Synthesis and characterization of bioactive forsterite nanopowder

Forsterite ceramic is a new bioceramic with good biocompatibility. However, the degradation rate of forsterite ceramic is extremely low, and the apatite-formation ability is also poor. On the other hand, nanostructured bioceramics are expected to have better bioactivity than coarser crystals. The aim of this work was preparation, characterization and bioactivity evaluation of forsterite nanopowder. Forsterite nanopowder was synthesized by the sol–gel process. Bioactivity evaluation was preformed by immersing the forsterite powder in the simulated body fluid (SBF) and apatite formation on the surface of the immersed forsterite nanopowders was investigated. Results showed the particle size of pure forsterite was 25–45 nm. During immersion in SBF, the dissolution rate of the forsterite nanopowder was higher than conventional forsterite powders and apatite was formed after soaking for 14 days. Our study indicated that forsterite nanopowder unlike micron-sized forsterite possessed apatite-formation ability and might be used for preparation of new biomaterials.     

In-vitro bioactivity of wollastonite materials derived from limestone and silica sand

This paper describes the behaviour of bioactive wollastonite materials containing Malaysian limestone and silica sand. Wollastonite, which is also known as calcium silicate (CaSiO₃), is an industrial mineral composed of calcium, silicon and oxygen. Pseudowollastonite, which is a primary crystal of wollastonite, was synthesised via a solid-state reaction at a temperature of 1450 °C. The in-vitro bioactivity of wollastonite was examined by soaking it in simulated body fluid (SBF) solution for 1–7 days at 36.5 °C. The soaked wollastonite samples were characterised using XRD, SEM-EDX, FTIR and ICP analyses. Apatite particles precipitated on the surface of the wollastonite sample after the sample was soaked in the SBF. The XRD analysis indicated the presence of an increasing amount of the hydroxyapatite phase as the soaking time increased. The SEM and EDX analyses indicated the formation of granules of agglomerated apatite particles on the surface of the soaked wollastonite sample. During the formation of apatite, phosphate ions from the SBF solution were consumed. This process was confirmed by ICP, which revealed a decrease in ion concentration after the soaking process. The FTIR analysis indicated that the peaks of the phosphate ions increase when the apatite layer forms on the surface of the wollastonite sample. After the soaking process, a calcium deficient hydroxyapatite layer was observed on the wollastonite sample. The study concludes that wollastonite produced from Malaysian limestone and silica sand is bioactive and may be used as an implantable biomaterial.     

Wollastonite/hydroxyapatite scaffolds with improved mechanical,bioactive and biodegradable properties for bone tissue engineering

Wollastonite/hydroxyapatite composite scaffolds are proposed as bone graft. An investigation on scaffold with varying reinforcing wollastonite content fabricated by polymeric sponge replica is reported. The composition, sintering behavior, morphology, porosity and mechanical strength were characterized. All the scaffolds had a highly porous well-interconnected structure. A significant increase in mechanical strength is achieved by adding a 50% wollastonite phase. The most mechanically resistant (50/50) wollastonite/hydroxyapatite scaffolds were soaked in both simulated body fluid (SBF) and Tris–HCl solution in order to assess bioactivity and biodegradability. A carbo-hydroxyapatite layer formed on their surfaces when immersed in SBF. The biodegradability tests reveals that the composite scaffold shows a higher degradation rate compared to pure hydroxyapatite used as comparison. These results demonstrate that the incorporation of a 50% of wollastonite phase in hydroxyapatite matrix is effective in improving the strength and the bioactive and biodegradable properties of the porous scaffolds.     

