains typically observed on the uncoated alloy surface. Comparison of the TGO morphologies observed with and without the CVD-Al₂O₃ layer suggested that the transient oxidation of the alloy surface was considerably reduced. Also, the CVD-Al₂O₃ layer significantly reduced the growth rate of the TGO and improved its spallation resistance, while slowing the internal oxidation of Ta-rich areas that were present in the superalloy as-casting defects. These results demonstrated that this thin α-Al₂O₃ coating could be used as a means of favorably altering the TGO morphology and growth kinetics for no bond coat thermal barrier coating (TBC) applications. Y.-F. SU, formerly Doctoral Candidate     

Effect of LiF as Sintering Agent on the Densification and Phase Formation in Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-4 Wt Pct Nb<Subscript>2</Subscript>O<Subscript>5</Subscript> Ceramic Compound

Different amounts of LiF were added to an Al₂O₃-4 pct Nb₂O₅ basic ceramic, as sintering agent. Improved new ceramics were obtained with LiF concentrations varying from 0.25 to 1.50 wt pct and three sintering temperatures of 1573 K, 1623 K, and 1673 K (1300 °C, 1350 °C, and 1400 °C). The addition of 0.5 wt pct LiF yielded the highest densification, 94 pct of the theoretical density, in association with a sintering temperature of 1673 K (1400 °C). Based on X-ray diffraction (XRD), this improvement was due not only to the presence of transformed phases, more precisely Nb₃O₇F, but also to the absence of LiAl₅O₈. The preferential interaction of LiF with Nb₂O₅, instead of Al₂O₃, contributed to increase the alumina sintering ability by liquid phase formation. Scanning electron microscopy (SEM) results revealed well-connected grains and isolated pores, whereas the chemical composition analysis by energy dispersive energy (EDX) indicated a preferential interaction of fluorine with niobium, in agreement with the results of XRD. It was also observed from thermal analysis that the polyethylene glycol binder burnout temperature increased for all LiF concentrations. This may be related to the formation of hydrogen bridge bonds.     

Effects of preoxidation on the nucleation and growth behavior of chemically vapor-deposited α-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> on a single-crystal Ni-based superalloy

A chemical vapor deposition (CVD) procedure was developed for preparing a high-quality α-Al₂O₃ coating layer on the surface of a single-crystal Ni-based superalloy using AlCl₃, CO₂ and H₂ as precursors. A critical part of this procedure was a short-time preoxidation step (1 min) with CO₂ and H₂ in the CVD chamber, prior to introducing the AlCl₃ precursor. Without this preoxidation step, extensive whisker formation was observed on the alloy surface. Characterization results showed that the preoxidation step resulted in the formation of a continuous oxide layer (∼50 nm) on the alloy surface. The outer part of this layer (∼20 nm) appeared to contain mixed oxides, whereas the inner part (∼30 nm) mainly consisted of α-Al₂O₃ grains with θ-Al₂O₃ as a minor phase. We observed that the nucleation of α-Al₂O₃ in the preoxidized layer was promoted by (1) rapid heating (10 seconds) of the alloy surface to the temperature region where α-Al₂O₃ was expected to nucleate; (2) the low oxygen pressure environment of the preoxidation step, which kept the rate of oxidation low; and (3) contamination of the reactor chamber with HfCl₄. The preoxidized layer served as an effective diffusion barrier for mitigating the interaction with some of the alloying elements such as Co and Cr with the CVD precursors and eliminating whisker formation on the alloy surface. L.M. HE, formerly Doctoral Candidate, Dept. of Chemical, Biomedical, and Material Engineering, Stevens Institute of Technology, Hoboken, NJ 07030 Y.-F. SU, formerly Doctoral Candidate     

Synthesis and Characterization of Lithium Borate Glasses Containing La<Subscript>2</Subscript>O<Subscript>3</Subscript>

The glass series with general formula 15 Li₂O–(85 − x) B₂O₃–x La₂O₃ was prepared. Electrical and optical properties of these glasses were studied. It is observed that the conductivity of these glasses decreases while density, glass transition temperature and refractive index increases with the addition of La₂O₃. Ion concentration of La³⁺ in glasses, polaron radius, field strength, molar refractivity and molar electronic polarizability were calculated. The absorption coefficient and direct optical band gaps are evaluated using the absorption edge calculations. The different factors that play a role for controlling the refractive indices such as electronic polarizability, field strength of cations and rigidity of glass structure are discussed in accordance with the obtained index data.     

