Viscosity and conductivity of melts of the GeO<Subscript>2</Subscript>-PbO system

The temperature dependence of the viscosity and conductivity of melts of the GeO₂-PbO system containing 25, 40, 50, 62.5, 66.8, and 75 mol % PbO is measured. The results are attributed to the structure of the studied melts. It is shown that current-carrying ions also determine the viscous flow.     

Distribution Ratios of Phosphorus Between CaO-FeO-SiO<Subscript>2</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/Na<Subscript>2</Subscript>O/TiO<Subscript>2</Subscript> Slags and Carbon-Saturated Iron

In order to effectively enhance the efficiency of dephosphorization, the distribution ratios of phosphorus between CaO-FeO-SiO₂-Al₂O₃/Na₂O/TiO₂ slags and carbon-saturated iron (\( L_{\text{P}}^{\text{Fe-C}} \)) were examined through laboratory experiments in this study, along with the effects of different influencing factors such as the temperature and concentrations of the various slag components. Thermodynamic simulations showed that, with the addition of Na₂O and Al₂O₃, the liquid areas of the CaO-FeO-SiO₂ slag are enlarged significantly, with Al₂O₃ and Na₂O acting as fluxes when added to the slag in the appropriate concentrations. The experimental data suggested that \( L_{\text{P}}^{\text{Fe-C}} \) increases with an increase in the binary basicity of the slag, with the basicity having a greater effect than the temperature and FeO content; \( L_{\text{P}}^{\text{Fe-C}} \) increases with an increase in the Na₂O content and decrease in the Al₂O₃ content. In contrast to the case for the dephosphorization of molten steel, for the hot-metal dephosphorization process investigated in this study, the FeO content of the slag had a smaller effect on \( L_{\text{P}}^{\text{Fe-C}} \) than did the other factors such as the temperature and slag basicity. Based on the experimental data, by using regression analysis, \( \log L_{\text{P}}^{\text{Fe-C}} \) could be expressed as a function of the temperature and the slag component concentrations as follows:

$$ \begin{aligned} \log L_{\text{P}}^{\text{Fe-C}} & = 0.059({\text{pct}}\;{\text{CaO}}) + 1.583\log ({\text{TFe}}) - 0.052\left( {{\text{pct}}\;{\text{SiO}}_{2} } \right) - 0.014\left( {{\text{pct}}\;{\text{Al}}_{2} {\text{O}}_{3} } \right) \\ \, & \quad + 0.142\left( {{\text{pct}}\;{\text{Na}}_{2} {\text{O}}} \right) - 0.003\left( {{\text{pct}}\;{\text{TiO}}_{2} } \right) + 0.049\left( {{\text{pct}}\;{\text{P}}_{2} {\text{O}}_{5} } \right) + \frac{13{,}527}{T} - 9.87. \\ \end{aligned} $$

     

Kinetics of CO-CO<Subscript>2</Subscript> reaction with CaO-SiO<Subscript>2</Subscript>-FeOx melts

Measurements of the rate of interfacial reaction between CO₂-CO mixtures and CaO-SiO₂-FeOx slags have been made using the ¹³CO₂-CO isotope exchange technique. Ranges of slag compositions from 0 to 100 wt pct ‘FeO’ and CaO/SiO₂ between 0.3 and 2.0 were examined in the experiments. For each slag, the dependence of the apparent rate constant on temperature and equilibrium oxygen potential was studied. The relationship between the rate constant and oxygen potential was found to be in the form k _a=k _a ^o (a_o)^-α. The parameter a, with values between 0.5 and 0.9, was dependent on the slag composition. The activation energy of the reaction was independent of iron oxide content and dependent on slag basicity.     

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)}.     

Influence of CaF<Subscript>2</Subscript> and Li<Subscript>2</Subscript>O on the Viscous Behavior of Calcium Silicate Melts Containing 12 wt pct Na<Subscript>2</Subscript>O