In-vitro evaluation of wollastonite nanopowder produced by a facile process using cheap precursors for biomedical applications

Wollastonite nanopowder (β-CaSiO₃) is the most nanoceramic powder that is most frequently applied in biomedical applications due to its good bioactivity and biocompatibility. Although the preparation of wollastonite in a solid-state is distinguished as a simple and cheap method with large-scale production, it requires high temperatures (=1400 °C) and consumes quite a long time. The wet methods are considered the best when it comes to preparing the wollastonite nanopowders. However, it has some drawbacks such as its extravagant raw materials and its shorting in preparation which inhibits successful coverage for large-scale production. Herein facile, one-pot modified co-precipitation approach with an easy procedure, shorter reaction time, and in-expensive precursor sodium meta-silicate-pentahydrate and CaCO₃ has been utilized for large-scale production of wollastonite nano-powders (76–150 nm). The precipitated product was calcined at different temperatures (800, 900, 1000, and 1100 °C). The phase composition and microstructure of the calcined powders were investigated. They were analyzed by XRD, FTIR, FESEM, and HRTEM. The in-vitro bioactivities of the calcined powders at 1000 &1100 °C were investigated by analyzing their abilities to form apatite on their surface after 21 days in SBF. The apatite mineralization of the powder surfaces was examined through FESEM, EDX, and Raman spectra. The results show that a single-phase wollastonite got formed at all calcined temperatures with a unique silkworm texture. SBF in-vitro test states the formation of HA on the powder surface. Therefore, these powders are expected to be valuable and promising for biomedical applications such as coating and bio cement.     

Preparation and in vitro apatite-forming ability of hydroxyapatite and β-wollastonite composite materials

This paper provides a one-step method of preparation of the ceramic powders, containing various amounts of hydroxyapatite (HA) and β-wollastonite (WT), based on the salt coprecipitation and subsequent thermal treatment of the synthesis products at 1000?°C. Aqueous solutions of Ca(OH)₂, H₃PO₄ and Na₂SiO₃ were used as precursors of Ca₁₀(PO₄)₆(OH)₂ and β-CaSiO₃, as a minimal amount of by-product is formed during such an interaction of reagents. Variation of the concentration of the initial reagents allows the preparation of ceramic powders containing from 0 to 100?wt% of apatite. All composites were examined by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), laser diffraction analysis and an adsorption method (BET). Degradability of composite powders was analyzed in the Tris-HCl buffer solution. The apatite-forming ability of synthetic composites was investigated by soaking composite ceramics in a simulated body fluid (SBF). The results that were obtained reveal an increase in the dissolution rate of powders with wollastonite addition. Soaking of the composite ceramics in SBF leads to the formation of a bone-like apatite spherical particle layer on their surfaces, which become thicker while the content of β-СаSiO₃ in the samples increases.     

Sol-gel and SPS combined synthesis of highly porous wollastonite ceramic materials with immobilized Au-NPs

Here we present a prospective method of sol-gel synthesis of highly porous wollastonite ceramic powders with controlled macroporous structure (mean pore size ~160 nm) and immobilized gold nanoparticles (particle size is less than 50 nm). The method's distinction is based on using the colloidal template (micelles of "core-shell" polymer latex) both as a poreforming agent and as nanoreactors for nanoparticle synthesis in the system wollastonite/Au-NPs. We revealed the impact of template thermal removal on the morphology of nanostructured wollastonite. We also optimized thermal treatment to obtain defect-free macroporous calcium silicates. Template functionalization by size stabilized gold nanoparticles with their following immobilization into the porous volume of synthesized wollastonite has been described. Besides, an original nonstandard method of combined sol-gel (template) synthesis and spark plasma sintering (SPS) is suggested to obtain the wollastonite ceramic compounds with bimodal pore size distribution (100–500 nm and not less than 1 µm), high mechanical strength (compressive strength limit ~120 MPa) and containing immobilized Au-NPs. Peculiarities of biporous silicate framework formation has been studied using two types of poreforming agents (templates) of various origin, shape and size, introduced during different stages of sol-gel and SPS processes. These templates are organoelemental polymer latex of “core-shell” type and nonorganic carbon filler. Developed approaches are innovative and provide to make new materials with unique characteristics and functional properties as bone-like structure, mechanical stability, antibacterial and anti-inflammatory effects and etc. The materials meet all the biomaterials requirements and are in high demand by modern medicine.     

