The field of bone tissue engineering (BTE) focuses on the repair of bone defects that are too large to be restored by the natural healing process. To that purpose, synthetic materials mimicking the ...natural bone extracellular matrix (ECM) are widely studied and many combinations of compositions and architectures are possible. In particular, the electrospinning process can reproduce the fibrillar structure of bone ECM by stretching a viscoelastic solution under an electrical field. With this method, nano/micrometer-sized fibres can be produced, with an adjustable chemical composition. Therefore, by shaping bioactive ceramics such as silica, bioactive glasses and calcium phosphates through electrospinning, promising properties for their use in BTE can be obtained. This review focuses on the in situ synthesis and simultaneous electrospinning of bioceramic-based fibres while the reasons for using each material are correlated with its bioactivity. Theoretical and practical considerations for the synthesis and electrospinning of these materials are developed. Finally, investigations into the in vitro and in vivo bioactivity of different systems using such inorganic fibres are exposed.
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Bone substitute fabrication is of interest to meet the worldwide incidence of bone disorders. Physical chitosan hydrogels with intertwined apatite particles were chosen to meet the bio-physical and ...mechanical properties required by a potential bone substitute. A set up for 3-D printing by robocasting was found adequate to fabricate scaffolds. Inks consisted of suspensions of calcium phosphate particles in chitosan acidic aqueous solution. The inks are shear-thinning and consist of a suspension of dispersed platelet aggregates of dicalcium phosphate dihydrate in a continuous chitosan phase. The rheological properties of the inks were studied, including their shear-thinning characteristics and yield stress. Scaffolds were printed in basic water/ethanol baths to induce transformation of chitosan-calcium phosphates suspension into physical hydrogel of chitosan mineralized with apatite. Scaffolds consisted of a chitosan polymeric matrix intertwined with poorly crystalline apatite particles. Results indicate that ink rheological properties could be tuned by controlling ink composition: in particular, more printable inks are obtained with higher chitosan concentration (0.19 mol·L
−1
).
2 Hardystonite scaffolds produced by ceramization of 3-D printed preceramic filled polymer were impregnated with chitosan solutions, later neutralized into physical hydrogels. Hardystonite bioceramic ...and chitosan physical hydrogel were chosen for their interesting biological properties as potential bone substitutes. Five impregnation protocols, differing in impregnation vacuum, chitosan concentration, chitosan to hardystonite mass ratio and base used for chitosan gelation were studied. The composition, micropore structure and surface morphology of impregnated scaffolds were determined. Impregnated hardystonite scaffolds were tested to find out the effect of impregnation protocols on elastic and dissipative mechanical properties of the composites. The capacity for energy dissipation and for load bearing increased as chitosan content increased in the composites. Thus, 3-D architectured biocomposites with enhanced mechanical properties can be manufactured following the method shown in this article.
The study of environmental DNA (eDNA) released by aquatic organisms in their habitat offers a fast, noninvasive and sensitive approach to monitor their presence. Common eDNA sampling methods such as ...water filtration and DNA precipitation are time‐consuming, require difficult‐to‐handle equipment and partially integrate eDNA signals. To overcome these limitations, we created the first proof of concept of a passive, 3D‐printed and easy‐to‐use eDNA sampler. We designed the samplers from hydroxyapatite (HAp samplers), a natural mineral with a high DNA adsorption capacity. The porous structure and shape of the samplers were designed to optimize DNA adsorption and facilitate their handling in the laboratory and in the field. Here we show that HAp samplers can efficiently collect genomic DNA in controlled set‐ups, but can also collect animal eDNA under controlled and natural conditions with yields similar to conventional methods. However, we also observed large variations in the amount of DNA collected even under controlled conditions. A better understanding of the DNA–hydroxyapatite interactions on the surface of the samplers is now necessary to optimize eDNA adsorption and to allow the development of a reliable, easy‐to‐use and reusable eDNA sampling tool.
Zirconia ceramics have found broad applications in a variety of energy and biomedical applications because of their unusual combination of strength, fracture toughness, ionic conductivity, and low ...thermal conductivity. These attractive characteristics are largely associated with the stabilization of the tetragonal and cubic phases through alloying with aliovalent ions. The large concentration of vacancies introduced to charge compensate of the aliovalent alloying is responsible for both the exceptionally high ionic conductivity and the unusually low, and temperature independent, thermal conductivity. The high fracture toughness exhibited by many of zirconia ceramics is attributed to the constraint of the tetragonal‐to‐monoclinic phase transformation and its release during crack propagation. In other zirconia ceramics containing the tetragonal phase, the high fracture toughness is associated with ferroelastic domain switching. However, many of these attractive features of zirconia, especially fracture toughness and strength, are compromised after prolonged exposure to water vapor at intermediate temperatures (∼30°–300°C) in a process referred to as low‐temperature degradation (LTD), and initially identified over two decades ago. This is particularly so for zirconia in biomedical applications, such as hip implants and dental restorations. Less well substantiated is the possibility that the same process can also occur in zirconia used in other applications, for instance, zirconia thermal barrier coatings after long exposure at high temperature. Based on experience with the failure of zirconia femoral heads, as well as studies of LTD, it is shown that many of the problems of LTD can be mitigated by the appropriate choice of alloying and/or process control.
