Functionalizing Ti-Surfaces through the EPD of Hydroxyapatite/NanoY₂O₃

Ceramic materials for skeletal repair and reconstruction are expanding to a number of different applications. Present research is addressing new compositions and performances to promote osseo-integration through metal coatings. Nanotechnology plays a key role in this research because nanostructures can be introduced into implants to functionalize them and/or to enhance their properties, such as the thermal or mechanical response. In this work, the insertion of Y₂O₃ nanoparticles into a hydroxyapatite (HA) coating of Ti using colloidal processing technology was developed. The suspensions of HA and Y₂O₃ nanoparticles were formulated with a focus on zeta potential, particle size distribution, and viscosity for the codeposition of both phases by electrophoresis. The microstructure of the nanocomposite coating was optimized by adjusting the main parameters of the electrophoretic deposition process. A threshold value of the applied electric field for the composite shaping was identified. The results demonstrate that the Y₂O₃ nanoparticles are homogeneously distributed in the coating and decrease in concentration as the distance from the substrate increases. As a consequence of the presence of the Y₂O₃, delays in the HA thermal decomposition and the improvement of metal–ceramic joining were observed.This work has been supported by the Spanish Ministry of Economy and Competitiveness (MINECO) under contracts MAT2009 14448 C02 01, MAT2012 38650 C02 02, and IPT 310000 2010 12

Colloidal approach for the design of Ti powders sinterable at low temperature

The colloid-chemistry control of metallic powders in aqueous slurries is proposed as a way to produce spherical granules of fine titanium particles able to be processed by powder metallurgy (PM) techniques. Significant improvement of sintering behavior is achieved, leading to high dense parts at reduced sintering temperature and time. Consequently the control of grain growth during sintering was achieved, as well as the oxygen content. This approach can be extended to other strategies for Ti design, such as the homogeneous dispersion of second phases for further control of grain size and modification of properties.The authors would like to acknowledge the financial support from Spanish Government through the projects MAT 2009-14448-C02-01 and 02, MAT2012-38650-C02-01 and 02En prens

Improvement of sintering behaviour of titanium by colloidal techniques

The conventional sintering of titanium requires high temperatures to obtain high densities and low porosity, giving rise to microstructures with high grain size, and high interstitial contents, both of which adversely affect the mechanical properties obtained. A novel approach is reported which uses fine (10 µm) spherical Ti powder to improve the sintering behaviour, together with a small percentage of alumina particles (0·5 µm) to restrict grain growth. Colloidal techniques were used to form spherical agglomerates, 50‐300 µm in size, of Ti powder with alumina particles dispersed homogenously on the Ti surface. These agglomerates present good compressibility and make it possible to sinter effectively at low temperatures, increasing the relative density and decreasing grain sizeThe authors acknowledgement the financial support from Spanish Ministry of Science and Innovation through projects MAT 2009-14448-C01, and MAT 2009-14448-C02. This is an edited version of a presentation at Euro PM 2012, organised by EPMA in Basel, Switzerland on 16–19 October 2012.Publicad

Role of stabilisers in the design of Ti aqueous suspensions for pressure slip casting

Colloidal processing has long been used in ceramics to achieve green bodies with high densities, complex shapes and homogeneous microstructures, but they are rarely used to shape metal powders because of their high density and high surface reactivity. However, the possibility of processing fine particles makes these techniques interesting for metals, such as titanium, with a low density and high melting point. This work presents encouraging results in the design of aqueous suspensions of Ti particles to be shaped into bulk pieces by pressure slip casting (PSC), which opens new paths for the processing of fine and complex microstructures. Ti powders, measuring 10 μm in size, and mixtures of Ti and Al₂O₃ powders (added up to 5 wt.%) were dispersed in water by the addition of different stabilisers. The influence of the stabilisers in the slurry behaviour (in terms of nature, stereochemistry and active functional groups) was determined, as well as the incorporation of ceramic particles. A polyacrylic-based dispersant was selected as the best stabiliser to incorporate a second component (Al₂O₃) into the Ti suspension, whereas shear-thinning additives, such as TIRON, are preferred for PSC shaping. Suspensions with 1 wt.% Al₂O₃ were selected for processing composites by PSC and sintering. Sintered materials were characterised by measuring the density, oxygen content, hardness and microstructure analysis by SEM. Ti bulk pieces with 97% density and fine and homogeneous microstructure, of which the relationship between the oxygen content and hardness agrees with that measured for CPTi grade 4 (249 ± 24 HV30), can be processed by PSC.The authors would like to acknowledge the financial support from the Spanish Government through the projects MAT 2009-14448-C02-01 and 02, MAT2012 38650-C02-01 and 02 and to the regional government of Madrid through the programme Estrumat (Ref. S2009/MAT-1585)