Mechanical and Bioactive Behavior of Hydroxyapatite–Wollastonite Sintered Composites

The effect of wollastonite amount on the mechanical and bioactive properties of several hydroxyapatite-wollastonite sintered composites was evaluated. The wollastonite reinforcement effect was assessed by measuring hardness and reduced elastic modulus on the materials, using nanoindentation methods. Bioactive properties were analyzed by soaking these materials in a simulated body fluid (SBF) for various periods of time. The analyses reveal an enhancement of hardness and reduced elastic modulus with the addition of wollastonite. In addition, the interaction of these materials with an SBF produces a bone-like apatite layer on their surfaces, which is thicker when the wollastonite is in a higher proportion.     

Synthesis and characterization of chlorapatite–ZnO composite nanopowders

The influence of zinc oxide content on the formation of chlorapatite-based composite nanopowders in the mechanically alloyed CaO–CaCl₂–P₂O₅–ZnO system was studied. To mechanosynthesize composite nanopowders, different amounts of hydrothermally synthesized zinc oxide nanoparticles (0–10 wt%) were mixed with ingredients and then were mechanically activated for 5 h. Results showed that in the absence of zinc oxide, high crystalline chlorapatite nanopowder was obtained after 5 h of milling. In the presence of 4 and 7 wt% zinc oxide, the main product of milling for 5 h was chlorapatite–zinc oxide composite nanopowder. On increasing the zinc oxide content to 10 wt%, composite nanopowder was not formed due to improper stoichiometric ratio of the reactants. The crystallite size, lattice strain, volume fraction of grain boundary, and crystallinity degree of the samples fluctuated significantly during the milling process. In the presence of 7 wt% zinc oxide, the crystallite size and crystallinity degree reached 51±2 nm and 79±2%, respectively. During annealing at 900 °C for 1 h, the crystallization of composite nanopowder occurred and as a result the crystallinity degree rose sharply to 96±3%. In addition, the crystallite size increased to 77±2 nm after annealing at 900 °C. According to SEM and TEM images, the composite nanopowder was composed of both ellipse-like and polygonal particles with a mean size of about 98 nm.     

Silicon carbide particle reinforced mullite composite foams

Silicon carbide particle reinforced mullite composite foams were produced by the polymer replica method using alumina and kaolin to form in situ mullite matrix. Up to 20 wt.% silicon carbide particles (SiCp) were added to aqueous ceramic slurry to explore its effect on the rheological behaviour of ceramic slurries and also properties of as sintered products. By means of solid loading optimisation and sintering enhancement by silicon carbide, mullite based ceramic composite foams of higher strength were obtained. The strength of the as sintered foams was found to depend greatly on the phase composition, relative density of the structures and the amount of SiCp addition. By studying the effect of the additive concentration, on the mechanical properties of the ceramic matrix, it is found that the optimal silicon carbide addition is 20 wt.%.     

Comparative study of interphase evolution in polysiloxane resin-derived matrix containing carbon micro and nanofibers during thermal treatment

The work presents the results of research on composite materials made of silicon-containing polymer-derived ceramic matrix composites (PDC-Cs) and nanocomposites (PDC-NCs). Carbon micro and nanofibers (CFs and CNFs) were used as reinforcements. The interactions between carbon micro and nanofibers and polysiloxane matrix, as well as interphase evolution mechanism in composite samples during their heating to 1000 °C were studied. CF/resin and CNF/resin composites were prepared via liquid precursor infiltration process of unidirectionally aligned fibers. After heating to 700 °C–800 °C, decomposition of the resin in the presence of CNFs led to the formation of fiber/organic-inorganic composites with pseudo-plastic properties and improved oxidation resistance compared to as-prepared fiber/resin composites. The most favourable mechanical properties and oxidation resistance were obtained for composites and nanocomposites containing the maximum amount of carbon nanoparticles precipitated in the SiOC matrix during the heat treatment at 800 °C. The precipitated carbon phase improves fiber/matrix adhesion of composites.     

