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In this paper, an updated analytical model for the kinetics of the tetragonal to monoclinic ( t → m ) polymorphic transformation in ZTA composites for hip joints is proposed and discussed. The model builds upon the so-called Mehl-Avrami-Johnson (MAJ) description of transformation kinetics, which combines two overlapping processes: nucleation of monoclinic sites, and their successive growth. Dependencies on two specific factors are introduced in the model, namely the initial fraction of monoclinic polymorph as received from the manufacturer, and the presence of different types of transition-metal stains ( e.g. , Ti, CoCr, and Fe) on the ZTA surface. These two factors were studied because clear indications of their potential roles on the environmental stability of implantable ZTA components were found in previous phenomenological analyses of retrievals. Nucleation and growth of monoclinic domains are two key processes whose interplay decides the actual kinetics of the overall transformation process according to two main parameters: an apparent activation energy value function of time and temperature, and a nuclei growth exponent. These parameters were clearly altered by the presence of transition metal contamination, whose effect was incorporated into the model to explain exacerbations of surface degradation. In accordance with a general analytical description of transformation kinetics for isothermal or isochronal evolutions in terms of time and temperature, the modified model of the MAJ description assesses the effect of the initial monoclinic fraction. The updated model has been validated using systematic in vitro experiments, and appears to partly reconcile in vitro and in vivo data of t → m transformation discrepancies in ZTA hip components. [ABSTRACT FROM AUTHOR]

Understanding the intrinsic reason(s) for the enhanced tetragonal to monoclinic ( t → m ) polymorphic phase transformation observed on metal-stained surfaces of zirconia-toughened alumina (ZTA) requires detailed knowledge of off-stoichiometry reactions at the molecular scale. In this context, knowledge of the mechanism(s) for oxygen vacancy creation or annihilation at the material surface is a necessary prerequisite. The crucial aspect of the surface destabilization phenomenon, namely the availability of electrons and holes that allow for vacancy creation/annihilation, is elucidated in this paper. Metal-enhanced alterations of the oxygen sublattice in both Al 2 O 3 and ZrO 2 of the ZTA composite play a decisive role in accelerating the polymorphic transformation. According to spectroscopic evidences obtained through nanometer-scale analyses, enhanced annihilation of oxygen vacancies triggers polymorphic transformation in ZrO 2 near the metal stain, while the overall Al 2 O 3 lattice tends to dehydroxylate by forming oxygen vacancies. A mechanism for chemically driven “reactive metastability” is suggested, which results in accelerating the polymorphic transformation. The Al 2 O 3 matrix is found to play a key-role in the ZrO 2 transformation process, with unambiguous confirmation of oxygen and hydrogen transport at the material surface. It is postulated that this transport is mediated by migration of dissociated O and H elements at the surface of the stained transition metal as they become readily available by the thermally activated surrounding. [ABSTRACT FROM AUTHOR]