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.     

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.     

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.     

Sol–gel derived alumina–hydroxyapatite–tricalcium phosphate porous composite powders

In this study, alumina–hydroxyapatite–tricalcium phosphate (α-Al₂O₃–HA–TCP) porous composite powders were produced and characterized. At first, boehmite sol (AlOOH) was obtained via sol–gel process by using aluminium isopropoxide (Al(OC₃H₇)₃) as the starting material. Bovine hydroxyapatite (BHA) powders derived from deproteinized bovine bones were added as 10, 20, 30 and 50% weight of the starting material to each boehmite sol. Also Na-alginate was added to the boehmite sol as the dispersive agent. Subsequently, gelation for 3 h at 110 °C was applied to each sol mixture. Finally, gelated samples were heat treated for 2 h at 500, 800, 1000 and 1300 °C. DTA–TGA, XRD, FTIR and SEM-EDS analyses were used to characterize the obtained composite powders composed of α-Al₂O₃–HA–TCP phases. In order to investigate porosity properties, powders were pressed with hydraulic manual press and formed into pellets. Later these pellets were sintered for 2 h at 1300 °C. Apparent porosity and bulk density tests were applied to the pellets. The evaluation of these tests results indicate that a novel α-Al₂O₃–HA–TCP composite material with ～38–44% apparent porosity has been produced.     

Chemical preparation of carbonated calcium hydroxyapatite powders at 37°C in urea-containing synthetic body fluids

An important inorganic phase of synthetic bone applications, calcium hydroxyapatite (HA, Ca₁₀(PO₄)₆(OH)₂), was prepared as a single-phase ceramic powder. Carbonated HA powders were formed from calcium nitrate tetrahydrate and di-ammonium hydrogen phosphate salts dissolved in aqueous ‘synthetic body fluid’ (SBF) solutions, containing urea (H₂NCONH₂), at 37 °C and pH of 7·4, by using a novel chemical precipitation technique. These powders were also found to contain trace amounts of Na and Mg impurities in them, originated from the use of SBF solutions, instead of pure water, during their synthesis. The characterization and chemical analysis of the synthesized powders were performed by powder X-ray diffraction (XRD), Fourier-transformed infra-red spectroscopy (FT–IR), and inductively-coupled plasma atomic emission spectroscopy (ICP–AES).     

Coating of nano-sized ionically conductive Sr and Ca doped LaMnO3 films by sol–gel route

In this study, Sr and Ca doped LaMnO₃ thin ceramic films were coated on Al₂O₃ substrates by using a sol–gel route as the cathode material for SOFC. Nitrate precursors were used for the preparation of the thin film coating solution, and methanol and acetyl acetone were also used as the solvent and chelating agent, respectively. After the solution was prepared, an Al₂O₃ single crystal substrate was dipped into the solution. Then it was fired at 500 °C and annealed at 1025 °C for the crystallization. Coated films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), focused ion beam (FIB) and atomic force microscopy (AFM). Conductivity of the coated films was measured by the four probe Van der Pauw method. XRD, SEM, AFM and FIB characterizations of the coated film showed that the LaMnO₃ phase was formed, surface of the films was uniform and had homogenously distributed pores sized about 10 nm, mean grain size was about 60–80 nm and the film thickness was about 180 nm. The specific resistivity of the film was calculated to be 0.524 Ω m.     

Synthesis and characterization of sol–gel derived calcium hydroxyapatite thin films spin-coated on silicon substrate

The goal of this study was to demonstrate that sol–gel processing route is suitable for the fabrication of calcium hydroxyapatite (Ca₁₀(PO₄)₆(OH)₂, CHA) thin films on Si substrate by spin-coating technique. The substrate was spin-coated by precursor sol solution 1, 5, 15 and 30 times. The samples were annealed after each spin-coating procedure at 1000 °C for 5 h in air. In the sol–gel process ethylendiamintetraacetic acid and 1,2-ethandiol, and triethanolamine and polyvinyl alcohol were used as complexing agents and as gel network forming agents, respectively. The coatings were characterized using X-ray diffraction (XRD) analysis, scanning electron microscopy (SEM), atomic force microscopy (AFM), Fourier transform infrared (FTIR) and Raman spectroscopies, profilometry and the contact angle measurements (CAM). It was demonstrated, that properties of calcium hydroxyapatite thin films depend on spinning and annealing times.     

