title: Size-dependent phase diagrams of metallic alloys: A Monte Carlo simulation study on order-disorder transitions in Pt-Rh nanoparticles.
abstract: Nanoparticles of Pt-Rh were studied by means of lattice-based Monte Carlo simulations with respect to the stability of ordered D0(22)- and 40-phases as a function of particle size and composition. By thermodynamic integration in the semi-grand canonical ensemble, phase diagrams for particles with a diameter of 7.8 nm, 4.3 nm and 3.1 nm were obtained. Size-dependent trends such as the lowering of the critical ordering temperature, the broadening of the compositional stability range of the ordered phases, and the narrowing of the two-phase regions were observed and discussed in the context of complete size-dependent nanoparticle phase diagrams. In addition, an ordered surface phase emerges at low temperatures and low platinum concentration. A decrease of platinum surface segregation with increasing global platinum concentration was observed, when a second, ordered phase is formed inside the core of the particle. The order-disorder transitions were analyzed in terms of the Warren-Cowley short-range order parameters. Concentration-averaged short-range order parameters were used to remove the surface segregation bias of the conventional short-range order parameters. Using this procedure, it was shown that the short-range order in the particles at high temperatures is bulk-like.
authors.affiliation: Institut für Materialwissenschaft, Technische Universität Darmstadt, Petersenstr. 32, D-64287 Darmstadt, Germany.
authors.forename: Johan
authors.initials: J
authors.lastname: Pohl
authors.forename: Christian
authors.initials: C
authors.lastname: Stahl
authors.forename: Karsten
authors.initials: K
authors.lastname: Albe