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    ZrO2 Phase Transition PDF

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    ZrO2 Phase Transition PDF

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    ZrO2 Phase Transition PDF

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    APPLICATION NOTE

    Temperature-Dependent Phase Transitions of ZrO2


    The temperature-induced phase transition from monoclinic to tetragonal ZrO2 is predicted from
    first principles calculations using a quasi-harmonic approach for the vibrational enthalpy and
    entropy. The computed transition temperature is within 15% of the experimental value. Relative
    trends due to vacancies, alloying elements, and mechanical stress can be expected to have a higher
    accuracy. The present results show the importance of thermal expansion, which is here also
    obtained from first principles.

    Keywords: zirconia, phase transition, computations, first-principles, phonon, vibrations,


    entropy, thermal expansion

    Experimental Facts tetragonal structure becomes thermodynamically


    stable. At 2650 K the tetragonal structure
    At low temperatures, the most stable phase of
    changes into a cubic calcium fluoride structure.
    ZrO2 is a monoclinic form, which occurs
    The mineral name zirconia is used for both the
    naturally as the mineral Baddeleyite. At a
    tetragonal and the cubic structures. ZrO2 melts
    temperature of 1478 K and ambient pressure, a
    at 2983 K (cf. Fig. 1).

    cubic 2650 K

    1478 K
    tetragonal

    monoclinic

    Figure 1. O-Zr phase diagram (after Ref. 1) and structures of ZrO2 in the room temperature (rt)
    monoclinic phase, the high temperature (ht1) tetragonal phase and the high temperature (ht2) cubic
    phase. The phase transitions are observed at 1205 C (1478 K) and 2377 C (2650 K).

    Copyright Materials Design 2009


    Materials Design Application Note Phase Transitions in ZrO2

    Figure 2. Difference in the free energy of the low-temperature monoclinic and the high-
    temperature tetragonal phases of zironia. The solid red line includes effects of thermal
    expansion. The results shown as dashed line use the computed lattice parameters at T=0 K.

    Computed results accurately described than the absolute value of a


    transition temperature.
    The present first-principles calculations
    correctly predict the monoclinic phase of ZrO2
    to be more stable at low temperatures with the
    tetragonal phase becoming more favorable at MedeA modules used for this application
    high temperatures. The computed transition
    The present calculations were performed with
    temperature is 1700 K compared with an the MedeA platform using the following
    experimental value of 1478 K. This deviation of integrated modules of the MedeA software
    15% is a respectable result given the subtle environment
    nature of temperature-induced phase transitions.
    Standard MedeA framework including
    crystal structure builders and geometric
    Significance analysis tools as well as JobServer and
    TaskServers
    The ability to predict temperature-dependent
    phase transitions with a first-principles method InfoMaticA with structural databases
    opens the door for systematic studies of the (ICSD, Pearson, Pauling) in this case each
    effect of vacancies, dopants, and external strains of these databases contains the various
    on the transition temperature providing useful phases of ZrO2
    materials property data as well as insight into
    VASP 4.6 and its graphical user interface as
    the role and mechanism of vacancies, doping,
    integrated in MedeA
    and mechanical load. Relative trends such as
    stress-induced changes are likely to be more Phonon as integrated in MedeA

    -2-
    Materials Design Application Note Phase Transitions in ZrO2

    Comments calculation of the vibrational entropy is critical.


    This task is accomplished with the MedeA-
    The phase transition of ZrO2 from the
    Phonon module, which computes the full
    monoclinic to the tetragonal structure is driven
    phonon dispersions of crystalline structures.
    by vibrational entropy. For a given temperature
    Integration over all phonon branches gives a
    the vibrational entropy of the tetragonal phase is
    phonon density of states, which leads directly to
    larger than that of the monoclinic phase. The
    the temperature-dependent terms of the
    electronic energy of the monoclinic phase is
    enthalpy, the zero-point energy, and the
    lower than that of the tetragonal phase even if
    vibrational entropy as a function of temperature.
    the lattice expands. Therefore, an accurate
    These results are shown in Fig. 3.

    Figure 2. Phonon dispersions and phonon densities of states for monoclinic and tetragonal
    ZrO2 computed from first-principles using MedeA with VASP and Phonon. Note that the
    monoclinic phase shows higher frequencies than the tetragonal phase.

    dependent functions of the enthalpy and entropy


    The coefficient of thermal expansion for the two
    are then used to include the effects of thermal
    phases of zirconia are obtain from a series of
    expansion.
    electronic structure and phonon calculations for
    different lattice parameters. Minimization of the
    The high-temperature cubic phase is
    free energy for each temperature gives an
    dynamically stabilized by cooperative
    equilibrium lattice parameter for that
    displacements of chains of oxygen atoms
    temperature. The computed temperature-
    oscillating in a double-well potential. The

    -3-
    Materials Design Application Note Phase Transitions in ZrO2

    prediction of this second phase transition is References


    more complicated and requires a theoretical 1. Binary Alloy Phase Diagrams, Second Edition,
    approach beyond the quasi-harmonic Ed. T. B. Massalski, ASM International, Materials
    approximation used in the present work. Park, Ohio (1990) 3, 2940-2941 as implemented
    in the Pauling File Binaries Edition, Version 1.0,
    The approach outlined in this application note Release 2002/1, P. Villars (editor-in-chief)
    has recently been used by the group of Prof. Isao
    2. A. Kuwabara, T. Tohei, T. Yamamoto, and I.
    Tanaka at Kyoto University as described in Ref. Tanaka, Ab initio lattice dynamics and phase
    [2]. transformations of ZrO2, Phys. Rev. B 71,
    064301 (2005)

    For further information please contact


    Materials Design, Inc.
    PO Box 2000,
    3465 Mountain View Blvd. #17
    Angel Fire, NM 87710, USA
    T +1 760 495-4924
    F +1 760 897-2179
    info@materialsdesign.com
    www.materialsdesign.com

    -4-

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