3D CaP porous scaffolds with grooved surface topography obtained by the sol-gel method

The influence of surface topography on cellular behaviour and its importance for the development of three-dimensional scaffolds for bone tissue engineering are a topic of growing interest. To date, the introduction of topographical patterns into the surface of 3D porous ceramic scaffolds has proven difficult, due partly to the brittle nature of ceramic materials as well as the currently available fabrication technologies. In this study, a grooved pattern was introduced into the surface of 3D multilayer porous ceramic scaffolds by the chemical etching technique. The patterned scaffolds were characterised by X-Ray Diffraction (XRD), Scanning Electron Microscopy with Energy Dispersive X-Ray Spectroscopy (SEM-EDX) and Digital Holographic Microscopy (DHM). Their bioactivity was also evaluated in vitro by immersion in simulated body fluid (SBF) for 12 h, 1, 7, 14 and 21 days. Scaffolds were constituted mainly with a mixture of the calcium pyrophosphate (Ca₂O₇P₂) and β-tricalcium phosphate (Ca?(PO?)?) phases. The pyrophosphate on the external layer was dissolved as a result of the etching process, leaving grooves on the surface. Ridges and grooves were nano-/micrometric, with dimensions of around 900 nm–1.5 μm in width and 200 nm–300 nm in depth. Moreover, the mechanical properties and bioactive capacity of the patterned scaffolds were not affected by chemical etching, making them suitable to be used in bone tissue engineering.     

Resistance of 2ZrO2·Y2O3 top coat in thermal/environmental barrier coatings to calcia‐magnesia‐aluminosilicate attack at 1500°C

Internally cooled, hollow SiC‐based ceramic matrix composites (CMCs) components that may replace metallic components in the hot section of future high‐efficiency gas‐turbine engines will require multilayered thermal/environmental barrier coatings (T/EBCs) for insulation and protection. In the T/EBC system, the thermally insulating outermost (top coat) ceramic layer must also provide resistance to attack by molten calcia‐magnesia‐aluminosilicate (CMAS) deposits. The interactions between a potential candidate for top coat made of air‐plasma‐sprayed (APS) 2ZrO₂·Y₂O₃ solid‐solution (ss) ceramic and two different CMASs (sand and fly ash) are investigated at a relevant high temperature of 1500°C. APS 2ZrO₂·Y₂O₃(ss) top coat was found to resist CMAS penetration at 1500°C for 24 hours via reaction products that block CMAS penetration pathways. In situ X‐ray diffraction (XRD) studies have identified the main reaction product to be an Ca‐Y‐Si apatite, and have helped elucidate the proposed mechanism for CMAS attack mitigation. Ex situ electron microscopy and analytical spectroscopy studies have identified the advantageous characteristics of the reaction products in helping the CMAS attack mitigation in the APS 2ZrO₂·Y₂O₃(ss) coating at 1500°C. Finally, the Y³⁺ solubility limit and transport behavior are identified as potential comparative tools for assessing the CMAS resistance ability of top‐coat ceramics.     

Nurse′s A‐Phase: Synthesis and Characterization in the Binary System Ca2SiO4–Ca3(PO4)2

In the present study, a new single phase Si–Ca–P‐based ceramic was obtained by conventional sintering of compacted mixtures of calcium hydrogen phosphate anhydrous, calcium carbonate, and silicon oxide. The synthesis conditions were the followings: heated up to 1550°C for a total period of time of 72 h (3 d), with quenching in liquid nitrogen, milling, pressing, and reheating every 24 h. Second, heating at 1300°C/3 h and subsequent annealed at 1200°C/24 h. Mineralogical and microstructural characterization of the obtained Si–Ca–P‐based material was determined by Differential Thermal Analysis, X‐ray diffraction, Scanning Electron Microscopy with attached wavelength dispersive spectroscopy, Micro‐Raman and Fourier Transform Infrared Spectrometer. The results showed a single Si–Ca–P phase material with a Ca₂SiO₄/Ca₃(PO₄)₂ molar ratio equal to 2:1. The parameters of the Weibull distribution of strength, determined by diametrical compression of disks, were: modulus, m = 13, and characteristic strength σ₀ = 0.60 MPa.     

