A comparison of bioactive glass scaffolds fabricated by robocasting from powders made by sol-gel and melt-quenching methods

Bioactive glass scaffolds are used in bone and tissue biomedical implants, and there is great interest in their fabrication by additive manufacturing/3D printing techniques, such as robocasting. Scaffolds need to be macroporous with voids ≥100 μm to allow cell growth and vascularization, biocompatible and bioactive, with mechanical properties matching the host tissue (cancellous bone for bone implants), and able to dissolve/resorb over time. Most bioactive glasses are based on silica to form the glass network, with calcium and phosphorous content for new bone growth, and a glass modifier such as sodium, the best known being 45S5 Bioglass®. 45S5 scaffolds were first robocast in 2013 from melt-quenched glass powder. Sol-gel-synthesized bioactive glasses have potential advantages over melt-produced glasses (e.g., greater porosity and bioactivity), but until recently were never robocast as scaffolds, due to inherent problems, until 2019 when high-silica-content sol-gel bioactive glasses (HSSGG) were robocast for the first time. In this review, we look at the sintering, porosity, bioactivity, biocompatibility, and mechanical properties of robocast sol-gel bioactive glass scaffolds and compare them to the reported results for robocast melt-quench-synthesized 45S5 Bioglass® scaffolds. The discussion includes formulation of the printing paste/ink and the effects of variations in scaffold morphology and inorganic additives/dopants

Studies of structural, magnetic and dielectric properties of X-type Barium Zinc hexaferrite Ba2Zn2Fe28O46 powder prepared by combustion treatment method using ginger root extract as a green reducing agent

Various quantities of ginger (Zingiber officinale) root extract were used to prepare X-type Barium–Zinc hexaferrite with the chemical composition Ba2Zn2Fe28O46. The powders were prepared using a combustion treatment method, being pre-heated at 550 °C for 4 h with the ginger as a fuel, followed by final heating to 900 °C for 5 h and natural cooling to room temperature to obtain Ba2Zn2Fe28O46 hexagonal ferrite powder. The phase composition of heated powder samples was investigated by X-ray diffraction (XRD), indicating the formation of a mixture of X-type and hematite (α-Fe2O3). Up to 82.6%, X-ferrite was formed at 900 °C with 52.5 g of ginger root extract. Dielectric analysis of the prepared samples shows the frequency-dependent phenomena. All samples were hard magnets, with coercivity values (HC) between 262.2 and 318.3 kA m−1, and squareness ratios > 0.5. The sample prepared with 52.5 g ginger root extract possesses the highest value of saturation magnetisation (MS = 33.87 Am2 kg−1) in comparison with the other prepared samples. Therefore, ginger was shown to be a useful natural plant extract as a reducing fuel for the low-temperature synthesis of X-ferrites. The sample prepared with 35 g ginger root extract shows a broad loss tangent resonance peak between 10 kHz and 100 kHz, while other samples show loss tangent resonance peaks between 300 kHz and 2 MHz frequency range

Studies of structural, magnetic and dielectric properties of X-type Barium Zinc hexaferrite Ba2Zn2Fe28O46 powder prepared by combustion treatment method using ginger root extract as a green reducing agent

Various quantities of ginger (Zingiber officinale) root extract were used to prepare X-type Barium–Zinc hexaferrite with the chemical composition Ba2Zn2Fe28O46. The powders were prepared using a combustion treatment method, being pre-heated at 550 °C for 4 h with the ginger as a fuel, followed by final heating to 900 °C for 5 h and natural cooling to room temperature to obtain Ba2Zn2Fe28O46 hexagonal ferrite powder. The phase composition of heated powder samples was investigated by X-ray diffraction (XRD), indicating the formation of a mixture of X-type and hematite (α-Fe2O3). Up to 82.6%, X-ferrite was formed at 900 °C with 52.5 g of ginger root extract. Dielectric analysis of the prepared samples shows the frequency-dependent phenomena. All samples were hard magnets, with coercivity values (HC) between 262.2 and 318.3 kA m−1, and squareness ratios > 0.5. The sample prepared with 52.5 g ginger root extract possesses the highest value of saturation magnetisation (MS = 33.87 Am2 kg−1) in comparison with the other prepared samples. Therefore, ginger was shown to be a useful natural plant extract as a reducing fuel for the low-temperature synthesis of X-ferrites. The sample prepared with 35 g ginger root extract shows a broad loss tangent resonance peak between 10 kHz and 100 kHz, while other samples show loss tangent resonance peaks between 300 kHz and 2 MHz frequency range.publishe

Efficiency of natural clay and titania P25 composites in the decolouring of methylene blue (MB) from aqueous solutions: dual adsorption and photocatalytic processes

