Characterization and in vitro-bioactivity of natural hydroxyapatite based bio-glass–ceramics synthesized by thermal plasma processing

Natural bovine hydroxyapatite/SiO₂–CaO–MgO glass–ceramics were produced using the transferred arc plasma (TAP) processing method. Homogeneous mixtures of HA/25 wt% SiO₂–CaO–MgO and HA/50 wt% SiO₂–CaO–MgO batches obtained by dry mixing the respective compositions in a ball mill were processed in argon plasma using the TAP torch at 5 kW for 1, 2 and 3 min, respectively. The synthesized glass–ceramic samples were studied for phase composition, microstructure and bioactivity. The phase study of the synthesized glass–ceramics revealed the formation of calcium phosphate silicate with traces of calcium silicate. The structural study by SEM revealed that the prepared samples possessed smooth glassy surface morphology. The in vitro-bioactivity of the TAP synthesized glass–ceramics was examined in simulated body fluid (SBF). The SBF test results confirmed the development of crystalline carbonated apatite phase after 12 days of immersion. The cytocompatibility was evaluated through human fibroblast cell proliferation. The fibroblasts culture results showed that the sample was non-toxic and promoted cell growth.     

Direct-write assembly of silicate and borate bioactive glass scaffolds for bone repair

Silicate (13-93) and borate (13-93B3) bioactive glass scaffolds were created by robotic deposition (robocasting) of organic solvent-based suspensions and evaluated in vitro for potential application in bone repair. Suspensions (inks) were developed, characterized, and deposited layer-by-layer to form three-dimensional scaffolds with a grid-like microstructure (porosity ≈50%; pore width 420 ± 30 μm). The mechanical response of the scaffolds was tested in compression, and the conversion of the glass to hydroxyapatite (HA)-like material in a simulated body fluid (SBF) was evaluated. As fabricated, the 13-93 scaffolds had a compressive strength 142 ± 20 MPa, comparable to the strength of human cortical bone, while the strength of the 13-93B3 scaffolds (65 ± 11 MPa), was far higher than that for trabecular bone. When immersed in SBF, the borate 13-93B3 scaffolds converted faster than the silicate 13-93 scaffolds to an HA-like material, but they also showed a sharper decrease in strength with immersion time. Based on their high compressive strength and bioactivity, the scaffolds fabricated in this work by robocasting could have potential application in the repair of load-bearing bone.     

Fabrication and characterization of 45S5 bioglass reinforced macroporous calcium silicate bioceramics

Bioactive and degradable macroporous bioceramics play an important role in clinical applications. In the present study, 45S5 bioglass reinforced macroporous calcium silicate ceramics (45BG-reinforced MCSCs) were fabricated. The effect of bioglass additives on compressive strength and open porosity of the samples was investigated, and the bioactivity and degradability of the obtained reinforced samples were also evaluated. The 45S5 bioglass additive was found to be effective to increase the strength of the MCSCs by the liquid-phase sintering mechanism. The optimum amount of bioglass additives was 5 wt.% and the compressive strength of the reinforced samples was approximately 2 times higher as compared to the pure macroporous calcium silicate ceramics (MCSCs). The compressive strength of the reinforced samples with about 50% porosity reached 112.47 MPa, which was similar to those of the cortical bones. After soaking in simulated body fluid (SBF), hydroxycarbonate apatite (HCA) layer was formed on the surface of the 45BG-reinforced MCSCs. Furthermore, the degradation rate of the reinforced samples was just about one-third of those pure MCSCs. Our results indicated that degradable 45BG-reinforced MCSCs possess excellent mechanical strength and bioactivity, and may be used as bioactive and degradable biomaterials for hard tissue prosthetics or bone tissue engineering applications.     

Gel-derived SiO2–CaO–P2O5 bioactive glasses and glass-ceramics modified by SrO addition