Bone-like forming ability of apatite-wollastonite glass ceramic

This research describes the preparation, characterisation and in vitro behavior of a bioactive glass ceramic containing 44.8 wt% apatite, 28.0 wt% wollastonite-2 M and 27.2 wt% of amorphous phase. The biomaterial was obtained by a specific thermal cycle process that caused the devitrification of the Ca₃(PO₄)₂-CaSiO₃ binary system's stoichiometric eutectic composition. Overall, the material combines the properties of a resorbable Si-Ca-rich glass, in addition to bioactive properties of wollastonite and apatite phases. The bioactivity of this material was studied by soaking the samples in a simulated body fluid (SFB) for 3, 7, 14 and 21 days at 36.5 °C. During the soaking, the amorphous phase and also wollastonite-2 M phase underwent steady dissolution by releasing Si and Ca ions into the SBF medium. After 7 days, a porous hydroxy-carbonate apatite (HCA) layer was formed at the SBF-glass ceramic interface. The micro-nanostructured apatite-wollastonite-2 M glass ceramics with improved mechanical properties, in comparison with the parent glass, could serve as a promising platform for hard tissue regeneration.     

Porous β-Ca2SiO4 ceramic scaffolds for bone tissue engineering: In vitro and in vivo characterization

The biodegradable ceramic scaffolds with desirable pore size, porosity and mechanical properties play a crucial role in bone tissue engineering and bone transplantation. A novel porous β-dicalcium silicate (β-Ca₂SiO₄) ceramic scaffold was prepared by sintering the green body consisting of CaCO₃ and SiO₂ at 1300 °C, which generated interconnected pore network with proper pore size of about 300 μm and high compressive strength (28.13±5.37–10.36±0.83 MPa) following the porosity from 53.54±5.37% to 71.44±0.83%. Porous β-Ca₂SiO₄ ceramic scaffolds displayed a good biocompatibility, since human osteoblast-like MG-63 cells and goat bone mesenchymal stem cells (BMSCs) proliferated continuously on the scaffolds after 7 d culture. The porous β-Ca₂SiO₄ ceramic scaffolds revealed well apatite-forming ability when incubated in the simulated body fluid (SBF). According to the histological test, the degradation of porous β-Ca₂SiO₄ ceramic scaffolds and the new bone tissue generation in vivo were observed following 9 weeks implantation in nude mice. These results suggested that the porous β-Ca₂SiO₄ ceramic scaffolds could be potentially applied in bone tissue engineering.     

Physicochemical and cytological properties of poorly crystalline calcium-deficient hydroxyapatite with different Ca/P ratios

Compared to highly crystalline hydroxyapatite (HA), poorly crystalline hydroxyapatite has been proved to have better bioactivity and degradability, owing to its similar crystallographic structure to natural bone. However, there are few systematic comparative studies on poorly crystalline HA with different Ca/P ratios. In this work, poorly crystalline HA with different Ca/P molar ratios (1.50, 1.55, 1.60 and 1.67) was prepared by chemical precipitation method. The effects of Ca/P ratio on its structure, composition, morphology, surface properties, protein adsorption behaviors, ion adsorption and release abilities, cytological properties were systematically investigated. Results showed that the prepared HA was poorly crystalline, nano-sized and with the gradient change of Ca/P ratios. Protein adsorption capacity and P release of calcium deficient HA (CDHA) were effectively improved by reducing the Ca/P ratio, but CDHA with lower Ca/P ratio would also adsorb more Ca ions in the culture medium, which jointly affected the cytological properties of CDHA. In vitro cell experiments indicated that when mouse bone mesenchymal stem cells were co-cultured with CDHA with a Ca/P ratio of 1.55, their proliferation, ALP activity and osteogenesis-related genes expression were the strongest. This study provides a theoretical support and potential for further improving the biological performance of poorly crystalline CDHA materials.     

Development of multi-phase B–Si–C ceramic composite by reaction sintering

A dense ceramic composite in the system B–C–Si has been synthesized by the reaction sintering technique based on infiltration of silicon melt at 1550 °C under vacuum into a porous compact made of boron carbide and petroleum coke powder. The final material is around 99% dense and microstructurally contains B₄C, SiC and Si as the major phases. The B₄C-phase reacted at its interface with Si-phase, which is explained in terms of dissolution of Si in the carbide phase.     

