First-principles calculations of binary Al compounds: Enthalpies of formation and elastic properties

Systematic first-principles calculations of energy vs. volume (E-V) and single crystal elastic stiffness constants (c_ij’s) have been performed for 50 Al binary compounds in the Al-X (X = Co, Cu, Hf, Mg, Mn, Ni, Sr, V, Ti, Y, and Zr) systems. The E-V equations of state are fitted by a four-parameter Birch-Murnaghan equation, and the c_ij’s are determined by an efficient strain-stress method. The calculated lattice parameters, enthalpies of formation, and c_ij’s of these binary compounds are compared with the available experimental data in the literature. In addition, elastic properties of polycrystalline aggregates including bulk modulus (B), shear modulus (G), Young’s modulus (E), B/G (bulk/shear) ratio, and anisotropy ratio are calculated and compared with the experimental and theoretical results available in the literature. The systematic predictions of elastic properties and enthalpies of formation for Al-X compounds provide an insight into the understanding and design of Al-based alloys.     

Effects of pressure and vibration on the thermal decomposition of cubic Ti1-x Al x N, Ti1-x Zr x N, and Zr1-x Al x N coatings: a first-principles study

Thermodynamic properties as well as the miscibility gap (binodal) and spinodal decompositions of the cubic Ti_1-x Al _x N, Ti_1-x Zr _x N, and Zr_1-x Al _x N coating alloys have been computed using first-principles calculations. Herein, the cluster expansion method and especially the special quasirandom structure are employed to describe the disordered alloys. The effects of pressure and lattice vibration on the miscibility gaps and spinodal decompositions of the above alloys have been investigated by means of Helmholtz free energy with the vibrational contribution depicted with the Debye-Grüneisen model. It is found that the application of hydrostatic pressure promotes the isostructural decomposition of Ti_1-x Al _x N, Ti_1-x Zr _x N, and Zr_1-x Al _x N alloys, whereas the vibrational contribution decreases the consolute temperature of the phase separation. Our results indicate that the improved age-hardening behavior of cubic Ti_1-x Al _x N coatings with the addition of Zr arises from the enlarged composition range of binodal and spinodal curves at specified temperatures. Our results are in good agreement with the available experimental data and provide a useful insight into the investigation of age-hardening and characterization of Ti–Al–Zr–N-based coatings for high-temperature applications.     

Thermodynamic Assessment of the Ag-Se System Aided by First-Principles Calculations

The substitution of Ag for Cu in CuIn_xGa_1?xSe₂-based photovoltaic absorber layers can be used to adjust the bandgap energy to better optimize the overall cell efficiency. Based on available thermochemical, equilibrium, and structural data, the Ag-Se system has been assessed and modeled. Given the order-disorder structure transition Ag₂Se, the 2- and 3-sublattice models were used to represent the low- and high-temperature phases of the intermetallic compound respectively. Density functional theory based first-principles calculations were used to calculate the Gibbs energy of formation of the end-member compounds. A set of modeling parameters was obtained by the CALculation of PHAse Diagram approach and reasonable agreement was obtained between the experimental thermodynamic properties of the stable phases and the phase relationships in the Ag-Se system.     

Summary of the CALPHAD XXXVI 2007 conference

From 6–11 May 2007, 147 registered participants met at State College, Pennsylvania, for the thirty-sixth CALPHAD meeting organized by Zi-Kui Liu, Steve Hansen, Joanne Murray and Phillip Spencer. Activities were held at Toftrees Golf Resort and Conference Center with logistics run by graduate students and postdoctoral fellows from The Pennsylvania State University. Over the course of six days, 57 oral presentations and 84 posters were offered, the abstracts and titles of which are summarized in this report. Posters were on display from Sunday evening until Friday morning. In addition to the continuous display of the posters, two dedicated poster sessions were held in the Monday and Tuesday evenings, which were overwhelmingly enjoyed by the participants.

The CALPHAD Gibbs Triangle Award, an honor given only every three to five years, was bestowed upon Gunnar Eriksson. Fourteen CALPHAD scholarships were awarded to promising students in the field, the Best Paper Award for papers published in 2006 in the CALPHAD journal was conferred, and a Best Poster Award was chosen for one of the conference’s posters.     

Revisiting the Phase Stability in Ni-X (X=Mo,Ti, In) Systems Using Ab Initio Calculations

In this paper, we report a theoretical prediction of the low-temperature phase diagrams for the Ni-Mo, Ni-Ti and Ni-In binary systems using ab initio evolutionary methodology. Our study uncovers two previously unreported intermetallic compounds that are thermodynamically stable at low temperatures: orthorhombic Ni₂Mo with Cmcm symmetry and tetragonal NiTi₂ with I4/mmm symmetry. Ni₂Mo and NiTi₂ will transform from their zero temperature ground state structures into their experimentally observed high temperature polymorphs above a critical temperature of 466 and 912 K, respectively. Finally, our DFT calculations with both PBE and LDA functional indicate that the experimentally observed Ni₃In, Ni₂In and Ni₁₃In₉ structures are all not stable at low temperature. Furthermore, no Ni₃In and Ni₂In structures that are stable at T?=?0 K can be identified by our evolutionary search.     

Thermodynamic Modeling of the Succinonitrile-Water System

Succinonitrile-water (SCN-H₂O) system is a widely used transparent metallic alloy system due to its analog solidification behavior to metals. In the present work, Gibbs energy of pure succinonitrile was derived utilizing temperature as well as enthalpy of transformations, and temperature dependencies of heat capacity available in the literature. The phase diagram for the binary SCN-H₂O system was assessed via the CALPHAD approach using phase equilibrium data available in the literature. Self-consistent thermodynamic parameters were obtained. A good agreement between the experimental and calculated data for the phase diagram has been achieved. The present work contributes to the development of the thermodynamic database of the SCN-H₂O system that can be incorporated into thermodynamic and kinetic codes for computational simulations.