Synthesis and characterization of bioactive zirconia toughened alumina doped with HAp and fluoride compounds

Alumina–zirconia nanostructured composites (ZrO₂ addition by 20 wt%) were prepared using combined gelation–precipitation process. A modified sol–gel process has been developed to prepare nano structured spinel [MgAl₂O₄], Al₂O₃, ZrO₂ and their composite materials. This process is useful in retaining tetragonal phase of zirconia at room temperature, which provides transformation toughening in the nano composites. Dried gels powders were calcined up to 1250 °C. Similarly, hydroxyapatite powders were produced by wet-chemical method and calcined at different temperatures. All the dried gel and calcined powders were characterized by using X-ray diffraction, DTA/TGA and SEM. Samples were prepared by uniaxial pressing the composites powders using ZTA, HAp, MgF₂ and CaF₂ in different ratio. Incorporation of CaF₂ and MgF₂ as a source for fluorine was also done to improve the sinterability of composites. The samples were sintered at 1400 °C for three hours. Densification and mechanical behaviour of sintered samples were observed. Bioactivities of all compositions were tested using SBF solution and then characterizing by FTIR. The main objective of work was to dope ZTA nano composites with HAp and fluoride compounds to obtain better sinterability at lower temperatures. Then evaluate the obtained ZTA based bioactive composite ceramics that have high mechanical strengths. This study verifies the bioactivities of HAp-added ZTA composites.     

In vitro biocompatibility of a nanocrystalline β-Ta2O5 coating for orthopaedic implants

To improve the durability and bioactivity of Ti–6Al–4V alloy used for medical implants, the β-Ta₂O₅ nano-crystalline coatings were introduced using double cathode glow discharge technique. The coating microstructure was characterized using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HRTEM). The coating exhibits an assembly of near-equiaxed grains, locally aligned normal to the coating surface. The β-Ta₂O₅ coating exhibits strong adhesion to substrate and a strong resistance to deformation and cracking under applied loads. Cells culture tests showed that the coating is more beneficial to the adhesion and proliferation of NIH-3T3 cells as compared to the uncoated alloy. In-vitro bioactivity was evaluated by immersion of the coating in simulated body fluids (SBF) for different periods up to 14 days at 37 °C. The results indicated that bioactivity of Ti–6Al–4V was dramatically improved after the deposition of β-Ta₂O₅, since the coating has a higher apatite forming ability than the Ti–6Al–4V substrate. Finally, the electrochemical behavior of the β-Ta₂O₅ coating after soaking in SBF at 37 °C for 0, 3, 7, and 14 days was studied through potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). EIS measurements also confirm that the presence of a hydroxyapatite layer on the coating becomes thicker and denser during soaking in SBF. Moreover, the coating exhibits better corrosion resistance than the bare alloy. Hence, the β-Ta₂O₅ coating is a promising candidate coating for protection of orthopedic implants with enhanced bioactivity and corrosion resistance.     

Pores occlusion in MCM-41 spheres immersed in SBF and the effect on ibuprofen delivery kinetics: A quantitative model

MCM-41 silica particles have been synthesized with size in the low submicron range, loaded with ibuprofen and characterized by means of XRD, N₂ adsorption and scanning electron microscopy, coupled with EDS analysis both before and after contact with different volumes of simulated body fluid (SBF) at 37 °C up to 10 h.The particles do not show any change in morphology, composition and mesostructure as a consequence of soaking. MCM-41 spheres, though, are not inert towards SBF. Two processes take place, showing features independent from the soaking volume: (i) one within 1–2 h, bringing about dissolution of silica into the liquid phase up to a concentration of 2.2 mM and no change in the mesopore volume; (ii) the second, after an induction period of 1–2 h, bringing about a limited increase in the concentration of dissolved silica, but affecting severely the mesoporous volume, which decreases exponentially with time.Delivery curves differ significantly when varying the volume of SBF used. To account for release kinetics under the circumstances observed, a mathematical model is proposed, based on the standard Noyes–Whitney equation, taking into account both the SBF volume used and the mesopores occlusion, this latter through a time-dependent diffusion coefficient. A satisfactory agreement is observed, without the intervention of any adjustable parameter.     