Preparation and in vitro degradation of novel bioactive polylactide/wollastonite scaffolds

Composite scaffolds for applications in bone engineering from poly(D,L ‐lactide) (PDLLA) incorporated with different proportional bioactive wollastonite powders were prepared through a salt‐leaching method, using NH₄HCO₃ as porogen. The pore structures and morphology of the scaffolds were determined by scanning electron microscopy (SEM). The bioactivity of composite materials was evaluated by examining its ability to initiate the formation of hydroxyapatite (Ca₁₀(PO₄)₆(OH)₂)(HAp) on its surface when immersed in simulated body fluids (SBF). The in vitro degradation behaviors of these scaffolds were systematically monitored at varying time periods of 1, 2, 4, 6, 8, 11, 14, 17, 20, 24, and 28 weeks postimmersion in SBF at 37°C. FT‐IR, XPS, XRD, and SEM measurements revealed that hydroxyapatite commenced to form on the surface of the scaffolds after 7 days of immersion in SBF. The measurements of weight loss, pH, and molecular weight of the samples indicated that PDLLA/wollastonite composite scaffolds degraded slower than the pure PDLLA scaffolds do. Addition of wollastonite enhanced the mechanical property of the composite scaffolds. The in vitro osteoblast culture experiment confirmed the biocompatibility of the scaffold for the growth of osteo‐blasts. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009.     

Preparation and characterization of wollastonite/titanium oxide nanofiber bioceramic composite as a future implant material

In this study, novel composites consisting of electrospun titanium dioxide (TiO₂) nanofibers incorporated into high-purity wollastonite glass ceramics were prepared as materials for use in hard tissue engineering applications. These materials were characterized and investigated by means of physical, mechanical and in vitro studies. The proposed composite showed greater densification and better mechanical characteristics compared to pure wollastonite. The influence of densification temperature and TiO₂ content was investigated. Typically, TiO₂/wollastonite composites having 0, 10, 20 and 30 wt% metal oxide nanofibers were sintered at 900, 1100 and 1250 °C. The results indicated that increasing TiO₂ nanofibers content leads to increase the bulk density, compressive strength and microhardness with negligible, high and moderate influence for the densification temperature, respectively. While porosity and water adsorption capacity decreased with increasing the metal oxide nanofibers with a considerable impact for the sintering temperature in both properties. Moreover, bone-like apatite formed on the surface of wollastonite and wollastonite/TiO₂ nanofibers soaked in simulated body fluid (SBF). All these results show that the inclusion of TiO₂ nanofibers improved the characteristics of wollastonite while preserving its in vitro bioactivity; hence, the proposed composite may be used as a bone substitute in high load bearing sites.     

Electrophoretic deposition of bioactive wollastonite and porcelain–wollastonite coatings on 316L stainless steel

Wollastonite and porcelain–wollastonite coatings on stainless steel were obtained by electrophoretic deposition using acetone as dispersive medium. A direct electric current of 800 V for 3 min was used for obtaining the single wollastonite coating. A well-sintered layer was observed after heat treatment at 1050 °C for 1 h in air. The two-layer coating was obtained by depositing dental porcelain at 400 V for 30 s followed by the deposition of wollastonite at 400 V for 3 min. After forming the two layers, this complex coating was heat treated at 800 °C for 5 min. Under these conditions, strong bonds of both the interface wollastonite–porcelain and that of porcelain–metallic substrate were observed. The in vitro bioactivity assessment of the coatings was performed by immersing the deposited substrates in simulated body fluid (SBF) for 21 days. All the materials showed to be highly bioactive through the formation of a homogeneous apatite layer.     