Control of the Dissolution of Ca and Si Ions from CaSiO3 Bioceramic via Tailoring Its Surface Structure and Chemical Composition

Owing to their good osseointegration property, calcium silicate (CS) bioceramics have been extensively studied in recent years. Nevertheless, the excessively high environmental pH value of CS bioceramics will limit their clinical application. The purpose of this work is to reduce the dissolution of Ca and Si ions from the pure CS bioceramics by modifying its surface structure and chemical composition with Zn₂SiO₄ nanoparticles (Zn–CS bioceramic). The results indicated that the dissolution of Ca and Si ions from the CS substrate obviously decreased by the surface modification, and the pH value of the soaking liquid was also effectively controlled. SEM observation and EDS analysis showed that apatite mainly formed on the wall of the internal pores under the Zn‐containing porous surface layer when the Zn–CS bioceramic was soaked in the simulated body fluids (SBF). Moreover, cell adhesion assay proved that mouse osteoblast cells (MC3T3) well adhered and spread on the Zn‐containing porous surface layer, and the apatite formed on the surface of the Zn‐containing porous layer during the incubation process. Better bioactivity and the osseointegration property can be expected for Zn–CS bioceramic. The surface modification with Zn₂SiO₄ nanoparticles is a promising route to control the dissolution and environmental pH value of CS bioceramics.     

Wettability and infiltration of Si melt on SiO2-Si3N4 composite ceramic

Non-wettable material with Si melt is preferred to manufacture crucible in order to avoid adhesion between Si and traditional fused silica crucible. In this work, wetting and infiltration behaviors of Si drop on porous/dense SiO₂-Si₃N₄ ceramic and SiO₂ ceramic were systematically studied via the sessile drop technology and microstructural analysis method. The porous SiO₂-Si₃N₄ ceramic exhibited non-wetting behavior with stable contact angle of about 130 °. Nevertheless, dense SiO₂-Si₃N₄ ceramic and SiO₂ ceramic displayed wetting features with Si drop. For both SiO₂-Si₃N₄ ceramics, three kinds of infiltrations were observed, including infiltration under Si drop, infiltration under substrate surface (beyond drop) and infiltration on substrate surface. Notably, the infiltration under Si drop had the slowest speed with tiny infiltration depth. The above non-wetting behavior and tiny infiltration under drop of porous SiO₂-Si₃N₄ ceramic were closely related to material pore characteristics and Si/substrate interfacial reaction.     

Corrosion mechanism of polycrystalline corundum and calcium hexaluminate by calcium silicate slags

The chemical reactions involved in the corrosion of polycrystalline alumina (Al₂O₃) and calcium hexaluminate–hibonite (CaAl₁₂O₁₉) ceramics by two dicalcium silicate slags with additions of fluorspar (CaF₂) were studied using a hot-stage microscopy (HSM) up to 1600 °C. The corrosion mechanism was investigated on post-mortem corroded samples and the phases formed at different stages of the dissolution process were characterised by reflected optical light microscopy (RLOM) and scanning electron microscopy (SEM) with energy dispersive X-ray spectrometry (EDS) microanalysis system.The attack of the fused slags on dense alumina substrates takes place through an interdiffusion mechanism producing successive layers of calcium aluminates. In porous hibonite samples chemical interactions were observed although only a layer of calcium dialuminate was formed. A sintering process in presence of liquid phase was also detected behind the reaction interphase.Thermodynamic calculations, based on the Al₂O₃–CaO–SiO₂, Al₂O₃–CaO–SiO₂–MgO, and Al₂O₃–CaO–SiO₂–CaF₂ phase equilibrium were used to further knowledge of the corrosion mechanism.     