Morphological,structural and ellipsometric investigations of Cr doped TiO2 thin films prepared by sol–gel and spin coating

Pure and chromium doped titanium dioxide (TiO₂) thin films at different atomic percentages (0.5%, 1.3% and 2.9%) have been elaborated on ITO/Glass substrates by sol–gel and spin–coating methods using titanium (IV) isopropoxide as a precursor. The surface morphology of films was investigated by scanning electron microscopy (SEM) and Atomic Force Microscopy (AFM), the structure was characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and high resolution transmission microscopy (HRTEM). SEM and HRTEM show homogenous and polycrystalline films. XRD patterns indicate a phase transition from anatase to anatase-rutile leading to expand the absorption band of TiO₂ molecules around 520 cm⁻¹ in FTIR spectra. The optical constants such as the refractive index (n), the extinction coefficient (K) and the band gap (E_g) as well as the film thickness are determined using spectroscopic ellipsometry technique and Fourouhi–Blommer dispersion model. Results show three major changes; (i) the thickness of pure TiO₂ layer is 54 nm, which linearly decreases when the layer is doped with chromium and reaches 33 nm for a doping concentration of 2.9%, (ii) the band gap energy (E_g) is also linearly reduced from 3.24 eV to 2.80 eV when the Cr-doping agent increases, and, (iii) a phase transition from anatase to anatase-rutile is observed causing an increase in values of n(λ) for wavelength greater than 350 nm.     

Structural and dielectrical properties of Mg3–Ca3(PO4)2 bioceramics obtained from hydroxyapatite by sol–gel method

Mg₃–Ca₃(PO₄)₂ bioceramics were prepared from hydroxyapatite (HAp) with high Mg contents using sol–gel method. The influence of magnesium on the phase composition, crystal structure, electrical properties, chemical structure and morphological characteristics of powder bioceramics was analyzed using X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM). Dielectrical properties of the bioceramics were investigated by a dielectric impedance spectroscopy method. It was observed that the crystallization degree for all the samples dramatically was decreased with the increasing Mg content. The average crystallite size of the samples was found to vary from 32 to 42 nm. The morphology, density and dielectric properties of the bioceramics were changed with the addition of the amount of Mg. The obtained results indicate that the Mg₃–Ca₃(PO₄)₂ bioceramics can be prepared by means of hydroxyapatite bioceramic.     

Triton X-100 directed synthesis of mesoporous γ-Al2O3 from coal-series kaolin

Mesoporous γ-Al₂O₃ has been successfully synthesized by using calcined coal-series kaolin as raw material and Triton X-100 (TX-100) as template. The effect of TX-100/Al^3 + ratio on the structural and textural properties of mesoporous γ-Al₂O₃ was investigated. Physical properties of obtained samples were characterized by X-ray diffraction (XRD), N₂ adsorption–desorption, transmission electron microscopy (TEM), thermogravimetric analysis (TG), scanning electron microscopy (SEM) with energy-dispersive X-ray analysis (EDAX) and Fourier transform infrared spectroscopy (FTIR). The results indicated that the amount of TX-100 influenced the structure and porous properties of mesoporous γ-Al₂O₃ significantly. When TX-100/Al^3 + ratio was in the range of 0.03–0.15, all samples had mesoporous structures with BET surface area of 193.0–261.0 m²/g and pore size of 5.04–6.71 nm. In addition, the reaction mechanism involved in the process was proposed and discussed.     

Facile synthesis of crystalline nanoporous Mg3(PO4)2 and its application to aerobic oxidation of alcohols

Nanoporous crystalline Mg₃(PO₄)₂ material was synthesized by a simple hydrothermal method using Poly ethylene glycol (PEG) as a template. The material was thoroughly characterized by XRD, FTIR, DT/TGA, CO₂-TPD, SEM, TEM, N₂ sorption and was readily explored for the industrially important oxidation of alcohols at solvent-less liquid phase aerobic conditions. At 100 °C and 4 bar pressure, the material successfully produced benzaldehyde (88% selectivity). The material also exhibited reusability and reaction time stability properties desired for industrial applications. The subject gains novelty in terms of the synthesis of nanoporous crystalline Mg₃(PO₄)₂ material as well as its first of its kind application to aerobic oxidation.     