Understanding the viscous behavior of silica-based molten fluxes is essential in maintaining the reliability of steel casting operations and in preventing breakouts. In particular, high concentrations of aluminum in recently developed transformation induced plasticity (TRIP) and twinning induced plasticity (TWIP) steels tend to promote reduction of silica in the mold fluxes that result in the formation of alumina, which in turn increases the viscosity. To counteract this effect, significant amounts of fluidizers such as CaF₂ and Li₂O are required to ensure that mold fluxes have acceptable lubrication and heat transfer characteristics. The viscous behavior of the slag system based on CaO-SiO₂-12 wt pct Na₂O with various concentrations of CaF₂ and Li₂O has been studied using the rotating spindle method to understand the effects on the viscosity with these additives. CaF₂ additions up to 8 wt pct were effective in decreasing the viscosity by breaking the network structure of molten fluxes, but CaF₂ concentrations above this level had a negligible effect on viscosity. Li₂O additions up to 2 wt pct were also effective in decreasing the viscosity, but the effect was comparatively negligible above 2 wt pct. Using Fourier transform infrared (FTIR) analysis of as-quenched slag samples, it was concluded that the viscosity was controlled more effectively by changing the larger complex silicate structures of rings and chains than by changing the amounts of simpler dimers and monomers.     

Raman spectroscopy of borosilicate and germanate-silicate glasses and melts

33 mol % Na₂O · 67 mol % SiO₂ + xB₂O₃ (GeO₂) glasses and melts with x = 0 and 20 mol % are studied by high-temperature Raman spectroscopy. The laws of formation of the anion structure of glasses and melts of borosilicate and germanate-silicate systems are shown to be different. The dominant anion groups in the systems are identified, and the structural changes occurring with increasing temperature and during a glass-melt transition are detected.     

Phase-equilibrium data and liquidus for the system “MnO”-CaO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> at Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/SiO<Subscript>2</Subscript> of 0.55 and 0.65

Phase-equilibrium data and liquidus isotherms for the system “MnO”-CaO-(Al₂O₃+SiO₂) at silicomanganese alloy saturation have been determined in the temperature range of 1373 to 1723 K. The results are presented in the form of the pseudoternary sections “MnO”-CaO-(Al₂O₃+SiO₂) with Al₂O₃/SiO₂ weight ratios of 0.55 and 0.65. The primary-phase fields have been identified in this range of conditions.     

Critical thermodynamic evaluation and optimization of the FeO-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>-MgO-SiO<Subscript>2</Subscript> system

A complete literature review, critical evaluation, and thermodynamic modeling of the phase diagrams and thermodynamic properties of all oxide phases in the FeO-Fe₂O₃-MgO-SiO₂ system at 1 bar total pressure are presented. Optimized model equations for the thermodynamic properties of all phases are obtained, which reproduce all available thermodynamic and phase-equilibrium data within experimental error limits from 25 °C to above the liquidus temperatures at all compositions and oxygen partial pressures. The complex phase relationships in the system have been elucidated, and discrepancies among the data have been resolved. The database of the model parameters can be used along with software for Gibbs-energy minimization in order to calculate all thermodynamic properties and any type of phase-diagram section. The modified quasichemical model was used for the liquid-slag phase. Sublattice models, based upon the compound-energy formalism, were used for the olivine, spinel, pyroxene, and monoxide solid solutions. The use of physically reasonable models means that the models can be used to predict thermodynamic properties and phase equilibria in composition and temperature regions where data are not available.     

Modeling of the solubilities of NiO/NiAl<Subscript>2</Subscript>O<Subscript>4</Subscript> and FeO/FeAl<Subscript>2</Subscript>O<Subscript>4</Subscript> in cryolite melts at 1300 K

Experiments to measure the solubilities of NiO/NiAl₂O₄ and FeO/FeAl₂O₄ were performed, and the results confirmed existing literature values. The solubilities of NiAl₂O₄ and FeAl₂O₄ in Al₂O₃-saturated cryolite melts at 1300 K were modeled thermodynamically in terms of the Ni-containing complexes Na₂NiF₄ and Na₄NiF₆, and the Fe-containing solutes FeF₂, Na₂FeF₄, and Na₄FeF₆. The experimental solubility data were fitted to multiple simultaneous equilibria. Equilibrium constants and ΔG _f ⁰ values for the formation reactions of the these solutes were thereby estimated. The solubilities of NiO/NiAl₂O₄ and FeO/FeAl₂O₄ and solute distributions in Al₂O₃-undersaturated cryolite melts were calculated for a number of melt compositions from the present model. The existence of several competitive solute species is inherent to highly buffered ionic cryolite solutions where the traditional log-log methodology had previously failed to identify dominant single solutes. In such solutions, individual solutes of oxides are not likely to dominate over a wide composition range so that a more global modeling is required. The principal solute species identified in the present study exhibit reasonable three-dimensional (3-D) anion geometries.     