Development of multiphase bioceramics from a filler-containing preceramic polymer

Multiphase bioceramics based on wollastonite and wollastonite/hydroxylapatite (W/HAp) have been successfully prepared by the heat treatment of a filler-containing preceramic polymer. CaO-bearing precursors (Ca-carbonate, Ca-acetate, and CaO nano-particles) were dispersed in a solution of silicone resin, subsequently dried and pyrolysed in nitrogen. The reaction between silica, deriving from the oxycarbide (SiOC) residue of the silicone resin, and CaO “active filler” led to the formation of several calcium silicates, mainly consisting of wollastonite (CaSiO₃), in both low and high temperature forms. The phase assemblage of the final ceramic varied with the pyrolysis temperature (varying from 1000 to 1200 °C). HAp was additionally inserted, as “passive filler” (i.e. not reacting with SiOC), for the preparation of bioceramics based on W/HAp mixtures.     

Preparation and characterisation of porous composite biomaterials based on silicon nitride and bioglass

The combination of bioinert and bioactive material offers new potentialities in bone tissue engineering. The present paper deals with preparation of novel biomaterial composite based on silicon nitride (Si₃N₄) and bioglass (in amount of 10 and 30 wt%) by free sintering at 980 °C for 1 h in nitrogen atmosphere. The obtained material was characterised by differential thermal analysis (DTA) and X-ray powder diffraction (XRD), porosity and pore size distribution were evaluated by means of mercury intrusion porosimetry (MIP). The bioactivity was examined in vitro with respect to the ability of hydroxyapatite layer formation on the surface of materials as a result of contact with simulated body fluid (SBF). All composites were studied by Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM) before and after immersion in SBF. The bioglass-free sample was prepared as a reference material to compare the microstructure and bioactivity to the composites.     

Influence of the sintering temperature on the structural feature and bioactivity of sol–gel derived SiO2–CaO–P2O5 bioglass

A sol–gel method was utilized to synthesize the gel with the composition of 58 mol% SiO₂–38 mol% CaO–4 mol% P₂O₅. The thermal properties were studied using thermogravimetric and differential thermal analysis (TG/DTA). Then the gels were sintered at 700, 900, 1000 and 1200 °C. The structure features were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM), in addition in vitro assays were carried out in simulated body fluid (SBF). The results revealed that at sintering temperature above 900 °C, crystallization occurred and glass-ceramics with pseudowollastonite and wollastonite were formed. Furthermore with the increase of sintering temperature, the amount of pseudowollastonite decreased while that of wollastonite increased. In vitro tests indicated that the crystallization did not inhibit the samples bioactivity. After soaking in SBF, the formation of apatite was confirmed on glass and glass-ceramics surface, and the bioactivity of the glass-ceramics was based on the formed pseudowollastonite and wollastonite.     

Hot Pressing of Infrared‐Transparent Y2O3–MgO Nanocomposites Using Sol–Gel Combustion Synthesized Powders

A sol–gel combustion method has been used to synthesize Y₂O₃–50 vol%MgO composite nanopowders. Solutions of the precursor nitrates were mixed with citric acid and ethylene glycol, heated from 200°C to a predetermined temperature gradually, giving nanocrystalline ceramic powders. The influence of the ratio of yttrium nitrate to the whole precursor mixture and the holding temperature on the properties of the composite nanopowder was investigated using a combination of thermal analysis, X‐ray diffraction, specific surface area analysis, and scanning electron microscopy techniques. When the ratio of yttrium nitrate to the whole precursor mixture reaches 22.5 mol%, the average particle size of synthesized composite nanopowder is 13 nm and the specific surface area is 45.9 m²/g. Then the synthesized Y₂O₃–MgO composite nanopowder was consolidated by the hot‐pressing technique at 1200°C with different dwell time. As a result, the nanocomposite ceramic prepared with a dwell time of 60 min got the highest transmittance of 75% at 5 μm wavelength. The cut‐off wavelength of Y₂O₃–MgO nanocomposite ceramic reaches 9.8 μm, which is superior to other mid‐IR transparent materials. In addition, the fabricated sample is more or less transparent in visible wavelengths and the transmittance at 0.8 μm is as high as 14.5%.     