Laser-assisted surface melting of Al2O3-YSZ eutectic ceramics

[ES] Se presenta un procedimiento para la densificación y/o texturado superficial de cerámicas de Al2O3-YSZ (circona estabilizada con itria) con composición eutéctica mediante fusión zonal asistida por láser. Haciendo un barrido con la radiación proveniente de un láser de potencia sobre piezas cerámicas conseguimos modificar la microestructura y densificar completatmente la capa superficial, con un espesor que va de 30 a 1000 μm. Por ejemplo, con línea estrecha de láser de diodo, fluencia de 1.23 kW/cm2 y velocidades de barrido de 0.14 mm/s, solidificamos capas de 560 μm. El resultado es una superficie de baja rugosidad y no porosa. La microestructura de la muestra es fina debido a su composición eutéctica. La interfase sólido-líquido en el proceso de crecimiento determina la orientación de la microestructura. Se estudia la forma de esta interfase tanto en cortes transversales como longitudinales, lo que permite analizar el efecto que sobre la microestructura tiene la superposición de barridos, que es una alternativa para tratar superficies extensas. Macroscópicamente la frontera entre barridos contiguos es suave. Sin embargo, su microestructura presenta discontinuidad en el espaciado entre las fases debido a la evolución microestructural en la región no fundida sometida a altas temperaturas y a la nucleación preferencial de Al2O3 al comenzar el crecimiento cristalino. Se analizan distintas posibilidades para disminuir el choque térmico inherente al proceso y que conduce a la formación de grietas paralelas a la dirección de procesado y de delaminación. Se observa una mejora importante cuando se precalienta la pieza a tratar, de modo que es posible procesar superficies de cerámicas eutécticas 99% densas.[EN] A procedure for surface densification and/or texturing of Al2O3-YSZ (yttria stabilised zirconia) ceramics with eutectic composition by means of laser surface melting is presented. By scanning a high-power laser beam on a ceramic surface, we achieve a textured and fully dense surface layer from 30 to 1000 microns thick. For example, using a thin diode laser line with fluence 1.23 kW/cm2 and 0.14 mm/s scan rate, the solidified layer has 560 μm depth. We get a low roughness and dense surface. The microstructure is fine (micron size) due to the eutectic composition. The orientation of the microstructure is determined by the shape of the solid-liquid interface in the solidification process. We study the shape of this interface in transverse and longitudinal cross-sections in single as well as overlapping scans, which are required to process large surfaces. From the macroscopic point of view, the transition between adjacent scans is smooth. However, the microstructure presents discontinuity in the interphase spacing due to microstructural evolution in the heat affected region as well as the nucleation of an Al2O3 layer at the beginning of the crystal growth. The thermal shock inherent to the procedure generates cracks longitudinal and transverse to the scanning direction, as well as delaminating cracks. We analyse different possibilities to reduce this thermal shock. The best results are obtained by preheating the substrate, allowing us to process surfaces of Al2O3-YSZ eutectic ceramics 99% dense.Financiación del Ministerio de Ciencia y Tecnología a través de los proyectos MAT2000-1495 y MAT2000-1533-C03-02.Peer reviewe

Positron annihilation study of defect distribution in 8YSZ nanostructure

The impact of the interfacial contribution on overall properties increases with decreasing grain size of polycrystalline materials. It is well known that distribution and size of cluster defects are rather different in bulk than grain boundaries. In light of "bottom-up" approaches, a study at the atomic level determining the distribution of crystallographic defects could clarify their contribution to the macroscopic properties, and then differentiate materials for outstanding or precise applications. In this work, Positron Annihilation Spectroscopy (PAS) is used to characterize the distribution of defects within 8 mol% Y₂O₃-stabilized zirconia (8YSZ) structures prepared by sintering through three different thermal treatments, i.e. a conventional thermal cycle in air and N₂/H₂ atmosphere, and a fast firing cycle in air, which lead to average grain sizes < 260 nm.The authors would like to acknowledge the financial support from the Spanish Government through the projects MAT2009-14448-C02-01 and IPT-310000-2010-12.Publicad

Microstructural characterization of alumina-zirconia layered ceramics using positron annihilation spectroscopy

Positron annihilation spectroscopy (PAS), indentation, nanoindentation experiments and scanning electron microscopy (SEM) observations were performed on Al₂O₃-ZrO₂ laminates samples to assess the effect of residual stresses on their mechanical and microstructural properties. Layered samples were implemented by slip-casting, constituted by two thin Al₂O₃ external layers and an intermediate thick one, consisting of a mixture of Al₂O₃ and monoclinic ZrO₂ in the range 0-30 vol.%. In these systems residual tensile stresses fields were generated inside the external layers during cooling from the sintering temperature, by the expansion of the adjacent ZrO₂-containing layer. SEM observations showed the microstructural effects due to the level of tension related to the zirconia content. A correlation between the PAS parameters and the microstructural changes caused by the presence of residual stresses was found. Nanoindentation measurements were used to trace the sign and magnitude of the residual stress gradient across the interface between the layers.This work was supported by Spanish Government under Contract MAT2006-01038. The authors gratefully acknowledge the financial support from the Comunidad de Madrid and the Ministry of Education and Science of Spain, through the ESTRUMAT-CM (MAT/77) programs.Publicad

Effect of highly dispersed yttria addition on thermal stability of hydroxyapatite

The capability of the colloidal method to produce yttria (Y₂O₃) dispersed hydroxyapatite (HA) has been investigated as an alternative method to the conventional method of mechanical mixing and sintering for developing HA-based materials that could exhibit controllable and enhanced functional properties. A water based colloidal route to produce HA materials with highly dispersed Y₂O₃ has been applied, and the effect of 10 wt.% Y₂O₃ addition to HA investigated by thermal analysis, X-ray diffraction and Fourier transform infrared spectroscopy. These measurements evidence a remarkable effect of this Y₂O₃ addition on decomposition mechanisms of synthetic HA. Results show that incorporation of Y₂O₃ as dispersed second phase is beneficial because it hinders the decomposition mechanisms of HA into calcium phosphates. This retardation will allow the control of the sintering conditions for developing HA implants with improved properties. Besides, substitution of Ca⁻2+ with Y⁻3+ ions appears to promote the formation of OH- vacancies, which could improve the conductive properties of HA favorable to osseointegration.This work has been supported by the Ministry of Science and Innova tion of Spain (MICINN) under contracts MAT2009 14448 C02 01 and IPT 310000 2010 12, and Regional Government of Madrid through the ESTRUMAT CM program (MAT 1585).Publicad