The effect of SrO substitution for CaO in two sol–gel glasses with different chemical compositions (mol%) A2Sr: (54−x)CaO–xSrO–6P₂O₅–40SiO₂ and S2Sr: (16−x)CaO–xSrO–4P₂O₅–80SiO₂ (x=0, 1, 3 and 5) stabilized at 700 °C on their structure (XRD, FTIR) and bioactive properties (SBF test) was investigated. Preliminary in vitro tests using human articular chondrocytes of selected A2Sr glass were also conducted. Moreover, the subject of this study was to detect the changes on material properties after heat treatment at 1300 °C. The results show that the effect of strontium substitution on structure, bioactivity and crystallization after treatment at both the above temperatures strongly depends on CaO/SiO₂ molar ratio. The presence of 3–5 mol% of strontium ions creates more expanded glass structure but does not markedly affect crystallization ability after low temperature treatment. Sintering at 1300 °C of A2 type glasses results in crystallization of pseudowollastonite, hydroxyapatite and also Sr-substituted hydroxyapatite for 3–5 mol% of SrO substitution. The increase of strontium concentration in silica-rich materials after sintering leads to appearance of calcium strontium phosphate instead of calcium phosphate. Bioactivity evaluation indicates that substitution of Sr for Ca delays calcium phosphate formation on the materials surface only in the case of silica-rich glasses treated at 700 °C. Calcium-rich glasses, after both temperature treatments, reveals high bioactivity, while crystal size of hydroxyapatite decreases with increasing Sr content. High temperature treatment of high-silica glasses inhibits their bioactivity. Preliminary in vitro tests shows Sr addition to have a positive effects on human articular chondrocytes proliferation and to inhibit cell matrix biomineralization.     

In vitro bioactivity assessment and mechanical properties of novel calcium titanate/borosilicate glass composites

Bioactive calcium titanate/borosilicate glass composites were developed. Powder mixtures of borosilicate glass and 10, 20 or 30 wt% of potassium polytitanate particles were uniaxially pressed and sintered at 850 °C for 1 h. After heat treatment the reaction between potassium polytitanate and borosilicate glass produced composites consisting of calcium titanate particles embedded in a B-rich amorphous phase. For the in vitro bioactivity assessment sintered samples were immersed in a simulated body fluid (SBF) for 21 days under physiological conditions of pH and temperature. The compressive strength of the composites was also evaluated. A homogeneous and thick apatite layer was formed on all the materials tested. Furthermore, an appropriate compressive strength was observed (68-85 MPa). These results indicate that these composites are potential materials for bone tissue replacement and regeneration.     

Microstructure and properties of needle punching chopped carbon fiber reinforced carbon and silicon carbide dual matrix composite

Chopped carbon fiber preform reinforced carbon and SiC dual matrix composites (C/C–SiC) were fabricated by chemical vapor infiltration (CVI) combined with liquid silicon infiltration. The preform was fabricated by repeatedly overlapping chopped carbon fiber web and needle punching technique. A geometry model of the pore structure of the preform was built and reactant gas transportation during the CVI was calculated. The microstructure and properties of the C/C–SiC composites were investigated. The results indicated that the CVI time for densification of the preform decrease sharply, and the model showed the permeability of the preform decreased with the increase of its density. The C/C–SiC exhibited good mechanical characteristics, especially excellent compressive behavior, with the vertical and parallel compressive strength reached to 359(±40) MPa and 257(±35) MPa, respectively. The coefficient of friction (COF) decreased from 0.60 (at 8 m/s) with the increase of sliding velocity, and finally stabilized at ~0.35 under the velocity of 20 m/s and 24 m/s, and the variations of COF were not sensitive to the sliding distance. The wear rates were between 0.012 cm³/MJ and 0.024 cm³/MJ under different velocities. These results showed that the chopped carbon fiber preform reinforced C/C–SiC are promising candidates for high-performance and low-cost friction composites.     

Improving compressive strength of fly ash-based geopolymer composites by basalt fibers addition

In this study, ASTM Class C fly ash used as an alumino-silicate source was activated by metal alkali and cured at low temperature. Basalt fibers which have excellent physical and mechanical properties were added to fly ash-based geopolymers for 10–30% solid content to act as a reinforced material, and its influence on the compressive strength of geopolymer composites has been investigated. XRD study of synthesized geopolymers showed an amorphous phase of geopolymeric gel in the 2θ region of 23°–38° including calcium-silicate-hydrate (C-S-H) phase, some crystalline phases of magnesioferrite, and un-reacted quartz. The microstructure investigation illustrated fly ash particles and basalt fibers were embedded in a dense alumino-silicate matrix, though there was some un-reacted phase occurred. The compressive strength of fly ash-based geopolymer matrix without basalt fibers added samples aged 28 days was 35 MPa which significantly increased 37% when the 10 wt%. basalt fibers were added. However, the addition of basalt fibers from 15 to 30 wt% has not shown a major improvement in compressive strength. In addition, it was found that the compressive strength was strong relevant to the Ca/Si ratio and the C-S-H phase in the geopolymer matrix as high compressive strength was found in the samples with high Ca/Si ratio. It is suggested that basalt fibers are one of the potential candidates as reinforcements for geopolymer composites development.     

