Stolyarova Valеntina L, Shilov Andrey L, Lopatin Sergey I, Vorozhtcov Viktor A, Yurchenko Dmitrii A, Knyazyan Nikolay B, Manukyan Goharik G
Saint Petersburg State University, Saint Petersburg, Russia.
Institute of Silicate Chemistry of the Russian Academy of Sciences, Saint Petersburg, Russia.
Rapid Commun Mass Spectrom. 2023 Feb 15;37(3):e9433. doi: 10.1002/rcm.9433.
Materials based on the Al O -SiO -ZrO system are promising for a wide range of high-temperature technological applications, such as thermal barrier coatings in the aviation and space industry or advanced materials in nuclear power reactors. Experimental studies of the ceramics based on this system by the Knudsen effusion mass spectrometric (KEMS) method are of significant interest in designing technological processes for the synthesis and exploitation of the Al O -SiO -ZrO materials.
Samples of ceramics in the Al O -SiO -ZrO system, including the Al O -ZrO and SiO -ZrO binaries, were prepared by solid-state synthesis. Analysis of the samples was performed by X-ray fluorescence and diffraction techniques. The vapor composition and thermodynamic properties of the components in this system were determined by KEMS. The derived thermodynamic functions were optimized within the generalized lattice theory of associated solutions (GLTAS).
In the temperature range 1900-2600 K, the SiO, Al, AlO, Al O, ZrO, ZrO , and O vapor species were identified over the samples in the systems under study. For the thermodynamic properties to be determined correctly, the samples of the Al O -SiO -ZrO system had to be vaporized at temperatures less than 2000 K, where data could be obtained only for the SiO species. The SiO activities obtained were taken as the experimental basis for the modeling within the GLTAS approach. This allowed evaluation of the component activities and excess Gibbs energy, and assessment of the relative number of bonds of different types.
At 1920 K, the Al O -SiO -ZrO system is characterized by negative deviations of its thermodynamic properties from the ideal behavior. The consistency of the obtained modeling results was illustrated by comparison of the values derived from the data for the ternary and the boundary binary systems and thereby indicates the reasonable uniformity of the energy parameters of the lattice model derived in the calculations, which may be used in further modeling of multicomponent systems.
基于Al₂O₃ - SiO₂ - ZrO₂体系的材料在广泛的高温技术应用中具有广阔前景，例如航空航天工业中的热障涂层或核电反应堆中的先进材料。通过克努森喷射质谱（KEMS）方法对基于该体系的陶瓷进行实验研究，对于设计Al₂O₃ - SiO₂ - ZrO₂材料的合成与应用工艺具有重要意义。
采用固态合成法制备了Al₂O₃ - SiO₂ - ZrO₂体系的陶瓷样品，包括Al₂O₃ - ZrO₂和SiO₂ - ZrO₂二元体系。通过X射线荧光和衍射技术对样品进行分析。利用KEMS测定该体系中各组分的蒸汽组成和热力学性质。在缔合溶液广义晶格理论（GLTAS）范围内对导出的热力学函数进行优化。
在1900 - 2600 K温度范围内，在所研究体系的样品上鉴定出了SiO、Al、AlO、Al₂O、ZrO、ZrO₂和O蒸汽物种。为了正确测定热力学性质，Al₂O₃ - SiO₂ - ZrO₂体系的样品必须在低于2000 K的温度下蒸发，在此温度下只能获得SiO物种的数据。所获得的SiO活度被用作GLTAS方法建模的实验基础。这使得能够评估组分活度和过量吉布斯自由能，并评估不同类型键的相对数量。
在1920 K时，Al₂O₃ - SiO₂ - ZrO₂体系的热力学性质表现出相对于理想行为的负偏差。通过比较从三元体系和边界二元体系数据得出的值，说明了所获得的建模结果的一致性，从而表明计算中导出的晶格模型能量参数具有合理的一致性，可用于多组分体系的进一步建模。
