Solid State Processing of BCZT Piezoceramics Using Ultra Low Synthesis and Sintering Temperatures.

Lead-free (Ba0.92Ca0.08) (Ti0.95 Zr0.05) O3 (BCZT) ceramics were prepared by a solid-state route (SSR) using ultra-low synthesis (700 °C/30 min and 700 °C/2 h) and sintering temperatures (from 1150 °C to 1280 °C), due to prior activation and homogenization by attrition milling of the starting high purity raw materials for 6 h before the synthesis and of the calcined powders for 3 h before the sintering. The comparison of the thermal analysis of the mixture of the starting raw materials and the same mixture after 6 h attrition milling allowed to evidence the mechanisms of activation, resulting in a significant decrease of the perovskite formation temperature (from 854 °C down to 582 °C). The secondary phases that limit the functional properties of the ceramic and their evolution with the sintering conditions were analyzed by X-ray diffraction (XRD) and scanning electron microscopy (SEM), which allowed the design of a two-step sintering method to eliminate them. A pure tetragonal BCZT perovskite phase (P4mm, c/a = 1.004) and homogeneous ceramic microstructure was obtained for synthesis at 700 °C for 2 h and sintering with the use of a two-step sintering treatment (900 °C for 3 h and 1280 °C for 6 h). The best electromechanical properties achieved were d33 = 455 pC/N, kp = 35%, Qm = 155.

Ceramic/metal biocidal nanocomposites for bone-related applications.

Hydroxyapatite/silver nanocomposites have been designed and synthesized as an engineering material for biomedical applications. The hydroxyapatite matrix was synthesized by a sol-gel method and, subsequently, the Ag nanoparticles were deposited by heterogeneous precipitation followed by two different reduction routes: thermal or chemical. Both sets were studied and compared and, in all cases, the metal nanoparticles appear perfectly isolated and attached to the surface of the hydroxyapatite. The average metal particle size is below 10 nm, allowing an important contact surface between silver and the microorganisms. The antimicrobial behavior against common bacteria showed a high effectiveness, well above the commercial level, as well as against yeast, in the case of the chemically reduced sample. Due to the nanocomposite microstructure, only a negligible portion of metal was released to the lixiviated liquid after the biocide tests, minimizing the risk of toxicity. These nanocomposites offer a solution to the infections on the surface of implants, one of the main problems in reaching a suitable level of osseointegration.

Biocompatibility assessment of spark plasma-sintered alumina-titanium cermets.

Alumina-titanium materials (cermets) of enhanced mechanical properties have been lately developed. In this work, physical properties such as electrical conductivity and the crystalline phases in the bulk material are evaluated. As these new cermets manufactured by spark plasma sintering may have potential application for hard tissue replacements, their biocompatibility needs to be evaluated. Thus, this research aims to study the cytocompatibility of a novel alumina-titanium (25 vol. % Ti) cermet compared to its pure counterpart, the spark plasma sintered alumina. The influence of the particular surface properties (chemical composition, roughness and wettability) on the pre-osteoblastic cell response is also analyzed. The material electrical resistance revealed that this cermet may be machined to any shape by electroerosion. The investigated specimens had a slightly undulated topography, with a roughness pattern that had similar morphology in all orientations (isotropic roughness) and a sub-micrometric average roughness. Differences in skewness that implied valley-like structures in the cermet and predominance of peaks in alumina were found. The cermet presented a higher surface hydrophilicity than alumina. Any cytotoxicity risk associated with the new materials or with the innovative manufacturing methodology was rejected. Proliferation and early-differentiation stages of osteoblasts were statistically improved on the composite. Thus, our results suggest that this new multifunctional cermet could improve current alumina-based biomedical devices for applications such as hip joint replacements.

Peptide-functionalized zirconia and new zirconia/titanium biocermets for dental applications.

