Alumina, Zirconia and Their Composite Ceramics with Properties Tailored for Medical Applications

Although in 1977 the first ceramic composite material had been introduced into the market, it was a long time before composite materials were qualified for medical applications. For a long period high purity alumina ceramics have been used as ball-heads and cups. Because of their brittleness, in 1986 yttria stabilized zirconia has been introduced into this application, because of higher strength and fracture toughness. However, due to its hydrothermal instability this material disappeared in orthopaedic applications in 2000. Meanwhile a composite materials based on an alumina matrix with dispersed metastable tetragonal zirconia particles and in-situ formed hexagonal platelets became the standard material for ceramic ball-heads, because of their excellent mechanical strength, hardness and improved fracture toughness. Especially fracture toughness can be improved further by special material formulations and tailored microstructure. It has been shown that a mixed stabilisation of zirconia by yttria and ceria with dispersed alumina and hexagonal platelets overcomes the hydrothermal instability and excellent materials properties can be achieved. Such materials do have big potential to be used in dental applications. Furthermore, these materials also can be seen as a new generation for ball-heads, because of their enhanced fracture toughness. All materials are described within these articles. In order to achieve the required properties of the materials, special raw materials are required. Therefore, it is quite important to understand and know the raw material manufacturing procedures.

Carbon Vacancy Ordered Non-Stoichiometric ZrC0.6

The starting nanopowders of non-stoichiometric zirconium carbide (ZrCx) were fabricated via milling Zr powders in toluene for different dwell times. The carbon content was determined to depend on the milling time and the used amount of toluene. The bulk non-stoichiometric ZrCx with different x were prepared by spark plasma sintering of the obtained ZrCx nanopowders. The microstructural features of a sintered ZrC0.6 sample were investigated via the measurements of XRD, TEM, and HRTEM. It was found that the carbon vacancies have an ordering arrangement in C sublattice, forming a Zr2C-type cubic superstructural phase with space group of . Moreover, it was observed that the superstructural phase exists in nano-domains with an average size of ~30 nm owing to the ordering length in nanoscale. During the heating treatment in air, it was recognized that the diffusion of oxygen atoms is significantly facilitated through the ordered carbon vacancies. For the heating treatment at low temperature (<300°C), the oxygen atoms diffuse easily into and occupy the ordered carbon vacancies, forming the oxy-carbide of ZrC0.6O0.4 with ordered oxygen atoms. At the heating temperature higher than 350°C an amorphous layer of ZrC0.6Oy>0.4 was identified to be formed due to the diffusion of superfluous oxygen atoms into Zr-tetrahedral centers. Inside the amorphous layer, the metastable tetragonal zirconia nanocrystals are recognized to be gradually developed.

Carbon Vacancy Ordered Non-Stoichiometric ZrC0.6

The starting nanopowders of non-stoichiometric zirconium carbide (ZrCx) were fabricated via milling Zr powders in toluene for different dwell times. The carbon content was determined to depend on the milling time and the used amount of toluene. The bulk non-stoichiometric ZrCx with different x were prepared by spark plasma sintering of the obtained ZrCx nanopowders. The microstructural features of a sintered ZrC0.6 sample were investigated via the measurements of XRD, TEM, and HRTEM. It was found that the carbon vacancies have an ordering arrangement in C sublattice, forming a Zr2C-type cubic superstructural phase with space group of Moreover, it was observed that the superstructural phase exists in nano-domains with an average size of ~30 nm owing to the ordering length in nanoscale. During the heating treatment in air, it was recognized that the diffusion of oxygen atoms is significantly facilitated through the ordered carbon vacancies. For the heating treatment at low temperature (<300°C), the oxygen atoms diffuse easily into and occupy the ordered carbon vacancies, forming the oxy-carbide of ZrC0.6O0.4 with ordered oxygen atoms. At the heating temperature higher than 350 °C an amorphous layer of ZrC0.6Oy>0.4 was identified to be formed due to the diffusion of superfluous oxygen atoms into Zr-tetrahedral centers. Inside the amorphous layer, the metastable tetragonal zirconia nanocrystals are recognized to be gradually developed.

Shrinkage reduction of dental composites by addition of expandable zirconia filler

A problem with dental resin composites is the polymerization shrinkage, which makes the filling loosen from the tooth or induces crack formation. We have developed an expandable metastable tetragonal zirconia filler, which upon reaction with water, is able to counter the polymer shrinkage. The shrinkage of the composite was calculated from density measurements using Archimedes method. The rate of the phase transformation in resin was measured by determining the volume fraction of monoclinic zirconia ( vm). The composite had a vm of 0.5 after 8 h of water storage. The overall shrinkage of the composites was reduced from 3.2% (initially) to 1.7%.