Plasma sprayed nanostructured GdPO4 thermal barrier coatings: Preparation microstructure and CMAS corrosion resistance

Nanostructured GdPO₄ thermal barrier coatings (TBCs) were prepared by air plasma spraying, and their phase structure evolution and microstructure variation due to calcium–magnesium–alumina–silicate (CMAS) attack have been investigated. The chemical composition of the coating is close to that of the agglomerated particles used for thermal spraying. Nanozones with porous structure are embedded in the coating microstructure, with a percentage of ~30%. CMAS corrosion tests indicated that nanostructured GdPO₄ coating is highly resistant to penetration by molten CMAS at 1250°C. Within 1 hour heat treatment duration, a continuous dense reaction layer forms on the coating surface, which are composed of P–Si apatite based on Ca_2+xGd_8?x(PO₄)_x(SiO₄)_6?xO₂, anorthite and spinel phases. This layer provides effective prevention against CMAS further infiltration into the coating. Prolonged heat treatment densifies the reaction layer but does not change its phase composition.     

Preparation and phosphorus recovery performance of porous calcium–silicate–hydrate

Porous calcium–silicate–hydrate was synthesized and used to recover phosphorus from wastewater. The principal objective of this study was to explore the phosphorus recovery performance of porous calcium–silicate–hydrate prepared by different Ca/Si molar ratios. Phosphorus recovery mechanism was also investigated via Field Emission Scanning Electron Microscopy (FESEM), Energy Dispersive Spectrum (EDS), Brunauer–Emmett–Teller (BET) and X-ray Diffraction (XRD). The law of Ca²⁺ release was the key of phosphorus recovery performance. Different Ca/Si molar ratios resulted in the changes of pore structures. The increase of specific surface area and the increase in concentration of Ca²⁺ release were well agreement together. The Ca/Si molar ratio of 1.6 for porous calcium–silicate–hydrate is more proper to recover phosphorus. The pore structure of porous calcium–silicate–hydrate provided a local condition to maintain a high concentration of Ca²⁺ release. Porous calcium–silicate–hydrate could release a proper concentration of Ca²⁺ and OH^? to maintain the pH values at 8.5–9.5. This condition was beneficial to the formation of hydroxyapatite. Phosphorus content of porous calcium–silicate–hydrate reached 18.64% after phosphorus recovery.     

Resolving the Interface of Calcium Phosphate Formation on the Porous Bioceramics In Vitro

Porous bioceramics have been widely studied for bone tissue engineering. A deep understanding on the mechanism of bone growth and biomineralization depends on the extracted interface information between the new precipitated calcium phosphates (CaPs) and the porous substrate at a nanometer scale. However, due to their intrinsic brittleness and the complexity of the sample shape, there is still lack of such information. Here, by a combination of focused ion beam (FIB) and transmission electron microscopy (TEM), in‐situ cross‐sectional electron transparent interface was prepared. The precipitated dense apatite layer is composed of individual microgranules which further consist of tiny flake‐like crystals. The new crystallites grow along c‐axis and are mostly oriented perpendicular to HA substrate. This preferred orientation is more pronounced in the presence of protein. This work offers a novel and feasible approach using FIB‐TEM to in situ image porous bioceramic scaffold and precipitated apatite layer interface and can be extended to study many other biointerfaces.     

A novel apatite-inspired Sr5(PO4)2SiO4 plasma-sprayed coating on Ti alloy promoting biomineralization,osteogenesis and angiogenesis

Osteoconductive, osteoinductive, anti-infection, and controlled ionic release properties are crucial for the long-term clinical success of orthopedic and dental metallic implants. In this study, we have successfully synthesized apatite chemical structure mimic Sr₅(PO₄)₂SiO₄ (SPS) nanopowder by sol-gel method to be used as a novel bioactive ceramics coatings on medical-grade titanium alloy by plasma-spray deposition technique. The deposited SPS coatings were analytically characterized by XRD and SEM-EDS analysis and confirmed that the coating possessed a pure crystalline phase of SPS without any other secondary phases, and exhibited a sharp needle-like morphology with the existence of Sr, P, O, Si elements. The cross-sectional view proved that the deposition of dense SPS layer with a thickness of 116 μm. The in vitro ionic dissolution behavior of SPS coatings was detected by ICP-OES analysis and confirmed their controlled releasing profile of ions such as Sr (120–55 ppm) and Si (0.14–9.86 ppm). In vitro biomineralization study demonstrated that the SPS coatings were remarkably encouraged the ball likes apatite crystals growth on their surface with a Ca/P ratio (1.677) similar to natural bone minerals. The SPS coatings exhibited notable cellular interactions with human umbilical card-derived mesenchymal stem cells (HUMSCs) in terms of cell proliferation, early-stage differentiation, and calcium nodule accumulation in ECM, also the osteogenic differentiation was found to be prominent for SPS coated Ti64 than sandblasted Ti64. Furthermore, the angiogenic property of SPS coated Ti64 was evaluated by Human umbilical vein endothelial cells (HUVECs) and confirmed their tremendous cell viability with non-toxicity and nominal angiogenic differentiation. Therefore, our study proved that the apatite-inspired SPS bioactive ceramics coatings could improve the biofunctional activities of orthopedic and dental implants for their better clinical success.     

