Iron phthalocyanines (FePc) adsorbed onto a Ag(110) substrate self-assemble into different monolayer phases going from rectangular to different oblique phases, with increasing molecular density. We ...have investigated the oxygen uptake capability of the different phases and their associated magneto-structural changes. Our study combines scanning tunneling microscopy and spectroscopy (STM/STS), X-ray magnetic circular dichroism (XMCD), and density functional theory (DFT) calculations. STM measurements reveal that the oxygenation reaction of the FePc/Ag(110) generally involves a displacement and a rotation of the molecules, which affects the electronic state of the Fe centers. The oxygen intercalation between FePc and the substrate is greatly obstructed by the steric hindrance in the high-density phases, to the point that a fraction of oblique phase molecules cannot change their position after oxidizing. Depending on the oxidation state and adsoption geometry, the STS spectra show clear differences in the Fe local density of states, which are mirrored in the XAS and XMCD experiments. Particularly, XMCD spectra of the oxidized phases reflect the distribution of FePc species (nonoxygenated, oxygenated-rotated, and oxygenated-unrotated) in the different cases. Sum rule analysis yields the effective spin (m s eff) and orbital (m L) magnetic moments of Fe in the different FePc species. Upon oxygenation, the magnetic moment of FePc molecules increases about an order of magnitude, reaching m TOT ∼ 2.2 μB per Fe atom.
Abstract Metals and ceramics are commonly used in orthopaedics, dentistry and other load bearing applications. However, the use of ceramic matrix composites reinforced with biocompatible metals for ...heavy load-bearing hard tissue replacement applications has not previously been reported. In order to improve the reliability and the mechanical properties of biomedical implants, new zirconia–Nb composites have been recently developed. The aim of this study was to investigate the biological tolerance of these new zirconia/Nb biocermets implants with both in vitro and in vivo approaches. At first, human bone marrow derived mesenchymal stem cells were cultured on sintered biocermet discs with polished surfaces and were compared with responses to niobium metal. In vitro, the biocermets showed no deleterious effect on cell proliferation, extra-cellular matrix production or on cell morphology. Furthermore, the biocermet showed a higher percentage of cell proliferation than Nb metal. On the other hand, the bone response to these new zirconia/Nb biocermets was studied. Cylinders of biocermets, as well as commercially Nb rod were implanted in the tibiae of New Zealand white rabbits. All the animals were euthanatized after 6 months. The specimens were processed to obtain thin ground sections. The slides were observed in normal transmitted light microscope. A newly formed bone was observed in close contact with material surfaces. No inflamed or multinucleated cells were present. This study concluded that zirconia/Nb composites are biocompatible and osteoconductive. The ceramic-metal composite has even better osteointegration ability than pure Nb. In conclusion, zirconia–Nb biocermet is suitable for heavy load-bearing hard tissue replacement from the point of view of both mechanical properties and biocompatibility.
Zirconia abutments with a titanium base are promising candidates to substitute for titanium abutments based on clinical studies reporting good short-term survival rates. However, information on the ...long-term performance of zirconia abutments supporting ceramic crowns is scarce.
This in vitro comparative and finite element analysis study compared the fatigue life performance of ceramic computer-aided design and computer-aided manufacturing (CAD-CAM) monolithic restorations and zirconia abutments fabricated with a chairside workflow connected to a titanium interface versus titanium abutments.
Twenty-two internal connection implants were divided into 2 groups, one with a zirconia abutment and monolithic ceramic zirconia crown (ZZ) and the other with a titanium abutment and zirconia crown (TiZ). They were subjected to a fatigue test to determine the fatigue limit and fatigue performance of each group as per International Organization for Standardization (ISO) 14801. Microstructural analysis of the fracture surfaces was conducted by using a scanning electron microscope (SEM). Simulations of the in vitro study were also conducted by means of finite element analysis (FEA) to assess the stress distribution over the different parts of the restoration.
The fatigue limit was 250 N for the TiZ group and 325 N for the ZZ group. In both groups, the screw was the part most susceptible to fatigue and was where the failure initiated. In the zirconia abutment models, the stress on the screw was reduced.
Chairside CAD-CAM zirconia abutments with a titanium base supporting zirconia crowns had higher fatigue fracture resistance compared with that of titanium abutments.