Bioactivity modulation of Bioglass® powder by thermal treatment

A discussion of the effects of Bioglass^® powder crystallisation on the in vitro bioactivity in simulated body fluid (SBF) is presented.Starting from Bioglass^® powder, different glass–ceramics were obtained by thermal treatments between 580 °C and 800 °C, with variable crystallisation content (from 10 to 92 wt%). All samples (glass and glass–ceramics) showed apatite formation at their surface when immersed in SBF. In case of the glass and the samples with lowest crystallinity, the first step of apatite formation involved a homogenous dissolution followed by an amorphous calcium phosphate (CaP) layer precipitation. For the samples with a high crystallisation content, heterogeneous dissolution occurred. For the first time, the Stevels number of the amorphous phase is used to explain the possible dissolution of the crystalline phase present in materials with a similar chemical composition of the Bioglass^®. All samples presented at 21 days of immersion in SBF B-type hydroxycarbonate apatite crystals.     

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.     

Synthesis and in vitro bioactivity assessment of injectable bioglass−organic pastes for bone tissue repair

The aim of this work was to study the bioactivity of systems based on a clinically tested bioactive glass (BG) particulates (mol%: 4.33 Na₂O−30.30 CaO−12.99 MgO−45.45 SiO₂−2.60 P₂O₅−4.33 CaF₂) and organic carriers. The cohesiveness of injectable bone graft products is of high relevance when filling complex volumetric bone defects. With this motivation behind, BG particulates with mean sizes within 11−14 μm were mixed in different proportions with glycerol (G) and polyethylene glycol (PEG) as organic carriers and the mixtures were fully injectable exhibiting Newtonian flow behaviors. The apatite forming ability was investigated using X-ray diffraction and field emission scanning electron microscopy under secondary electron mode after immersion of samples in simulated body fluid (SBF) for time durations varying between 12 h and 7 days. The results obtained revealed that in spite of the good adhesion of glycerol and PEG carriers to glass particles during preparation stage, they did not hinder the exposure of bioactive glass particulates to the direct contact with SBF solution. The results confirmed the excellent bioactivity in vitro for all compositions expressed by high biomineralization rates with the formation of crystalline hydroxyapatite being identified by XRD after 12 h of immersion in SBF solution.     

Grafting of epoxy chains onto graphene oxide for epoxy composites with improved mechanical and thermal properties

Epoxy composites filled with both graphene oxide (GO) and diglycidyl ether of bisphenol-A functionalized GO (DGEBA–f–GO) sheets were prepared at different filler loading levels. The correlations between surface modification, morphology, dispersion/exfoliation and interfacial interaction of sheets and the corresponding mechanical and thermal properties of the composites were systematically investigated. The surface functionalization of DGEBA layer was found to effectively improve the compatibility and dispersion of GO sheets in epoxy matrix. The tensile test indicated that the DGEBA–f–GO/epoxy composites showed higher tensile modulus and strength than either the neat epoxy or the GO/epoxy composites. For epoxy composite with 0.25 wt% DGEBA–f–GO, the tensile modulus and strength increased from 3.15 ± 0.11 to 3.56 ± 0.08 GPa (∼13%) and 52.98 ± 5.82 to 92.94 ± 5.03 MPa (∼75%), respectively, compared to the neat epoxy resin. Furthermore, enhanced quasi-static fracture toughness (K_IC) was measured in case of the surface functionalization. The GO and DGEBA–f–GO at 0.25 wt% loading produced ∼26% and ∼41% improvements in K_IC values of epoxy composites, respectively. Fracture surface analysis revealed improved interfacial interaction between DGEBA–f–GO and matrix. Moreover, increased glass transition temperature and thermal stability of the DGEBA–f–GO/epoxy composites were also observed in the dynamic mechanical properties and thermo-gravimetric analysis compared to those of the GO/epoxy composites.     

Synthesis,characterization and bioactivity investigation of bioglass/hydroxyapatite composite

Bioactive glass of the type CaO–P₂O₅–SiO₂ was obtained by the sol–gel processing method. The obtained material was characterized by X-ray powder diffraction (XRD). Composite samples of hydroxyapatite with synthesized bioglass were prepared at 1000 °C and characterized by XRD, Fourier transform infrared spectroscopy (FTIR), and surface electron microscopy (SEM). The bioactivity was examined in vitro with respect to the ability of hydroxyapatite layer to form on the surface as a result of contact with simulated body fluid (SBF). XRD, FTIR and SEM studies were conducted before and after contact of the material with SBF. It could be detected that the bioglass was crystallized partly. Furthermore, silicated hydroxyapatite may have formed due to the diffusion of silicate groups to the apatite phase and these may have substituted for the phosphate groups. It can be concluded from SEM and FTIR results that apatite phase formed after 14 days in SBF.     