Diffusion bonding of Ti-coated Cf-SiCf/SiBCN composites to Nb using Ag–Pd interlayer

The Ti-coated C_f-SiC_f/SiBCN ceramic was diffusion-bonded to Nb using an Ag–Pd interlayer. At a ceramic/Ag–Pd interface, it is found that Ti first reacted with C and Pd to form a TiC_x/Ti(Pd) double-layer structure, and then Ti(Pd) completely converted into TiC_x with the increase of holding time or temperature. Meanwhile, the infiltration of Pd along TiC_x grain boundary reacted with Si to form brittle Pd₂Si compound. By contrary, only a simple NbPd₃ layer was formed at the Nb/Ag–Pd interface during the whole process. A maximum shear strength of 16 ± 3 MPa is obtained for the joint prepared at 900°C for 30 min. The plastic deformation of the Ag–Pd interlayer and pullout of fibers inside ceramic contributed to the superior performance. Nevertheless, as the holding time and temperature reached 90 min and 950°C, the high chemical affinity of the Pd–Si system and enhanced atomic diffusion led to the massive formation of Pd₂Si, which increased the joint brittleness and degraded the ceramic performance.     

Mechanical properties and wear behavior of Tin+1(Al,A)Cn (A = Ga,In, Sn,n = 1, 2) via quasi-high-entropy of single atomic thick A layer

The strengthening method of multi-element M-site solid solution is a common approach to improve mechanical properties of MAX phase ceramic. However, the research on capability of multi-element A-site solid solution to improve mechanical properties has rarely been reported. Thereupon, quasi-high-entropy MAX phase ceramic bulks of Ti₂(Al_1?xA_x)C and Ti₃(Al_1?xA_x)C₂ (A = Ga, In, Sn, x = 0.2, 0.3, 0.4) were successfully synthesized by in situ vacuum hot pressing via multi-elements solid solution. The multi-elements solid solution in single-atom thick A layer was confirmed by X-ray diffraction and X-ray photoelectron spectroscopy as well as by energy dispersive X-ray spectroscopy mappings. Effects of doped multi-elements contents on the phase, microstructure, mechanical properties, and high temperature tribological behaviors were studied. Results demonstrated that the Vickers hardness, anisotropic flexural strength, fracture toughness, and tribological properties of Ti–Al–C based MAX ceramics could be remarkably improved by constitution of quasi-high-entropy MAX phase in A layers. Moreover, the strengthening and wear mechanisms were also discussed in detail. This method of multi-element solid solution at A-site provides new way to enhance mechanical properties of other MAX phase ceramics.     

Microstructure and mechanical properties of ZrB2–SiC porous ceramic by camphene-based freeze casting

Camphene-based freeze casting technique was adopted to fabricate ZrB₂–SiC porous ceramic with 3-dimensional (3D) pore network. ZrB₂–SiC/camphene slurries (initial solid loading: 20 vol%, 25 vol% and 30 vol%) were prepared for freeze casting. Regardless of initial solid loading, the fabricated sample had dense/porous dual microstructure. The thickness of dense layer was about 200–300 μm. The microstructures of ZrB₂–SiC porous ceramics were significantly influenced by the initial solid loading, which determines the pore size, porosity and mechanical properties of the final products.     

