Ab initio atomistic description of temperature-induced phase changes: The cases of zirconia and Ti-Y-co-doped zirconia

Zirconium dioxide, or zirconia, is a common and useful ceramic with a wide range of applications, from fuel cells to odontology. Its phase diagram is simple and well understood, having a structure which is monoclinic at temperatures up to 1500 K, tetragonal up to 2700 K and cubic up to 3000 K. Zirconia is rarely used in its pure form, being typically doped with Y2O3, MgO or TiO2, and in this regime its phase diagram becomes much more complex. In this context, ab initio molecular dynamics (AIMD) can provide a detailed atomistic description of the phase diagram of this system, accurately describing its stable phases and transition regions. In this work, 3 mol-% Y2O3 (3YSZ) crystals doped with different Ti contents were studied at the density-functional level. For Ti contents varying from 0 to 30 at%, a global search algorithm was first used to explore the 0 K potential-energy surface and determine the most stable sites for the added Ti atoms. It was found that, at low Ti compositions XTi, small TiO2 clusters form, followed by TiO2 channels and infinite TiO2 planes at larger XTi values, and that the highest stability is achieved at 9% Ti. AIMD simulations within the isothermal-isobaric NPT ensemble were then performed to characterize the temperature-dependent phase changes as a function of the Ti content, where it was found that the Ti-doped structures presented considerably smaller volume changes near the phase-change critical temperatures. These findings suggest that YSZ materials doped with a small amount of Ti are both energetically and kinetically more stable than the undoped counterparts, in the ideal proportion of 3% TiO2 for every 1% Y2O3 doping.Fil: Negreiros Ribeiro, Fábio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Ribeiro Ricci Lazar, Dolores. Comissao Nacional de Energia Nuclear. Centro de Lasers e Aplicacoes. Instituto de Pesquisas Energéticas e Nucleares; BrasilFil: Ussui, Valter. Comissao Nacional de Energia Nuclear. Centro de Lasers e Aplicacoes. Instituto de Pesquisas Energéticas e Nucleares; BrasilFil: De Lima, Nelson Batista. Comissao Nacional de Energia Nuclear. Centro de Lasers e Aplicacoes. Instituto de Pesquisas Energéticas e Nucleares; BrasilFil: Marchi, Juliana. Universidad Federal do Abc; BrasilFil: Dalpian, Gustavo Martini. Universidad Federal do Abc; Brasi

Analysis in vitro of the cytotoxicity of potential implant materials. I: Zirconia-titania sintered ceramics

Zirconia (ZrO(2)) is a bioinert, strong, and tough ceramic, while titania (TiO(2)) is bioactive but has poor mechanical properties. It is expected that ZrO(2)-TiO(2) mixed ceramics incorporate the individual properties of both ceramics, so that this material would exhibit better biological properties. Thus, the objective of this study was to compare the biocompatibility properties of ZrO(2)-TiO(2) mixed ceramics. Sintered ceramics pellets, obtained from powders of TiO(2), ZrO(2), and three different ZrO(2)-TiO(2) mixed oxides were used. Roughnesses, X-ray diffraction, microstructure through SEM, hardness, and DRIFT characterizations were performed. For biocompatibility analysis cultured FMM1 fibroblasts were plated on the top of disks and counted in SEM micrographs 1 and 2 days later. Data were compared by ANOVA complemented by Tukey`s test. All samples presented high densities and similar microstructure. The H(2)O content in the mixed ceramics was more evident than in pure ceramics. The number of fibroblasts attached to the disks increased significantly independently of the experimental group. The cell growth on the top of the ZrO(2)-TiO(2) samples was similar and significantly higher than those of TiO(2) and ZrO(2) samples. Our in vitro experiments showed that the ZrO(2)-TiO(2) sintered ceramics are biocompatible allowing faster cell growth than pure oxides ceramics. The improvement of hardness is proportional to the ZrO(2) content. Thus, the ZrO(2)-TiO(2) sintered ceramics could be considered as potential implant material. (C) 2010 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater 94B: 305-311, 2010.CNPqFAPES

Y-TZP ceramic processing from coprecipitated powders: A comparative study with three commercial dental ceramics

