Sensitivity estimation for calculated phase equilibria

The development of a consistent framework for Calphad model sensitivity is necessary for the rational reduction of uncertainty via new models and experiments. A sensitivity theory for Calphad was developed, and a closed-form expression for the log-likelihood gradient and Hessian of a phase coexistence 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 uncertainty reduction.