Effect of Slag Composition on the Crystallization Kinetics of Synthetic CaO-SiO<Subscript>2</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-MgO Slags

The crystallization kinetics of CaO-SiO₂-Al₂O₃-MgO (CSAM) slags was studied with the aid of single hot thermocouple technique (SHTT). Kinetic parameters such as the Avrami exponent (n), rate coefficient (K), and effective activation energy of crystallization (E _A ) were obtained by kinetic analysis of data obtained from in situ observation of glassy to crystalline transformation and image analysis. Also, the dependence of nucleation and growth rates of crystalline phases were quantified as a function of time, temperature, and slag basicity. Together with the observations of crystallization front, they facilitated establishing the dominant mechanisms of crystallization. In an attempt to predict crystallization rate under non-isothermal conditions, a mathematical model was developed that employs the rate data of isothermal transformation. The model was validated by reproducing an experimental continuous cooling transformation diagram purely from isothermal data.     

Reactive synthesis of <Emphasis Type="Italic">in-situ</Emphasis> ZrAl<Subscript>3</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-Al composites

In this work, a reactive synthesis process is proposed to obtain ZrAl₃-Al₂O₃ particulate-reinforced aluminum matrix composites. The process involves the in-situ formation of Al₂O₃ and ZrAl₃ from Al-ZrO₂ green compacts. Upon compact heating, it is found that reduction of ZrO₂ by molten aluminum occurs at temperatures above 750 °C, leading to the development of ZrAl₃ and Al₂O₃ phases. Thermodynamically, it is found that the reduction of zirconium oxide is driven mainly by the dissolution of Zr in molten aluminum. Because the solubility of Zr in liquid aluminum is extremely small, the formation of ZrAl₃ is favored after relatively small Zr dissolutions. The first Zr-Al intermetallics to form at the lowest temperatures seem to be metastable, as infered from the measured atom ratios for Al : Zr of 2.83 : 1. At increasing temperatures, the reaction comes into completion, resulting in the formation of equilibrium intermetallic ZrAl₃ phases. The results obtained from differential scanning calorimetry (DSC) indicate that by increasing the scanning rates, both the reaction temperature and the exothermic peak intensity also increase. Alternatively, it is found that by reducing the amount of ZrO₂ in the green compact, the in-situ reaction temperatures also shift toward higher values.     

Evaluating the Diffusion Coefficient of Sulfur in Low-Silica CaO-SiO<Subscript>2</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Slag

The chemical diffusion coefficient of sulfur in the ternary slag of composition 51.5 pct CaO-9.6 pct SiO₂-38.9 pct Al₂O₃ slag was measured at 1680 K, 1700 K, and 1723 K (1403 °C, 1427 °C, and 1450 °C) using the experimental method proposed earlier by the authors. The P_\textS2 P_{{{\text{S}}_{2} }} and P_\textO2 P_{{{\text{O}}_{2} }} pressures were calculated from the Gibbs energy of the equilibrium reaction between CaO in the slag and solid CaS. The density of the slag was obtained from earlier experiments. Initially, the order of magnitude for the diffusion coefficient was taken from the works of Saito and Kawai but later was modified so that the concentration curve for sulfur obtained from the program was in good fit with the experimental results. The diffusion coefficient of sulfur in 51.5 pct CaO-9.6 pct SiO₂-38.9 pct Al₂O₃ slag was estimated to be in the range 3.98 to 4.14 × 10⁻⁶ cm²/s for the temperature range 1680 K to 1723 K (1403 °C to 1450 °C), which is in good agreement with the results available in literature