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钆(Gd)-钇(Y)-铪(Hf)氧化物体系中蒸发过程及热力学性质的高温质谱研究

High-temperature mass spectrometric study of the vaporization processes and thermodynamic properties in the Gd O -Y O -HfO system.

作者信息

Kablov Eugene N, Stolyarova Valentina L, Lopatin Sergey I, Vorozhtcov Viktor A, Karachevtsev Fedor N, Folomeikin Yuriy I

机构信息

All-Russian Research Institute of Aviation Materials, Radio st.17, 105005, Moscow, Russia.

Saint Petersburg State University, Universitetskaya nab.7/9, 199034, Saint Petersburg, Russia.

出版信息

Rapid Commun Mass Spectrom. 2017 Jul 15;31(13):1137-1146. doi: 10.1002/rcm.7892.

Abstract

RATIONALE

The refractory properties of the Gd O -Y O -HfO system are considered promising for the production of many high-temperature materials, e.g., thermal barrier coatings and casting molds for gas turbine engine blades. At high temperatures, components of the Gd O -Y O -HfO system may vaporize selectively and this may significantly change the physicochemical properties of the materials. Therefore, information on vaporization processes and thermodynamic properties of the Gd O -Y O -HfO system is of great importance.

METHODS

The vaporization processes and thermodynamic properties of the Gd O -Y O -HfO system were studied using high-temperature Knudsen effusion mass spectrometry with a MS-1301 mass spectrometer. Vaporization was carried out using a tungsten twin effusion cell containing the samples under study and pure Gd O as a reference substance. Electron ionization at an energy of 25 eV was employed in the present study.

RESULTS

It was shown that at a temperature of 2500 K the vapor over the samples in the Gd O -Y O -HfO system consisted of the GdO, YO and O vapor species. The Gd O and Y O activities in the samples in the Gd O -Y O -HfO system as well as their vaporization rates were derived from the partial pressures of the vapor species. Using these data the HfO activities, the Gibbs energy of mixing and the excess Gibbs energy in this system were calculated at 2500 K.

CONCLUSIONS

The thermodynamic properties of the Gd O -Y O -HfO system, i.e., the component activities in the samples and the excess Gibbs energy, obtained in the present study at 2500 K, exhibited negative deviations from ideal behavior. The concentration dependence of excess Gibbs energy of the Gd O -Y O -HfO system was approximated with an empirical equation. Copyright © 2017 John Wiley & Sons, Ltd.

摘要

原理

Gd₂O₃ - Y₂O₃ - HfO₂体系的耐火性能被认为在许多高温材料的生产中具有前景,例如用于燃气涡轮发动机叶片的热障涂层和铸模。在高温下,Gd₂O₃ - Y₂O₃ - HfO₂体系的组分可能会选择性蒸发,这可能会显著改变材料的物理化学性质。因此,关于Gd₂O₃ - Y₂O₃ - HfO₂体系蒸发过程和热力学性质的信息非常重要。

方法

使用配备MS - 1301质谱仪的高温努森 effusion 质谱法研究了Gd₂O₃ - Y₂O₃ - HfO₂体系的蒸发过程和热力学性质。蒸发使用一个钨双 effusion 池进行,池中装有研究样品和作为参考物质的纯Gd₂O₃。本研究采用能量为25 eV的电子电离。

结果

结果表明,在2500 K的温度下,Gd₂O₃ - Y₂O₃ - HfO₂体系样品上方的蒸气由GdO、YO和O蒸气物种组成。Gd₂O₃ - Y₂O₃ - HfO₂体系样品中的Gd₂O₃和Y₂O₃活度以及它们的蒸发速率由蒸气物种的分压推导得出。利用这些数据,计算了该体系在2500 K时的HfO₂活度、混合吉布斯自由能和过量吉布斯自由能。

结论

本研究在2500 K时获得的Gd₂O₃ - Y₂O₃ - HfO₂体系的热力学性质,即样品中的组分活度和过量吉布斯自由能,表现出与理想行为的负偏差。Gd₂O₃ - Y₂O₃ - HfO₂体系过量吉布斯自由能的浓度依赖性用一个经验方程进行了近似。版权所有© 2017 John Wiley & Sons, Ltd。

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