Synthesis of apatite structure based BiNaCa3(PO4)3OH and its application for condensation reaction

Mono, di and trivalent ions containing hydroxyapatite of the formula BiNaCa₃(PO₄)₃OH has been synthesized and the compound's catalytic activity in three component Biginelli condensation was studied. The compound was characterized by powder XRD, FT-IR, SEM and TGA/DTA techniques. The unit cell dimensions of the compound were determined to be a = 9.412(2) Å, C = 6.92(2) Å and the unit cell volume is 530.9 Å³. The substituted hydroxyapatite phase showed enhanced reactivity in the one pot synthesis of 3,4-dihydropyrimidin-2(1H)-one by Biginelli reaction and resulted in an increased yield of the product.     

Cytocompatibility,bioactivity and mechanical strength of calcium phosphate cement reinforced with multi-walled carbon nanotubes and bovine serum albumin

This paper reports on the in vitro cytotoxicity, bioactivity behaviour and mechanical properties of novel injectable calcium phosphate cement filled with hydroxylated multi-walled carbon nanotubes and bovine serum albumin (CPC/MWCNT-OH/BSA). To predict the in vitro bioactivity of the calcium phosphate composites, we investigated apatite formation on CPC/MWCNT-OH/BSA composites after soaking in simulated body fluid (SBF) for up to 28 days. Compressive strength tests, scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and cell culture experiments with human CCD-18Co fibroblasts cell lines were performed to evaluate the effect of SBF pre-treatment on the mechanical, structural and biological properties of the CPC/MWCNT-OH/BSA composites. Although apatite formation increased significantly with SBF immersion period, the results showed that all soaked CPC/MWCNT-OH/BSA composites exhibited up to 2.5 times lower compressive strength (13–20 MPa), which were however higher than values reported for the strength of trabecular bone (2–12 MPa). Cell culture experiments showed that low concentrations (6.25 and 12.5 μg/ml) of bio-mineralised CPC/MWCNT-OH/BSA composites led to cell proliferative rather than cytotoxic effects on fibroblasts, evidenced by high cell viabilities (104–113%). The novel CPC/MWCNT-OH/BSA composites presented in this study showed favourable cytocompatible and bioactive behaviour along with high compressive strength (13–32 MPa) and are therefore considered as an attractive bone filling material.     

Optical,thermal and dielectric properties of Bi4(TiO4)3 ceramic powders

Bismuth titanate (Bi₄(TiO₄)₃) ceramic powders have been synthesized by using a solid state reaction method. Prominently intense blue emission at 480 nm has been measured with an excitation at 418 nm. The reason for the observance of such a blue emission from this ceramic powder has been explained. The phase formation has been investigated by X-ray diffraction analysis (XRD). The morphology and composition of the ceramic powders have been studied from the measurement of SEM and EDS profiles. FTIR and Raman spectra have also been recorded to analyze the presence of functional groups and Raman active modes in the Bi₄(TiO₄)₃ ceramic powders. The sintering temperature has been optimized to be 1100 °C based on the measured TG–DTA profiles of the as prepared material. Besides these, dielectric properties of ceramic powder in the frequency range of 200 Hz–3 MHz at 300 K have also been carried out.     

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.     

A novel SiCN@TiO2 core–shell ceramic microspheres derived from a polymeric precursor

A novel core–shell ceramic microspheres, composed of a SiCN inner core and TiO₂ nanoparticles outer shell, were prepared via emulsion technique and polymer-derived ceramics (PDCs) method. The forming process of SiCN@TiO₂ core–shell ceramic microspheres were controlled by adjusting the ratio of raw material, curing temperature and pyrolysis temperature. The morphology, chemical composition and phase transformation were characterized by scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD). PVSZ@TiO₂ microspheres with good spherical structure and uniform-dispersed TiO₂ surface were fabricated at 200 °C with raw material ratio of 25%. After pyrolyzed at 1400 °C, the obtained SiCN@TiO₂ core–shell ceramic microspheres retained spherical structure. The XRD showed that the products were mainly composed of rutile TiO₂, SiC and Si₃N₄ crystalline phase, which were generated by polyvinylsilazane.