论文标题
计算相位平衡的灵敏度估计
Sensitivity estimation for calculated phase equilibria
论文作者
论文摘要
对于通过新模型和实验的不确定性降低，必须开发一致的calphad模型灵敏度框架。在目前的工作中，开发了对calphad的灵敏度理论，并提出了对数可能性梯度的封闭式表达，并提出了多相平衡测量的Hessian。通过使用蒙特卡洛平均，可以减轻定义灵敏度度量的固有位置。使用CR-NI系统的案例研究被用来证明由发达的理论启用的可视化和分析。基于经典Cramér-Rao结合的标准被证明是评估来自马尔可夫链蒙特卡洛的参数协方差估计准确性的有用诊断。与热化学测量相比，开发的灵敏度框架用于估计相位平衡测量值的统计值，这对Calphad模型不确定性的降低含义。
The development of a consistent framework for Calphad model sensitivity is necessary for the rational reduction of uncertainty via new models and experiments. In the present work, a sensitivity theory for Calphad was developed, and a closed-form expression for the log-likelihood gradient and Hessian of a multi-phase equilibrium measurement was presented. The inherent locality of the defined sensitivity metric was mitigated through the use of Monte Carlo averaging. A case study of the Cr-Ni system was used to demonstrate visualizations and analyses enabled by the developed theory. Criteria based on the classical Cramér-Rao bound were shown to be a useful diagnostic in assessing the accuracy of parameter covariance estimates from Markov Chain Monte Carlo. The developed sensitivity framework was applied to estimate the statistical value of phase equilibria measurements in comparison with thermochemical measurements, with implications for Calphad model uncertainty reduction.
