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

Abstract

RATIONALEThe 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.METHODSHigh‐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.RESULTSPb, 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.CONCLUSIONSPartial 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. Copyright © 2013 John Wiley & Sons, Ltd.