Achieving good piezoelectric properties, such as the widely reported d33 charge coefficient, is a good starting point in establishing the potential applicability of piezoceramics. However, ...piezoceramics are only completely characterized by consistent piezoelectric-elastic-dielectric material coefficient matrices in complex form, i.e., including all losses. These matrices, which define the various alternative forms of the constitutive equations of piezoelectricity, are required for reliable virtual prototyping in the design of new devices. To meet this need, ten precise and accurate piezoelectric dielectric and elastic coefficients of the material, including all losses, must be determined for each alternative. Due to the difficulties arising from the coupling of modes when using the resonance method, this complete set of parameters is scarcely reported. Bi0.5Na0.5TiO3-based solid solutions are already commercially available in Europe and Japan. Here, we report a case study of the determination of these sets of material coefficients (diα, giα, eiα and hiα; sE,Dαβ and cE,Dαβ; εTik and εSik; and βTik and βSik), including all losses, of the commercial PIC700 eco-piezoceramic. Plate, disk, and cylinder ceramic resonators of a manageable aspect ratio were used to obtain all the material coefficients. The validation procedure of the matrices is also given by FEA modeling of the considered resonators.
Alumina toughened zirconia (ATZ) and zirconia toughened alumina (ZTA) are currently the materials of choice to meet the need for tough, strong, and bioinert ceramics for medical devices. However, the ...mechanical properties of ZrO2/Al2O3 dispersion ceramics could be considerably increased by reducing the corresponding grain sizes and by improving the homogeneity of the phase dispersion. Here, we prepare nanoparticles with an intraparticular phase distribution of Zr(1-x)Al(x)O(2-x/2) and (γ-, δ-)Al2O3 by the simultaneous gas phase condensation of laser co-vaporized zirconia and alumina raw powders. During subsequent spark plasma sintering the zirconia defect structures and transition alumina phases transform to a homogeneously distributed dispersion of tetragonal ZrO2 (52.4 vol%) and α-Al2O3 (47.6 vol%). Ceramics sintered by spark plasma sintering are completely dense with average grain sizes in the range around 250 nm. Outstanding mechanical properties (flexural strength σf = 1500 MPa, fracture toughness KIc = 6.8 MPa m(1/2)) together with a high resistance against low temperature degradation make these materials promising candidates for next generation bioceramics in total hip replacements and for dental implants.
Dense (>98 th%) and homogeneous ceramic/metal composites were obtained by spark plasma sintering (SPS) using ZrO
and lamellar metallic powders of tantalum or niobium (20 vol.%) as starting materials. ...The present study has demonstrated the unique and unpredicted simultaneous enhancement in toughness and strength with very high flaw tolerance of zirconia/Ta composites. In addition to their excellent static mechanical properties, these composites also have exceptional resistance to fatigue loading. It has been shown that the major contributions to toughening are the resulting crack bridging and plastic deformation of the metallic particles, together with crack deflection and interfacial debonding, which is compatible with the coexistence in the composite of both, strong and weak ceramic/metal interfaces, in agreement with predictions of ab-initio calculations. Therefore, these materials are promising candidates for designing damage tolerance components for aerospace industry, cutting and drilling tools, biomedical implants, among many others.
(computer-aided design-computer-aided manufacturing) CAD/CAM monolithic restorations connected to zirconia abutments manufactured with a chairside workflow are becoming a more common restorative ...option. However, their mechanical performance is still uncertain. The aim of this study was to evaluate the mechanical behavior of a combination of a zirconia abutment and monolithic all-ceramic zirconia and lithium disilicate crown manufactured with a chairside workflow, connected to titanium implants with two types of internal connection—tube in tube connection and conical connection with platform switching. They were thermally cycled from 5 °C to 55 °C and were subjected to a static and fatigue test following ISO 14801. The fractured specimens from the fatigue test were examined by SEM (scanning electron microscopy). Simulations of the stress distribution over the different parts of the restorative complex during the mechanical tests were evaluated by means of (finite element analysis) FEA. The mechanical performance of the zirconia abutment with an internal conical connection was higher than that of the tube in tube connection. Additionally, the use of disilicate or zirconia all-ceramic chairside CAD/CAM monolithic restorations has similar results in terms of mechanical fracture and fatigue resistance. Stress distribution affects the implant/restoration complex depending on the connection design. Zirconia abutments and monolithic restorations seem to be highly reliable in terms of mechanical resistance.
Lead-free (Ba
Ca
) (Ti
Zr
) O
(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 d
= 455 pC/N, k
= 35%, Q
= 155.
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