High-temperature mass spectrometric study and modeling of thermodynamic properties of binary glass-forming systems containing Bi2O3.

RATIONALE: Binary glass-forming systems containing bismuth(III) oxide, especially the Bi2O3-SiO2 system, are of great importance in modern materials science: preparation of thin films, fiber optics, potential solar converters, and radiation shields in nuclear physics. Information on vaporization processes and thermodynamic properties obtained in the present study and the results of modeling of this system will be useful for optimization of the synthesis and applications of Bi2O3-containing materials at high temperatures. METHODS: High-temperature Knudsen effusion mass spectrometry was used to study the vaporization processes and to determine the partial pressures of components of the Bi2O3-SiO2 system. Measurements were performed with a MS-1301 mass spectrometer. Vaporization was carried out using two iridium-plated molybdenum effusion cells containing the sample under study and pure bismuth(III) oxide (reference substance). Modeling of the thermodynamic properties and structure of glasses and melts in the Bi2O3-SiO2 and Bi2O3-B2O3 systems was performed using a modified approach based on the generalized lattice theory of associated solutions (GLTAS). RESULTS: At a temperature of 1000 K, Bi and O2 were found to be the main vapor species over the samples studied. The Bi2O3 activity as a function of composition of the Bi2O3-SiO2 system was obtained from the measured partial pressures of the vapor species. The thermodynamic properties of mixing from oxides in this system were calculated. The advantages of GLTAS for modeling of glasses and melts in the binary systems containing Bi2O3 were demonstrated. CONCLUSIONS: The thermodynamic functions of mixing in glasses and melts of the Bi2O3-SiO2 system determined at 1000 K in the present study, as well as in the Bi2O3-B2O3 system, demonstrated negative deviations from ideality. Modeling of the obtained experimental data using GLTAS allowed a correlation to be found between the thermodynamic properties and the relative number of bonds of various types formed in the glasses and melts of these systems.

High-temperature mass spectrometric study of the vaporization processes and thermodynamic properties of melts in the PbO-B2O3-SiO2 system.

RATIONALE: The unique properties of the PbO-B2O3-SiO2 system, especially its extensive range of glass-forming compositions, make it valuable for various practical applications. The thermodynamic properties and vaporization of PbO-B2O3-SiO2 melts are not well established so far and the data obtained on these will be useful for optimization of technology and thermodynamic modeling of glasses. METHODS: High-temperature Knudsen effusion mass spectrometry was used to study vaporization processes and to determine the partial pressures of components of the PbO-B2O3-SiO2 melts. Measurements were performed with a MS-1301 mass spectrometer. Vaporization was carried out using two quartz effusion cells containing the sample under study and pure PbO (reference substance). Ions were produced by electron ionization at an energy of 25 eV. To facilitate interpretation of the mass spectra, the appearance energies of ions were also measured. RESULTS: Pb, PbO and O2 were found to be the main vapor species over the samples studied at 1100 K. The PbO activities as a function of the composition of the system were derived from the measured PbO partial pressures. The B2O3 and SiO2 activities, the Gibbs energy of formation, the excess Gibbs energy of formation and mass losses in the samples studied were calculated. CONCLUSIONS: Partial pressures of the vapor species over PbO-B2O3-SiO2 melts were measured at 1100 K in the wide range of compositions using the Knudsen mass spectrometric method. The data enabled the PbO, B2O3, and SiO2 activities in these melts to be derived and provided evidence of their negative deviations from ideal behavior.

High-temperature mass spectrometric study of the vaporization processes of V2O3 and vanadium-containing slags.

A Knudsen effusion mass spectrometric method was used to study the vaporization processes and thermodynamic properties of pure V(2)O(3) and 14 samples of vanadium-containing slags in the CaO-MgO-Al(2)O(3)-SiO(2) system in the temperature range 1875-2625 K. The system was calibrated using gold in the liquid state as the standard. Vaporization was carried out from double tungsten effusion cells. First it was shown that, in vapor over V(2)O(3) and the vanadium-containing slags in the temperature range 1875-2100 K, the following vapor species were present: VO(2), VO, O, WO(3) and WO(2), with the latter two species being formed as a result of interaction with the tungsten crucibles. The temperature dependencies of the partial pressures of these vapor species were obtained over V(2)O(3) and the slags. The ion current comparison method was used for the determination of the V(2)O(3) activities in slags as a function of temperature with solid V(2)O(3) as a reference state. The V(2)O(3) activity coefficients in the slags under investigation indicated positive deviations from ideality at 1900 K and a tendency to ideal behavior at 2100 K. It was shown that the V(2)O(3) activity as a function of the slag basicity decreased at 1900 K and 2000 K and was practically constant in the slag melts at 2100 K. The results are expected to be valuable in the optimization of slag composition in high-alloy steelmaking processes as well as for their environmental implications.

High-temperature mass spectrometric study of the vaporization processes in the system CaO-MgO-Al2O3-Cr2O3-FeO-SiO2.

Knudsen effusion mass spectrometry was used to study vaporization processes and thermodynamic properties of twenty samples of chromium-containing slags in the CaO-MgO-Al2O3-Cr2O3-FeO-SiO2 system in the temperature range 1850-2750 K. Tungsten cells were used and Cr2O3 solid was used as a reference material. The system was calibrated using liquid gold. As FeO was the first emanating vapor species, monitoring of the chromium-containing species could be carried out only after the complete vaporization of FeO. This, however, was found to have very little impact on the concentration of the slags investigated. During the measurements, the ion current intensities of CrO+ and CrO2+ species in the mass spectra of the vapor over the CaO-MgO-Al2O3-Cr2O3-FeO-SiO2 samples were monitored and compared with those corresponding to solid Cr2O3. Data on the partial pressures of vapor species as well as the activities of Cr2O3 as a function of temperature were obtained. The results are expected to be valuable in the optimization of slag composition in high alloy steelmaking processes.

A mass spectrometric study of Al(2)O(3)-SiO(2) melts using a Knudsen cell.

The thermodynamic activities of SiO(2) in Al(2)O(3)-SiO(2) liquid slags were measured by the high-temperature Knudsen cell mass spectromeric method in the present work. The measurements were carried out in the temperature range 1863-2169 K. Tungsten crucibles were used to hold the slags. The system was calibrated using a CaF(2) standard. The mass spectra obtained for pure SiO(2) were in agreement with earlier data. The activities of silica, measured in the present work at 2150 K, show a slight negative deviation at very low alumina mole fractions which changed to a positive deviation at higher alumina contents. The activity values are in reasonable agreement with the assessment carried out by Hillert et al. The results were analysed on the basis of a slag model developed earlier at KTH, Stockholm. The present results are found to be compatible with the phase diagram proposed by Klug et al.