Fabrication and compressive strength of porous hydroxyapatite scaffolds with a functionally graded core/shell structure

A novel type of porous hydroxyapatite (HA) scaffolds with a functionally graded core/shell structure was fabricated by freeze casting HA/camphene slurries with various HA contents into fugitive molds containing a graphite template with three-dimensionally interconnected pores for the creation of a highly porous core. All the fabricated samples had functionally graded core/shell structures with 3-D periodic pore networks in a core surrounded by a relatively dense shell. The overall porosity of the sample decreased from 60 to 38 vol% with increasing HA content in the HA/camphene slurry from 20 to 36 vol% due to a decrease in porosity in both the core and shell regions. In addition, the compressive strength was improved remarkably from 12 ± 1.1 to 32 ± 3.0 MPa. The in vitro cell test using a pre-osteoblast cell line showed that the samples had good biocompatibility.     

Formation of dicalcium phosphate dehydrate coating on carbon fibers with in-situ grown graphene nanosheet interlayer

A dicalcium phosphate dehydrate (DCPD) coating was successfully fabricated on carbon fiber with in-situ grown graphene (IGN) interlayer. The obtained coating was analyzed using XRD, SEM, XPS, Raman, TEM and Thermo-gravimetric analysis(TGA). The in-vitro bioactivity of the obtained coating was investigated by simulated body fluid (SBF) immersion test. The results showed that the IGN interlayer grew homogenously on the carbon fiber with a wavy shape. The IGN interlayer was 40–90 nm in length and less than 10 nm in thickness. The DCPD exhibited a flake shape with a size of 10–50 nm. The IGN could bond with the DCPD tightly and form a uniform distribution within the DCPD coating. TGA test revealed that the carbon fiber with IGN interlayer was more effective for DCPD attachment and deposition than pure carbon fiber. The SBF tests showed that the DCPD coating could induce the formation of a cloud shaped apatite layer. The DCPD coated carbon fiber with IGN interlayer would be possible for potential application in tissue engineering.     

Effects of oxide addition on the microstructure and mechanical properties of lamellar SiC scaffolds and Al–Si–Mg/SiC composites prepared by freeze casting and pressureless infiltration

Silicate-bonded porous SiC scaffolds with lamellar structures were prepared by freeze casting and liquid-phase sintering. It was found that the viscosity and solidification velocity of SiC water-based slurries with 30 vol% solid loading decreased with increasing Al₂O₃–MgO (AM) addition. As the AM content increased from 10 to 30 wt%, the lamellae of the sintered scaffolds became denser and the porosity decreased from 69±0.5% to 62±0.5%, while the compressive strength improved from 25±2 to 51±2 MPa. The dynamics of pressureless infiltration for an Al–12 Si–10 Mg alloy on the SiC porous scaffold was measured and the composites with lamellar-interpenetrated structures were successfully produced. Both the compressive strength and the elastic modulus of the composites increased with increasing AM content. The maximum strength reached 952±24 MPa and the highest elastic modulus about 156 GPa, respectively, in a longitudinal direction, increasing about 32% and 11% as compared with those of the composites without AM.     

Preparation and characterization of novel bioactive dicalcium silicate ceramics

The beta- and gamma-dicalcium silicate (β- and γ-Ca₂SiO₄) ceramics were prepared by sintering β-Ca₂SiO₄ greens at 1100, 1300, and 1450 °C, respectively, after compacting with cold isostatic pressure. The phase transition from β- to γ-phase of polymorphic ceramics occurred at 1100–1300 °C. Bending strength and Vickers hardness of β-Ca₂SiO₄ ceramic sintered at 1100 °C were only 25.6 ± 3.8 MPa and 0.41 ± 0.05 GPa. In contrast, the mechanical properties of the γ-Ca₂SiO₄ were improved remarkably when the ceramics were sintered at 1450 °C, corresponding to bending strength, 97.1 ± 6.7 MPa; Vickers hardness, 4.34 ± 0.35 GPa, respectively. The ceramics were soaked in the simulated body fluid (SBF) for various periods were characterized by SEM, XRD, FTIR, and EDS analysis, and the results indicated that the carbonated hydroxyapatite (CHA) was formed on the surface of the ceramics within 3 days. In addition, cell attachment assay showed that the ceramics supported the mesenchymal stem cells adhesion and spreading, and the cells established close contacts with the ceramics after 1 day of culture. These findings indicate that the γ-Ca₂SiO₄ ceramic possesses good bioactivity, biocompatibility and mechanical properties, and might be a promising bone implant material.     