In this paper, we use Tunisian clay materials as alternative low-cost adsorbents, as well as substrates to immobilise TiO2 for the decolouration of methylene blue (MB) dye solutions. The collected raw clay from the mine of Tamra was characterised by various techniques, such as X-ray diffraction (XRD), scanning electron microscopy (SEM) and X-ray fluorescence (XRF). XRD patterns of the raw clay showed halloysite as the main phase (61%), with a lower content of kaolinite (39%). For MB adsorption, the experimental data were fitted by Langmuir and Freundlich adsorption equations. It was found that the studied clays alone were not very efficient at adsorbing MB dye molecules. The decolouration of MB was improved by adding a photocatalytic function to the clay, by adding various amounts of TiO2 nanopowder (20–80 wt%) to the clay, imbuing it with photocatalytic capabilities. These combined effects of the phenomena of adsorption and photocatalysis for MB removal by the TiO2-doped clay resulted in a very satisfactory performance, even with the relatively low quantity of 20 wt% added TiO2 photocatalyst. This gave 48.6% removal after only 30-min adsorption in the dark, increasing to 84.1% removal after a further 3 h under UV light, through combined chemo-physical adsorption and photocatalytic decolouration phenomena

Robocasting: Prediction of ink printability in solgel bioactive glass

Bioactive glass powders synthesized by solgel are usually porous and exhibit high specific surface areas, conferring them poor ability for scaffolds fabrication using colloidal processing approaches. The difficulties associated with colloidal processing of solgel glass have hindered so far the processing of 3-D scaffolds by robocasting. This research paper investigates the importance of calcination temperature (CT) and balls to powder ratio (BPR) used upon wet milling on the maximum achievable solid loading in aqueous media. The effects of CT, BPR, and solid loading on the flow behavior and viscoelastic properties of the suspensions/pastes were evaluated in this preliminary work. The aim is to disclose the sets of experimental variables that are most promising for the formulation of printable inks, and open the way for the future fabrication of porous scaffolds by robocasting and other 3-D additive manufacturing techniques

Robocasting of Cu 2+ & La 3+ doped sol–gel glass scaffolds with greatly enhanced mechanical properties: Compressive strength up to 14 MPa

This research details the successful fabrication of scaffolds by robocasting from high silica sol–gel glass doped with Cu 2+ or La 3+ . The parent HSSGG composition within the system SiO 2 –CaO–Na 2 O–P 2 O 5 [67% Si – 24% Ca – 5% Na – 4% P (mol%)] was doped with 5 wt% Cu 2+ or La 3+ (Cu5 and La5). The paper sheds light on the importance of copper and lanthanum in improving the mechanical properties of the 3–D printed scaffolds. 1 h wet milling was sufficient to obtain a bioglass powder ready to be used in the preparation of a 40 vol% solid loading paste suitable for printing. Moreover, Cu addition showed a small reduction in the mean particle size, while La exhibited a greater reduction, compared with the parent glass. Scaffolds with macroporosity between 300 and 500 µm were successfully printed by robocasting, and then sintered at 800 °C. A small improvement in the compressive strength (7–18%) over the parent glass accompanied the addition of La. However, a much greater improvement in the compressive strength was observed with Cu addition, up to 221% greater than the parent glass, with compressive strength values of up to ∼14 MPa. This enhancement in compressive strength, around the upper limit registered for human cancellous bones, supports the potential use of this material in biomedical applications. Statement of Significance: 3D porous bioactive glass scaffolds with greatly improved compressive strength were fabricated by robocasting from a high silica sol–gel glasses doped with Cu 2+ or La 3+ . In comparison to the parent glass, the mechanical performance of scaffolds was greatly improved by copper-doping (>220%), while a modest increase of ∼9% was registered for lanthanum-doping. Doping ions (particularly La 3+ ) acted as glass modifiers leading to less extents of silica polymerisation. This favoured the milling of the glass powders and the obtaining of smaller mean particle sizes. Pastes with a high solid loading (40 vol%) and with suitable rheological properties for robocasting were prepared from all glass powders. Scaffolds with dimensions of 3 × 3 × 4 mm and macro-pore sizes between 300 and 500 µm were fabricated

The role of calcium (source & content) on the in vitro behaviour of sol–gel quaternary glass series

To highlight the effect of salt precursors on the final properties, bioactivity and biocompatibility, five quaternary (Si–Ca–P–Na) glass compositions were successfully prepared through two distinct rapid sol–gel routes; one using acetate salt precursors (A) catalysed by nitric acid, and the other using nitrate salts (N) and citric acid as a catalyst. The sols dried rapidly, and stabilised at 550 & 800 °C to be characterised by X–ray diffraction (XRD), Magic angle spinning–Nuclear magnetic resonance (29Si MAS–NMR) and Fourier transform infra–red spectroscopy (FTIR). Upon immersion in simulated body fluid (SBF), hydroxyapatite (HAp) formation was initially enhanced by increasing Ca–content up to 40 mol%, but the formation of calcite was favoured with further increments of Ca to 45 and 48 mol%. The A–glasses exhibited lower density and lower network connectivity compared with N–glasses. The chemical surface modifications after 4 h in SBF were more evident for N–glasses in comparison to A–glasses. The biocompatibility is favoured for the samples treated at 800 °C and for the samples of the higher silica contents