Hyperpolarization by dissolution dynamic nuclear polarization (dDNP) has enabled promising applications in spectroscopy and imaging, but remains poorly widespread due to experimental complexity. ...Broad democratization of dDNP could be realized by remote preparation and distribution of hyperpolarized samples from dedicated facilities. Here we show the synthesis of hyperpolarizing polymers (HYPOPs) that can generate radical- and contaminant-free hyperpolarized samples within minutes with lifetimes exceeding hours in the solid state. HYPOPs feature tunable macroporous porosity, with porous volumes up to 80% and concentration of nitroxide radicals grafted in the bulk matrix up to 285 μmol g
. Analytes can be efficiently impregnated as aqueous/alcoholic solutions and hyperpolarized up to P(
C) = 25% within 8 min, through the combination of
H spin diffusion and
H →
C cross polarization. Solutions of
C-analytes of biological interest hyperpolarized in HYPOPs display a very long solid-state
C relaxation times of 5.7 h at 3.8 K, thus prefiguring transportation over long distances.
Further development and upscaling of the Solid Oxide fuel and electrolysis Cell (SOCs) technologies would significantly benefit from improvement of their mechanical robustness. In this work, ...microstructure, crystalline phase composition, fracture toughness and susceptibility to low- and high-temperature degradation of six different Ni(O)‒Zirconia fuel electrode supports, manufactured from six different stabilized zirconia compounds, are investigated.
In the oxidized state, tetragonal zirconia-based supports have higher fracture toughness than cubic zirconia-based substrate, due to the transformation toughening effect and a finer grained microstructure. The NiO‒1.5CeO2 4.5YO1.5-SZ support exhibits the highest fracture toughness, showing a 30 and 10 % improvement compared to the state-of-the-art NiO‒5.8YO1.5-SZ support at room temperature and 800 °C, respectively. In the reduced state on the other hand, the tetragonal and cubic zirconia-based substrates have comparable fracture toughness. The Ceria-Yttria co-doped materials possess superior resistance to hydrothermal degradation due to the stabilizing effect of Ce3+ formed during reduction.
Bioinert zirconia and alumina ceramic devices are widely used, both in orthopaedics and in dentistry. In order to improve their bonding with bone tissues or dental resin cements, their surfaces are ...often roughened at different scales. In this work, we have investigated the effects of the same sandblasting treatment on alumina, zirconia and a zirconia-toughened alumina, focusing on their mechanical performance and the interplay between surface defects and residual stresses. Additionally, we explored the impact of the treatment on the hydrothermal aging of the two zirconia-containing materials. Residual stresses generated during sandblasting were always predominant over surface defects but their effect varied with the material: while they had a weakening effect on alumina, they reinforced both zirconia-containing materials. Finally, we found that the monoclinic grains at the surface of sandblasted zirconia recrystallized into tetragonal nanograins after annealing and this led to an increased resistance to aging.
Abstract Objectives Based on the current lack of standards concerning zirconia dental implants, we aim at developing a protocol to validate their functionality and safety prior their clinical use. ...The protocol is designed to account for the specific brittle nature of ceramics and the specific behavior of zirconia in terms of phase transformation. Methods Several types of zirconia dental implants with different surface textures (porous, alveolar, rough) were assessed. The implants were first characterized in their as-received state by Scanning Electron Microscopy (SEM), Focused Ion Beam (FIB), X-Ray Diffraction (XRD). Fracture tests following a method adapted from ISO 14801 were conducted to evaluate their initial mechanical properties. Accelerated aging was performed on the implants, and XRD monoclinic content measured directly at their surface instead of using polished samples as in ISO 13356. The implants were then characterized again after aging. Results Implants with an alveolar surface presented large defects. The protocol shows that such defects compromise the long-term mechanical properties. Implants with a porous surface exhibited sufficient strength but a significant sensitivity to aging. Even if associated to micro cracking clearly observed by FIB, aging did not decrease mechanical strength of the implants. Significance As each dental implant company has its own process, all zirconia implants may behave differently, even if the starting powder is the same. Especially, surface modifications have a large influence on strength and aging resistance, which is not taken into account by the current standards. Protocols adapted from this work could be useful.
This paper presents a new aqueous precipitation method to prepare silicon-substituted hydroxyapatites Ca10(PO4)6−y(SiO4)y(OH)2−y(VOH)y (SiHAs) and details the characterization of powders with varying ...Si content up to y=1.25molmolSiHA−1. X-ray diffraction, transmission electron microscopy, solid-state nuclear magnetic resonance and Fourier transform infrared spectroscopy were used to accurately characterize samples calcined at 400°C for 2h and 1000°C for 15h. This method allows the synthesis of monophasic SiHAs with controlled stoichiometry. The theoretical maximum limit of incorporation of Si into the hexagonal apatitic structure is y<1.5. This limit depends on the OH content in the channel, which is a function of the Si content, temperature and atmosphere of calcination. These results, particularly those from infrared spectroscopy, raise serious reservations about the phase purity of previously prepared and biologically evaluated SiHA powders, pellets and scaffolds in the literature.