The rate of antimony elimination from molten copper by the use of Na<Subscript>2</Subscript>CO<Subscript>3</Subscript> slag

The rate of Sb elimination from molten copper by the use of Na₂CO₃ slag was measured at 1523 K. The results obtained under the present experimental conditions show that Sb in molten copper is eliminated in a tri-valent or a penta-valent form, depending on the oxygen concentration at the slag-metal interface, and its elimination rate increases with increasing initial oxygen concentration in molten copper. The overall elimination rate of Sb is affected by the stirring condition of the molten copper, which indicates a rate control by mass transfer in that phase. The mass-transfer coefficients of Sb and oxygen in molten copper at 1523 K without external stirring were determined, respectively, to be

Effect of Na<Subscript>2</Subscript>CO<Subscript>3</Subscript> Addition on Inclusions in High-Carbon Steel for Saw Wire

Inclusions cannot be sufficiently stretched to adapt extremely strict requirement of saw wire with only conventional inclusion softening art. In order to explore a potential new method to further enhance the deformability of inclusions, Na₂CO₃ addition should be comprehensively investigated due to the extremely low melting temperature of inclusions containing Na₂O. In the present study, an effective method of Na₂CO₃ addition was put forward and a presumable reaction mechanism between Na₂CO₃/steel/inclusion/slag was deduced by studying the effect of Fe/Na₂CO₃ (weight ratio), Na₂CO₃ addition amount and reaction time on inclusions using a graphite tube resistance furnace. The relations between Na₂O content, melting temperature, deformability and crystallization of inclusions were also briefly discussed. Through these studies, the deformability of inclusions was significantly improved on the whole.     

Temperature dependence of the refractive index of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-Na<Subscript>2</Subscript>O-SiO<Subscript>2</Subscript> melts: Role of electronic polarizability of oxygon controlled by network structure

Refractive indexes for the Al₂O₃-Na₂O-SiO₂ system have been measured using an ellipsometer for a wavelength of 632.8 nm over a wide temperature range (1100 to 1800 K). Two kinds of sample were used: xAl₂O₃-(40-x)Na₂O-60SiO₂ and yAl₂O₃-yNa₂O-(100-2y)SiO₂, where x ranged between 6 and 20 mol pct and y between 12.5 and 25 mol pct. In the former samples, the temperature coefficient of refractive indexes changed from negative to positive on increasing the concentration of Al₂O₃. In the latter samples, the refractive indexes increased monotonically with decreasing concentration of SiO₂, and the temperature coefficient was always positive. It has been found that the temperature dependence of refractive indexes in these melts is determined by the coefficient of thermal expansion, which would be relevant to the degree of polymerization of the melts. In addition, the electronic polarizability of oxygen derived from the refractive indexes increased with increasing temperature in each melt. This suggests that the basicity of the alumino-silicate melts increases as temperature increases. The positive temperature coefficient of the electronic polarizability of oxygen can be attributed to an increase in the distance between cation and oxygen ion due to thermal expansion. The dependence of the electronic polarizability of oxygen on the concentration of Al₂O₃ has also been discussed in terms of the electronic polarizabilities of three types of oxygen contained in the melts. This article is based on a presentation given in the Mills Symposium entitled “Metals, Slags, Glasses: High Temperature Properties & Phenomena,” which took place at The Institute of Materials in London, England, on August 22–23, 2002.     

A reinvestigation of phase equilibria in the system Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript>-ZnO

The phase equilibria and liquidus temperatures in the binary SiO₂-ZnO system and in the ternary Al₂O₃-SiO₂-ZnO system at low Al₂O₃ concentrations have been experimentally determined using the equilibration and quenching technique followed by electron probe X-ray microanalysis. In the SiO₂-ZnO system, two binary eutectics involving the congruently melting willemite (Zn₂SiO₄) were found at 1448±5 °C and 0.52±0.01 mole fraction ZnO and at 1502±5 °C and 0.71±0.01 mole fraction ZnO, respectively. The two ternary eutectics involving willemite previously reported in the Al₂O₃-SiO₂-ZnO system were found to be at 1315±5 °C and 1425±25 °C, respectively. The compositions of the eutectics are 0.07, 0.52, and 0.41 and 0.05, 0.28, and 0.67 mole fraction Al₂O₃, SiO₂, and ZnO, respectively. The results of the present investigation are significantly different from the results of previous studies.