Design and development of Ga-substituted Z-type hexaferrites for microwave absorber applications: Mössbauer, static and dynamic properties

Gallium substituted Z-type Sr3GaxCo2-xFe24O41 (x = 0.0–2.0 in steps of 0.4) hexaferrites were synthesised by the sol-gel auto-combustion process, and sintered at 1150 °C. The structural, morphology, magnetic, Mössbauer, dielectric and microwave absorption properties were examined. XRD results of x = 0.0, 0.4, 0.8, and 1.2 samples show the formation of a single Z-type hexagonal phase. The samples x = 1.6 and 2.0 show the formation of Z and M phases. Hysteresis loops analysis suggest that samples x < 1.6 possess a soft magnetic nature, while the samples x = 1.6 and 2.0 show a hard ferrite characteristics. All samples possess multi-domain microstructures. The composition x = 0.4 [maximum MS = 97.94 Am2kg−1] was fitted with seven sextets (Fe3+) and a paramagnetic doublet-A (Fe3+), while beyond x ≥ 0.8 two more doublets (Fe2+) were observed along with seven sextets in Mössbauer spectra. The maximum values of Fe2+ ions (1.26%) and relative area of paramagnetic doublets (1.91%) were observed for x = 1.6 composition, which is also responsible for the lowest value of MS (69.99 Am2kg−1) for this composition. The average hyperfine magnetic field was found to decrease, whereas average quadrupole splitting was found to increase, with Ga-substitution. The substitution of Ga ions enhanced permeability, dielectric constant, magnetic loss and dielectric loss, in a non-linear fashion. The reflection loss was maximum at lower frequencies for samples x = 0.0 and 0.8, and decreases with frequency. Sample x = 0.8 has maximum reflection loss of −12.44 dB at 8 GHz, a measured thickness of 3 mm, and a bandwidth of −10 dB at 1.18 GHz. The observed absorption has been discussed with the help of the input impedance matching mechanism and quarter wavelength mechanism. The observed coercivity in different samples also influenced microwave absorption which demonstrated potenial in microwave absorber applications

Design and development of Ga-substituted Z-type hexaferrites for microwave absorber applications: mössbauer, static and dynamic properties

Gallium substituted Z-type Sr3GaxCo2-xFe24O41 (x = 0.0–2.0 in steps of 0.4) hexaferrites were synthesised by the sol-gel auto-combustion process, and sintered at 1150 °C. The structural, morphology, magnetic, Mössbauer, dielectric and microwave absorption properties were examined. XRD results of x = 0.0, 0.4, 0.8, and 1.2 samples show the formation of a single Z-type hexagonal phase. The samples x = 1.6 and 2.0 show the formation of Z and M phases. Hysteresis loops analysis suggest that samples x < 1.6 possess a soft magnetic nature, while the samples x = 1.6 and 2.0 show a hard ferrite characteristics. All samples possess multi-domain microstructures. The composition x = 0.4 [maximum MS = 97.94 Am2kg−1] was fitted with seven sextets (Fe3+) and a paramagnetic doublet-A (Fe3+), while beyond x ≥ 0.8 two more doublets (Fe2+) were observed along with seven sextets in Mössbauer spectra. The maximum values of Fe2+ ions (1.26%) and relative area of paramagnetic doublets (1.91%) were observed for x = 1.6 composition, which is also responsible for the lowest value of MS (69.99 Am2kg−1) for this composition. The average hyperfine magnetic field was found to decrease, whereas average quadrupole splitting was found to increase, with Ga-substitution. The substitution of Ga ions enhanced permeability, dielectric constant, magnetic loss and dielectric loss, in a non-linear fashion. The reflection loss was maximum at lower frequencies for samples x = 0.0 and 0.8, and decreases with frequency. Sample x = 0.8 has maximum reflection loss of −12.44 dB at 8 GHz, a measured thickness of 3 mm, and a bandwidth of −10 dB at 1.18 GHz. The observed absorption has been discussed with the help of the input impedance matching mechanism and quarter wavelength mechanism. The observed coercivity in different samples also influenced microwave absorption which demonstrated potenial in microwave absorber applications.publishe

Robocasting of ceramic glass scaffolds: Sol–gel glass, new horizons

This article reports the first robocasting of a sol–gel based glass ceramic scaffold. Sol–gel bioactive glass powders usually exhibit high volume fractions of meso– and micro–porosities, bad for colloidal processing as this adsorbs significant portion of the dispersing medium, affecting dispersion and flow. We circumvent these practical difficulties, to achieve pastes with particle size distributions, high solids loading and appropriate rheological properties for extrusion through fine nozzles for robocasting. Scaffolds with different macro-pore sizes (300–500 μm) with solid loadings up to 40 vol.% were robocast. The sintered (800 °C, 2 h) scaffolds exhibited compressive strength of 2.5–4.8 MPa, formed hydroxyapatite after 72 h in SBF, and had no cytotoxicity and a considerable MG63 cells viability rate. These features make the scaffolds promising candidates for tissue engineering applications and worthy for further in vivo investigations