Alumina ceramic tool material with enhanced properties through the addition of bionic prepared nano SiC@graphene

Graphene-coated SiC nanoparticles containing graphene floating bands (SiC@G) were prepared by a liquid-phase laser irradiation technique, and SiC@G nanoparticles with high dispersivity were incorporated into an Al₂O₃ matrix. An Al₂O₃-based composite ceramic tool was prepared by spark plasma sintering (SPS), and the effects of SiC@G nanoparticles on the mechanical and cutting properties and microstructure of the materials were further investigated. Analysis of the cross-sectional morphology shows that SiC@G nanoparticles containing graphene floating bands were homogeneously dispersed in the composite, which resulted in tighter bonds between the Al₂O₃ particles. This particular core-shell structure increased the contact area between the graphene and the matrix due to the formation of a graphene 3D mesh by extrusion, which enhanced the difficulty of relative sliding of graphene. Second, this special core-shell structure also made the crack propagation path more tortuous, further increasing the energy consumed in the fracture process, which is conducive to improving the mechanical properties of ceramic tools. The addition of SiC@G nanoparticles improves the mechanical properties of Al₂O₃-based composite ceramic tools. The fracture toughness (7.2 Mpa·m^1/2) and flexural strength (709 MPa) increased by 75.6% and 28.7%, respectively. Cutting experiments with Al₂O₃/SiC/G composite ceramic tool and Al₂O₃/SiC@G composite ceramic tools on 40Cr hardened steel were performed. The results prove that the addition of SiC@G nanoparticles improves the cutting life by 18.1% and reduces the cutting force and friction coefficient by 6.3% and 14.8%, respectively.     

Densification and enhancement of SiC particulate-reinforced fine-grain SiC ceramic

Dense sintering of SiC nanopowder under low temperature and pressure remains a big challenge, because of the great resistance caused by the severe agglomeration of nanopowder. A novel sintering strategy is proposed to prepare SiC composite ceramics by sintering the mixture of SiC nanopowder and SiC micron powder at low temperature and pressure. The SiC micron powder was in the size of 100 µm with little sintering activity, which was designed as a pressure conductor to promote the densification of SiC nanopowder. Experimental results showed that the SiC micron powder had a significant effect on increasing of the sintering density of nanopowder and improving the mechanical properties of SiC ceramics. An SiC composite ceramic with a relative density of 98%, a Vickers hardness of 22.6 GPa, and a fracture toughness of 5.43 MPa m^1/2 could be sintered by spark plasma sintering under 1700°C and 30 MPa by adding 30 wt.% 100 µm SiC micron powder as reinforcements.     

Three routes for the synthesis of the bioceramic powder of the CaO-MgO-SiO2 system

We report three routes for the synthesis of CaO-MgO-SiO₂ (CMS) bioceramic powder using different Si sources and synthesis procedures. The ceramic powders were synthesized from Na₂SiO₃ waste solution by the sol-gel process combined with co-precipitation (synthesis route I and synthesis route II), and from TEOS (tetraethyl orthosilicate) by conventional sol-gel (synthesis route III). Ceramic powders of the CMS multiphase system were obtained, including diopside, wollastonite, akermanite, monticellite and merwinite, which are suitable for application as biomaterial. These powders were sintered at 1200 °C for 2 h to obtain the CMS ceramics. The ceramics mostly contained diopside and wollastonite crystalline phases. Those ceramics when submitted to cytotoxicity tests revealed to be non-cytotoxic, according to ISO10993-5:2009. The ceramics were tested for in vitro bioactivity while soaked in simulated body fluid (SBF) solution. After 14 days, the presence of hydroxyapatite particles on the surface of ceramics was confirmed by Fourier Transform Infrared (FTIR) spectroscopy and Scanning Electron Microscopy (SEM) micrographs. The surfaces were completely covered with hydroxyapatite, after 21 days. In summary, CaO-MgO-SiO₂ (CMS) ceramic powder derived from three routes of synthesis have potential application in the biomedical area. However, further in-vitro and in-vivo studies are needed.