Objectives. (1) To synthesize 3 mol% yttria-stabilized zirconia (3Y-TZP) powders via coprecipitation route, (2) to obtain zirconia ceramic specimens, analyze surface characteristics, and mechanical properties, and (3) to compare the processed material with three reinforced dental ceramics. Methods. A coprecipitation route was used to synthesize a 3 mol% yttria-stabilized zirconia ceramic processed by uniaxial compaction and pressureless sintering. Commercially available alumina or alumina/zirconia ceramics, namely Procera AllCeram (PA), In-Ceram Zirconia Block (CAZ) and In-Ceram Zirconia (IZ) were chosen for comparison. All specimens (6 mm x 5 mm x 5 mm) were polished and ultrasonically cleaned. Qualitative phase analysis was performed by XRD and apparent densities were measured on the basis of Archimedes principle. Ceramics were also characterized using SEM, TEM and EDS. The hardness measurements were made employing Vickers hardness test. Fracture toughness (K(IC)) was calculated. Data were analyzed using one-way analysis of variance (ANOVA) and Tukey's test (alpha = 0.05). Results. ANOVA revealed that the Vickers hardness (p <0.0001) and fracture toughness (p <0.0001) were affected by the ceramic materials composition. it was confirmed that the PA ceramic was constituted of a rhombohedral alumina matrix, so-called alpha-alumina. Both CAZ and IZ ceramics presented tetragonal zirconia and alpha-alumina mixture of phases. The SEM/EDS analysis confirmed the presence of aluminum in PA ceramic. In the IZ and CAZ ceramics aluminum, zirconium and cerium in grains involved by a second phase containing aluminum, silicon and lanthanum were identified. PA showed significantly higher mean Vickers hardness values (H(V)) (18.4 +/- 0.5 GPa) compared to vitreous CAZ (10.3 +/- 0.2 GPa) and IZ (10.6 +/- 0.4 GPa) ceramics. Experimental Y-TZP showed significantly lower results than that of the other monophased ceramic (PA) (p <0.05) but it showed significantly higher fracture toughness (6.0 +/- 0.2 MPa m(1/2)) values when compared to the other tested ceramics (p <0.05). Significance. The coprecipitation method used to synthesize zirconia powders and the adopted ceramic processing conditions led to ceramics with mechanical properties comparable to commercially available reinforced ceramic materials. (C) 2008 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved

Physico-chemical characterization and biocompatibility of hydroxyapatite derived from fish waste

The aim of this study was to synthesize hydroxyapatite (HAP) powder from fish waste. The powder was characterized through X-ray diffraction, Fourier transform infrared spectroscopy, ion exchange chromatography, scanning electron microscopy and plasma emission spectrometry. The cyto- and genotoxicity was carried out to demonstrate biocompatibility in vivo by means of rat subcutaneous tissue test. The results showed that the visible crystalline nature of typical apatite crystal structure when they were calcined at 800 degrees C. Infrared spectroscopy analysis showed similar composition to HAP standard with the presence of carbonate ion demonstrated by wave number values of 871 cm(-1) and 1420 cm(-1) for calcinations at 800 degrees C. The scanning electronmicrographies depicted the crystal morphology and porous nature with average pore size of similar to 10 mu m. Plasma emission spectrometry and ion exchange chromatography confirmed the presence of Ca and P in the samples. The mean of calcium content was 36.8Mg was 0.8, Na was 0.7 and K was 0.5. Rat subcutaneous tissue test revealed that HAP presented biocompatibility. Furthermore, the lack of cyto- and genotoxicity in blood, liver, kidney and lung were noticed after 30 days of HAP implantation. Taken together, our results demonstrated that HAP from fish waste exhibits a great potential for using as biomaterial since is represents a simple, effective, low-cost process and satisfactory degree of biocompatibility.CNPq (Conselho Nacional de Desenvolvimento Cientifico e Tecnologico)Fed Univ Sao Paulo UNIFESP, Dept Biosci, Av Ana Costa 95, BR-11060001 Santos, SP, BrazilIPEN, Nucl & Energy Res Inst, Sao Paulo, SP, BrazilFed Univ Sao Paulo UNIFESP, Dept Biosci, Av Ana Costa 95, BR-11060001 Santos, SP, BrazilCNPq: 442149/2014-0Web of Scienc

Influence of the starting materials on performance of high temperature oxide fuel cells devices

High temperature solid oxide fuel cells (SOFCs) offer an environmentally friendly technology to convert gaseous fuels such as hydrogen, natural gas or gasified coal into electricity at high efficiencies. Besides the efficiency, higher than those obtained from the traditional energy conversion systems, a fuel cell provides many other advantages like reliability, modularity, fuel flexibility and very low levels of NOx and SOx emissions. The high operating temperature (950-1000 °C) used by the current generation of the solid oxide fuel cells imposes severe constraints on materials selection in order to improve the lifetime of the cell. Besides the good electrical, electrochemical, mechanical and thermal properties, the individual cell components must be stable under the fuel cell operating atmospheres. Each material has to perform not only in its own right but also in conjunction with other system components. For this reason, each cell component must fulfill several different criteria. This paper reviews the materials and the methods used to fabricate the different cell components, such as the cathode, the electrolyte, the anode and the interconnect. Some remarkable results, obtained at IPEN (Nuclear Energy Research Institute) in São Paulo, have been presented