Collaborative research: experimental and computational study of structure and thermodynamics of rare earth oxides above 2000 C

合作研究：2000℃以上稀土氧化物结构和热力学的实验和计算研究

• 批准号: 1835939
• 负责人: Axel van de Walle
• 金额: $ 21.38万
• 依托单位: Brown University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2018
• 资助国家: 美国
• 起止时间: 2018-07-01 至 2022-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1835939&HistoricalAwards=false
• 关键词: Collaborative; research; experimental; computational; study

NON-TECHNICAL DESCRIPTION: Materials that can withstand ultrahigh temperatures are important to ceramic processing, aerospace, and nuclear applications. Oxides containing rare earth elements have high melting points, do not evaporate easily, and are generally chemically unreactive. This refractory nature favors high temperature applications, but at the same time makes the determination of their heat and energy relationships (thermodynamic) properties challenging, and current data are incomplete. Such data are essential for prediction of material stability or degradation during use in both simple and complex systems in a variety of extreme environments (such as high-temperature or high-pressure environments). New experimental and computational approaches to determine thermodynamics above 2000 degrees C form the primary focus of the project, which represents collaboration between Navrotsky's group at University of California at Davis performing thermochemical measurements and structural studies, and van de Walle's group at Brown University undertaking calculations and phase diagram assessments. The project provides university-level students an opportunity to participate in state-of-the-art experimental and computational research applied to high temperature processes. TECHNICAL DETAILS: The goals are to develop, test and apply new methodology (i) to determine temperatures and heats of phase transitions (both solid-solid and melting) of rare earth oxides and oxycarbides above 2000 degrees C, (ii) to measure structural parameters, including thermal expansion and volume change upon phase transition by synchrotron X-ray diffraction on levitated samples above 1500 degrees C, (iii) to calculate high-temperature thermodynamic properties using ab initio density functional theory (with hybrid functionals) and molecular dynamics in conjunction with statistical mechanical techniques, and (iv) to generate a unified picture, based on both theory and experiment, of thermodynamic properties, to be made publicly available for use in calculation of phase diagrams (CalPhaD) modeling and other applications. The combination of calorimetry, X-ray diffraction, and computation provides both needed thermodynamic data and physical insight into the properties of refractory rare earth oxides, with extensions into more complex systems. In addition to international journals and meetings on ceramics, dissemination is taking place through smaller focused conferences and lectures on their websites. Newly developed ab initio computational techniques are being integrated within the widely used and freely distributed ATAT software.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

非技术描述：能够承受高温的材料对于陶瓷加工、航空航天和核应用都很重要。含有稀土元素的氧化物具有高熔点，不易蒸发，并且通常不发生化学反应。这种耐火性质有利于高温应用，但同时使其热和能量关系（热力学）性质的确定具有挑战性，并且目前的数据不完整。这些数据对于预测材料在各种极端环境（如高温或高压环境）中用于简单和复杂系统时的稳定性或降解至关重要。新的实验和计算方法来确定2000摄氏度以上的热力学形成该项目的主要焦点，这代表了Navrotsky在戴维斯的加州大学进行热化学测量和结构研究的小组之间的合作，以及布朗大学的货车de Walle小组进行计算和相图评估。该项目为大学生提供了一个参与应用于高温过程的最先进的实验和计算研究的机会。技术规格：目标是开发、测试和应用新的方法（i）确定相变的温度和热量（ii）在高于2000摄氏度的温度下测量稀土氧化物和碳氧化物的结构参数，包括在高于1500摄氏度的温度下通过同步加速器X射线衍射对悬浮样品进行相变时的热膨胀和体积变化，（iii）使用从头算密度泛函理论计算高温热力学性质（与混合泛函）和分子动力学结合统计力学技术，和（iv）产生一个统一的图片，基于理论和实验，热力学性质，公开用于相图计算（CalPhaD）建模和其他应用。 量热法，X射线衍射和计算的结合提供了所需的热力学数据和对难熔稀土氧化物性质的物理见解，并扩展到更复杂的系统。除了关于陶瓷的国际期刊和会议外，还通过其网站上的小型重点会议和讲座进行传播。新开发的从头计算技术正在被广泛使用和免费分发的ATAT软件中集成。该奖项反映了NSF的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

Reentrant melting of sodium, magnesium, and aluminum: General trend

• DOI: 10.1103/physrevb.100.140102
• 发表时间: 2019-10
• 期刊: Physical Review B
• 影响因子: 3.7
• 作者: Qi-Jun Hong;A. van de Walle

Energetics of melting of Yb2O3 and Lu2O3 from drop and catch calorimetry and first principles computations

• DOI: 10.1016/j.jct.2019.01.008
• 发表时间: 2019-05-01
• 期刊: JOURNAL OF CHEMICAL THERMODYNAMICS
• 影响因子: 2.6
• 作者: Fyhrie, Matthew;Hong, Qi-Jun;Navrotsky, Alexandra
• 通讯作者: Navrotsky, Alexandra

A simple method for computing the formation free energies of metal oxides

• DOI: 10.1016/j.commatsci.2021.110692
• 发表时间: 2021-10
• 期刊: Computational Materials Science
• 影响因子: 3.3
• 作者: Hantong Chen;Qi-Jun Hong;S. Ushakov;A. Navrotsky;A. Walle

Software tools for thermodynamic calculation of mechanically unstable phases from first-principles data

• DOI: 10.1016/j.cpc.2019.01.008
• 发表时间: 2020-01-01
• 期刊: COMPUTER PHYSICS COMMUNICATIONS
• 影响因子: 6.3
• 作者: Kadkhodaei, Sara;van de Walle, Axel
• 通讯作者: van de Walle, Axel