High-Temperature Chemistry Applications of Mass Spectrometry

Sidorov, L.N.; Lopatin, S.I.

doi:10.1016/b978-0-12-409547-2.05239-2

Cited by 2 publications

(3 citation statements)

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“…Another reason may be sintering of the sample powders being kept for a long time at such high temperatures, which changes the state of the sample surface and rate of transition into the gaseous phase. These limitations of the complete isothermal vaporization method, that were discussed in more detail previously, are more pronounced for ternary systems since it has repeatedly been shown that, in the binary systems, the data determined for samples directly and based on the vaporization isotherms are in agreement within experimental uncertainty. Thus, the results obtained from the vaporization isotherm of sample N 1 (Figure ) should be regarded as estimated, and the data determined for samples NN 2–4 directly are to be preferred.…”

Section: Resultsmentioning

confidence: 97%

“…% Y 2 O 3 , and 25 mol. % HfO 2 , was examined by the complete isothermal vaporization method . This allowed the determination of not only changes in the condensed phase of the sample when it was kept isothermally at a high temperature (Equation ) but also the partial pressures of the vapor species for the compositions obtained during vaporization:

q_{i} = italicksL \sqrt{\frac{{TM}_{i}}{2 π R}} \int_{0}^{t} I ((), i) italicdt,

where L is the Clausing coefficient, s is the area of the effusion orifice, and q i is the mass of the sample that vaporized at temperature T during vaporization time t in the form of the i vapor species with the mole mass M i .…”

Section: Methodsmentioning

confidence: 99%

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Vaporization and thermodynamics of ceramics in the Sm₂O₃‐Y₂O₃‐HfO₂ system

Каблов

Stolyarova

Vorozhtcov

et al. 2020

Rapid Comm Mass Spectrometry

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Rationale The Sm2O3‐Y2O3‐HfO2 system holds promise for applications in the sphere of high‐temperature technologies, particularly the development of ultra‐high‐temperature ceramics. However, the reliability of refractory materials is dependent on the possible selective vaporization of their components leading to changes in their physicochemical properties. Thus, information about vaporization processes and thermodynamic properties of ceramics based on the Sm2O3‐Y2O3‐HfO2 system may be of importance for the production of high‐temperature materials as well as for the prediction of the physicochemical properties of ultra‐high‐temperature ceramics. Methods The Knudsen effusion mass spectrometric method was used, with an MS‐1301 magnetic mass spectrometer equipped with a tungsten twin effusion cell used to examine the samples in the Sm2O3‐Y2O3‐HfO2 system. Electron ionization of vapor species effusing from the cell was carried out at an ionization energy of 25 eV. Results It was shown that at a temperature of 2373 K, selective vaporization of Sm2O3 and Y2O3 occurred in the samples of the Sm2O3‐Y2O3‐HfO2 system, with the main vapor species being SmO, Sm, YO, and O. The partial pressures of these vapor species were obtained by the ion current comparison method. The Sm2O3 activities in the Sm2O3‐Y2O3‐HfO2 system were determined and allowed the evaluation of the excess Gibbs energies at 2373 K. The direction of change of the condensed phase of the samples because of selective vaporization of the components was examined. Conclusions The Sm2O3‐Y2O3‐HfO2 system was characterized by negative deviations from the ideal behavior at 2373 K. The excess Gibbs energies evaluated in the present study were approximated using the Redlich‐Kister representation and visualized in the form of curves of constant values in the concentration triangle. The data obtained in the Sm2O3‐Y2O3‐HfO2 system were optimized using the Barker‐Guggenheim theory of associated solutions.

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Section: Resultsmentioning

confidence: 97%

q_{i} = italicksL \sqrt{\frac{{TM}_{i}}{2 π R}} \int_{0}^{t} I ((), i) italicdt,

Section: Methodsmentioning

confidence: 99%

Vaporization and thermodynamics of ceramics in the Sm₂O₃‐Y₂O₃‐HfO₂ system

Каблов

Stolyarova

Vorozhtcov

et al. 2020

Rapid Comm Mass Spectrometry

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“…The instrument was calibrated on pressure in each experiment by a procedure based on the isothermal evaporation method. 24 In accordance with this, the sensitivity constant of the mass spectrometer can be determined using the Hertz-Knudsen equation in the following form:…”

Section: Introductionmentioning

confidence: 99%

Thermodynamics of heterogeneous equilibria in the In–In₂O₃ system using Knudsen effusion mass spectrometry

Smirnov

Грибченкова

Alikhanyan

2022

Rapid Comm Mass Spectrometry

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RATIONALEThe In–In2O3 system is regarded as a potential low‐temperature source of gaseous indium oxide (In2O) when obtaining functional materials by physical vapor deposition techniques. To date the vaporization thermodynamics of the system have been investigated in few studies, the results of which are contradictory.METHODSThe study of the In–In2O3 system was performed using Knudsen effusion mass spectrometry in the temperature range 930–1210 K, with a magnet mass spectrometer (MS‐1301). Quartz effusion cells heated by a resistance furnace were employed.RESULTSIt was established that In(g) and In2O(g) are the major vapor species over heterogeneous mixtures (In(l) + In2O3(s)) and the gaseous oxide In2O is predominant. The partial pressures of the vapor species were determined and the quantitative vapor composition was calculated. Based on the experimental data, a p–x section of the In–In2O3 system phase diagram at 1060 K was constructed. The standard enthalpies of reactions accompanying vaporization of the In and In2O3 mixtures were evaluated using the second‐ and third‐law methods. The standard enthalpy of formation of In2O(g) was derived from the enthalpies of reactions obtained.CONCLUSIONSThe predominance of In2O in the equilibrium vapor over heterogeneous mixtures (In(l) + In2O3(s)), along with its high partial pressure at relatively low temperatures, substantiate the In–In2O3 system to be suitable for physical vapor deposition methods. The obtained results can be used for physical vapor deposition parameter adjustment and optimization. The standard enthalpy of formation of In2O(g) obtained in an independent way in the present work is in good agreement with that from our previous In2O3(s) vaporization study.

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High-Temperature Chemistry Applications of Mass Spectrometry

Cited by 2 publications

References 9 publications

Vaporization and thermodynamics of ceramics in the Sm₂O₃‐Y₂O₃‐HfO₂ system

Vaporization and thermodynamics of ceramics in the Sm₂O₃‐Y₂O₃‐HfO₂ system

Thermodynamics of heterogeneous equilibria in the In–In₂O₃ system using Knudsen effusion mass spectrometry

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High-Temperature Chemistry Applications of Mass Spectrometry

Cited by 2 publications

References 9 publications

Vaporization and thermodynamics of ceramics in the Sm2O3‐Y2O3‐HfO2 system

Vaporization and thermodynamics of ceramics in the Sm2O3‐Y2O3‐HfO2 system

Thermodynamics of heterogeneous equilibria in the In–In2O3 system using Knudsen effusion mass spectrometry

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Vaporization and thermodynamics of ceramics in the Sm₂O₃‐Y₂O₃‐HfO₂ system

Vaporization and thermodynamics of ceramics in the Sm₂O₃‐Y₂O₃‐HfO₂ system

Thermodynamics of heterogeneous equilibria in the In–In₂O₃ system using Knudsen effusion mass spectrometry