Preparation strategy for low-stress and uniform SiC-on-diamond wafer: A silicon nitride dielectric layer

Reducing the self-heating of SiC- and GaN/SiC-based high-powered devices by integrating diamond films offers promising performance enhancement of these devices. However, such a reduction strategy faces serious problems, such as diamond nucleation on SiC and stress accumulation greater than 10 GPa. In this work, a SiN_x dielectric layer (～50 nm) was coated onto the C polar face of a 4H–SiC wafer using microwave plasma chemical vapor deposition (MPCVD) to improve direct dense diamond nucleation and growth, significantly reduce the stress, and build Si–C(SiC)?Si?C(diamond) bond bridges. This SiN_x thin layer, prepared by activating Si ions under Ar/N plasma during magnetron sputtering, gave rise to local Si₃N₄ crystal features and a low effective work function (EWF) for promoting surface dipoles with electronegative carbon-containing groups. In the H plasma environment during diamond growth, the local Si₃N₄ crystal was amorphized, and the N atoms escaped as a result of atomic H and the high temperature. At the same time, C atoms diffused into the SiN_x and formed C–Si bonds (49.7% of the total C bonds) by replacing N–Si and Si–Si, thus increasing the direct nucleation density of the diamond grains. The diamond thin film grew rapidly and uniformly, with a grain size of approximately 2 μm in mixed orientation, and the stress of the 2-inch SiC-on-diamond wafer was extremely low (to ～0.1–0.2 GPa). In comparison, partially connected diamond grains (>10 μm) on the bare SiC in the preferential (110) orientation resulted in a film with twin-grain features and significant stress, which was associated with the hexagonal lattice interface of 4H–SiC. These results are considered the material and surface/interface bases for actively controlling wafer fabrication and enhancing the heat dissipation of SiC and GaN/SiC electronics.     

Tailoring bioactive and mechanical properties in polycrystalline CaO–SiO2–P2O5 glass-ceramics

Biological functions and mechanical properties are vital factors for artificial bone materials, with great clinic demand for bone injuries and defects. This study highlights mechanical strengths, in vitro and in vivo biological behaviors of the bioactive CaO–SiO₂–P₂O₅ glass-ceramics tailored by the nucleating agent P₂O₅. A high mechanical flexural strength of ～170 MPa and hardness of ～720 HV were achieved, owing to strengthened Si–O bonds in the network. In vitro cell tests demonstrate remarkable viability (using L929 cells) and bioactivity (using bone marrow-derived mesenchymal stromal cells), associated with the release of Ca²⁺ ions in the solution due to weakened Ca–O bonds in the glass-ceramic network. The assay in the simulated body ?uid revealed a formation of the hydroxyapatite-phase layer, which may act as a bridge to facilitate bioactivity on the CaO–SiO₂–P₂O₅ glass-ceramics. In vivo assay shows a significant bone-ingrowth capability on the CaO–SiO₂–P₂O₅ glass-ceramic. This work paves a promising route to utilize P₂O₅–nucleated CaO–SiO₂–P₂O₅ glass-ceramics for load-bearing bone replacement.     

Interfacial microstructure characterization and strength evaluation of Si3N4/Si3N4 joints with Si–Mg composite filler for high-temperature applications

Silicon-nitride (Si₃N₄) components were joined under vacuum at 1100 °C for 10 min using Si–Mg composite fillers with Mg contents (X_Mg) that ranged from 0 at.% to 59 at.%. The Si₃N₄/Si₃N₄ joints were fabricated via Si layer formation at the joint interface; the molten Si–Mg liquid was transformed into a solid Si layer after Mg-evaporation-induced isothermal solidification. The joint tensile strength at room temperature increased considerably when X_Mg exceeded the liquidus composition of 37 at.% because of the enhanced densification/thinning of the Si layer. In these cases, some Mg atoms reacted with Si₃N₄ to form a fine-grained MgSiN₂-based layer, whereas relatively large (>0.1 μm) and smaller MgO precipitates (<10 nm) were observed in the Si layer. At a high X_Mg, the MgO precipitates were arranged in a network-like structure, which improved the fracture strength of the Si layer. The joints with a high strength at room temperature were examined using a three-point bending test at 1200 °C in air and endured a maximum fracture stress of ~200 MPa, which confirmed their potential for use in oxidizing atmospheres at least 100 °C above the bonding temperature.