Synthesis and mechanical properties of porous alumina from anisotropic alumina particles

A porous alumina body was synthesized from anisotropic alumina particles (platelets). The uniaxial pressure in fabricating the green compact body had an influence on the relative density of the alumina body after heating. When green compacts, which had been uniaxially pressed at 1 and 3 MPa, were heated at 1400 °C for 1 h, the relative densities of the resulting alumina bodies were 25.0% and 35.5%, respectively. The compressive strength of compacts that were uniaxially pressed at 1 and 3 MPa were 0.8 and 4.3 MPa, respectively. In an attempt to increase the compressive strength of these porous alumina bodies, aluminum nitrate and magnesium nitrate solution treatments were performed, followed by reheating to 1400 °C for 1 h. When a 0.5 mol/l aluminum nitrate solution was used, the compressive strength of the porous alumina body uniaxially pressed at 1 MPa changed from 0.8 MPa (without solution treatment) to 1.5 MPa. Furthermore, when 0.1 mol/l magnesium nitrate solution was used, the compressive strength of the porous alumina increased to 1.7 MPa. Thus, solution treatment of the porous alumina body had a strong positive effect on its mechanical strength.     

Graphene oxide/hydroxyapatite composite coatings fabricated by electrophoretic nanotechnology for biological applications

Graphene oxide (GO) was firstly employed as nanoscale reinforcement fillers in hydroxyapatite (HA) coatings by a cathodic electrophoretic deposition process, and GO/HA coatings were fabricated on pure Ti substrate. The transmission electron microscopy observation and particle size analysis of the suspensions indicated that HA nanoparticles were uniformly decorated on GO sheets, forming a large GO/HA particle group. The addition of GO into HA coatings could reduce the surface cracks and increase the coating adhesion strength from 1.55 ± 0.39 MPa (pure HA) to 2.75 ± 0.38 MPa (2 wt.% GO/HA) and 3.3 ± 0.25 MPa (5 wt.% GO/HA), respectively. Potentiodynamic polarization and electrochemical impedance spectroscopy studies indicated that the GO/HA composite coatings exhibited higher corrosion resistance in comparison with pure HA coatings in simulated body fluid. In addition, superior (around 95% cell viability for 2 wt.% GO/HA) or comparable (80–90% cell viability for 5 wt.% GO/HA) in vitro biocompatibility were observed in comparison with HA coated and uncoated Ti substrate.     

Amorphous carbonated apatite formation on diamond-like carbon containing titanium oxide

Thin films of diamond-like carbon (DLC) containing titanium oxide (DLC-TiO_x, x ≤ 2) were synthesized using a pulsed DC metal–organic plasma activated chemical vapor deposition (MOCVD) technique. X-ray photoelectron spectroscopy (XPS) results confirmed the presence of TiO₂ on the surface of the films. The compressive stress, elastic modulus and hardness of the films decreased with increasing Ti content. The water contact angle reduced from 62° for DLC to 45° for DLC-TiO_x films containing 13.3 at.% of Ti. The biomimetic growth of amorphous carbonated apatite on the DLC-TiO_x in simulated body fluid (SBF) was found and dependent on the Ti content of the film. UV light exposure prior to immersion in SBF increased the growth rate of apatite formation significantly as a result of increased hydrophilicity of the surface.     

Mechanical and dielectric properties of SiCf/SiC composites fabricated by PIP combined with CIP process

2D KD-1 SiC fiber fabrics were employed to fabricate SiC_f/SiC composites by an improved polymer infiltration and pyrolysis (PIP) process, combined with cold isostatic pressing (CIP). The effect of CIP process on the microstructure, mechanical and dielectric properties of SiC_f/SiC composites was investigated. The infiltration efficiency was remarkably improved with the introduction of CIP process. Compared to vacuum infiltration, the CIP process can effectively increase the infiltrated precursor content and decrease the porosity resulting in a dense matrix. Thus SiC_f/SiC composites with high density of 2.11 g cm⁻³ and low porosity of 11.3% were obtained at 100 MPa CIP pressure, together with an increase of the flexural strength of the composites from 89 MPa to 213 MPa. Real part (ε′) and the imaginary part (ε″) of complex permittivity of SiC_f/SiC composites increase and vary from 11.7-i9.7 to 15.0-i12.8 when the CIP pressure reaches 100 MPa.