Sub-surface assessment of hydrothermal ageing in zirconia-containing femoral heads for hip joint applications.

Zirconia-based materials have been used in orthopaedics since the 1980s, with large success, mainly thanks to transformation toughening. On the other hand, their main drawback is their potential sensitivity to hydrothermal ageing, i.e. tetragonal to monoclinic phase transformation on their surface in the presence of water. Hydrothermal ageing may result in roughness increase and microcracking of the surface. In this article the hydrothermal ageing behaviour of three medical-grade zirconia-based materials is assessed at high temperature and extrapolated to room or body temperature. The degradation is also characterized by FIB/SEM nano-tomography to better assess sub-surface evolutions. In both zirconia and alumina-toughened zirconia (ATZ), ageing results in the presence of a homogenous transformed layer of constant thickness whose growth rate is about 8 times slower in ATZ than in zirconia. Microcracking occurs in the entire transformed layer in zirconia, but was much less relevant in ATZ. Zirconia-toughened alumina (ZTA) is much less prone to ageing. In ZTA ageing results in a thin transformed layer in which the monoclinic fraction decreases with depth. No microcracking was observed in ZTA. STATEMENT OF SIGNIFICANCE: This article details the microstructural evolution of the surface of three zirconia-based ceramics when exposed to water (hydrothermal ageing), and establishes a time-temperature equivalences of these evolutions. It shows that different zirconia-alumina composites do not degrade the same way: zirconia and alumina-toughened zirconia present a homogeneous degraded zone of constant thickness, whereas zirconia-toughened-alumina presents a gradient of transformation. These new findings will help understanding better the hydrothermal degradation of zirconia based materials, and in particular will facilitate a better prediction of the durability of zirconia-based devices such as orthopaedic implants and dental devices (implants, crowns, abutments…).

[PVD-silicoating before cementation of zirconia-based knee prostheses effects better cement adhesion and lower aseptic loosening rates]. / PVD-Silikat-Beschichtung für die verbesserte Zementhaftung auf Endoprothesen aus ATZ-Dispersionskeramik.

AIM: CoCrMo alloys are contraindicated for allergy patients. For these patients, cemented or uncemented prostheses made of titanium alloy are indicated. Uncemented prostheses, however, have low primary retention, particularly the tibial components of knee joint prostheses because of the lack of a positive locking. Therefore, for knee replacement cemented CoCrMo prostheses may be suitable also for allergy sufferers if these are masked by ZrN or TiNbN layers. Alternatively the CoCrMo alloy may be replaced by high-strength oxide ceramics. For adhesion of bone cement to the ceramic surface, however, only inefficient mechanical retention spots are exposed as compared with a metal surface. Undercuts generated by corundum blasting, although highly efficient on a CoCrMo surface, are not such efficient centres on a ceramic surface due to its brittleness. Therefore, the mechanical component of retention is significantly reduced. When specific adhesion between bone cement and surface does not exist due to physical and chemical forces, the hydrolytic stability will be insufficient. Micromotions are promoted and early aseptic loosening is predictable. Silicoating of the ceramic surface will allow specific adhesion and can result in better hydrolytic stability of bonding. METHODS: In order to evaluate the effectiveness of silicoating the bond strengths of blasted (mean size of corundum grains 50 µm) and silicate layered alumina-toughened zirconia (ATZ) surfaces were compared with "as fired" surfaces by utilising TiAlV probes (diameter 6 mm) for traction-adhesive strength testing. Samples machined out of CoCrMo alloy were utilised for reference. After preparing the samples for traction-adhesive strength testing (sequence: substrate, silicate and silane, protective lacquer [PolyMA], bone cement, TiAlV probe) they were aged up to 360 days at 37 °C in Ringer's solution. RESULTS: The bond strengths observed for all ageing intervals were well above 20 MPa and much higher and more hydrolytically stable for blasted and silicate-layered compared with "as fired" ATZ samples. CONCLUSION: Silicoating may be effective for achieving a high initial bond strength of bone cement on surfaces of oxide ceramics and also suitable to stabilise bond strength under hydrolytic conditions as present in the human body. Activation by low grain size corundum (mean grain size 50 µm) seems to be effective for activation without deteriorating the bending strength of the ceramics investigated. Due to the proposed layer system migration, micromotions and debonding should be widely reduced or even eliminated.