OBJECTIVE: Titanium materials have been functionalized with biomolecules as a modern strategy to incorporate bioactive motifs that will expand and improve their biomedical applications. Here, we have biofunctionalized biomaterials based on zirconia of much interest for dentistry: the widely used bioceramic 3Y-TZP and a newly developed 3Y-TZP/Ti biocermet. METHODS: The biosurfaces were activated, silanized, and functionalized with coatings made of oligopeptides. Surface activation by plasma or alkaline-etching was optimized. The surfaces were coated by tethering a purposely-designed RGD-containing peptide. We selected this oligopeptide as a model peptide to validate the effectiveness of the biofunctionalization process. Successful treatments after each step of the process were assessed by surface physical and chemical characterization with water contact angles and XPS, respectively. Coatings' stability was evaluated after 2h sonication in water. Pre-osteoblasts adhesion on the functionalized surfaces was also studied. RESULTS: 10-min air-plasma treatment effectively activated all types of materials with no detrimental effects on the material structure and hardness. Nitrogen XPS-peak confirmed that RGD-peptides were chemically-attached on the silanized samples. This was further confirmed by visualizing the functionalized surfaces with flourescence-labelled RGD-peptides before and after ultrasonication. Furthermore, RGD-functionalized surfaces significantly enhanced osteoblast adhesion on all types of substrates, which demonstrated their successful bioactivation. CONCLUSIONS: We successfully developed stable functional biocoatings on zirconia and biocermets made of oligopeptides. Surface bioactivation of zirconia-containing components for dental implant applications will enable their improved clinical performance by incorporating signalling oligopeptides to accelerate osseointegration, improving permucosal sealing, and/or incorporating antimicrobial properties to prevent peri-implant infections.

Osteoblastic cell response to spark plasma-sintered zirconia/titanium cermets.

Ceramic/metal composites, cermets, arise from the idea to combine the dissimilar properties in the pure materials. This work aims to study the biocompatibility of new micro-nanostructured 3 Y-TZP/Ti materials with 25, 50 and 75 vol.% Ti, which have been successfully obtained by spark slasma sintering technology, as well as to correlate their surface properties (roughness, wettability and chemical composition) with the osteoblastic cell response. All samples had isotropic and slightly waved microstructure, with sub-micrometric average roughness. Composites with 75 vol.% Ti had the highest surface hydrophilicity. Surface chemical composition of the cermets correlated well with the relative amounts used for their fabrication. A cell viability rate over 80% dismissed any cytotoxicity risk due to manufacturing. Cell adhesion and early differentiation were significantly enhanced on materials containing the nanostructured 3 Y-TZP phase. Proliferation and differentiation of SaOS-2 were significantly improved in their late-stage on the composite with 75 vol.% Ti that, from the osseointegration standpoint, is presented as an excellent biomaterial for bone replacement. Thus, spark plasma sintering is consolidated as a suitable technology for manufacturing nanostructured biomaterials with enhanced bioactivity.

Nanotechnology in joint replacement.

This paper reviews the most relevant achievements and new developments in the field of nanomaterials and their possible impact on the fabrication of a new generation of reliable and longer lasting implants for joint replacement. Special emphasis is given to the role of nanocomposites with different microstructural designs: micro-nano composites, nano-nano composites, macro-micro-nano composites as well as bioinspired hierarchical composite materials. These nanostructured materials have opened up an exciting avenue in the design of non-metallic biocompatible, crack growth resistant, tough, and mechanically resistant implants with a lifespan close to the life expectancy of the patients.

Spreading of viscous liquids at high temperature: silicate glasses on molybdenum.

The spreading of Si-Ca-Al-Ti-O glasses on molybdenum has been investigated. By controlling the oxygen activity in the furnace, spreading can take place under reactive or nonreactive conditions. As the nucleation of the reaction product under reactive conditions is slow in comparison to the spreading kinetics, in both cases the glass front moves on the metal surface with similar spreading velocities. Spreading can be described using a molecular dynamics model where the main contribution to the wetting activation energy comes from the viscous interactions in the liquid. Enhanced interfacial diffusions in low-oxygen activities (reactive cases) form triple-line ridges that can pin the wetting front and cause a stick-slip motion.