The influence of processing parameters on morphology and granulometry of a wet-milled sol-gel glass powder

A quaternary bioactive sol-gel glass of high silica content was heat treated at different temperatures, and then wet ball milled under different balls-to-powder ratios. A total of sixteen experiments were performed to study in detail the effects of both experimental variables on the structure, morphology, particle size distributions and nitrogen adsorption isotherms. The balls–to–powder ratio exerts a tremendous influence on the final particle size distribution of the powders, while its effects on the pore volume and morphology are minimal. These structural features are mostly governed by the changes in calcination temperature. Therefore, understanding the specific roles of each experimental parameter is of paramount importance towards achieving optimum powders with the desired properties. This work sheds light on the importance of using a suitable combination of these two parameters for tuning the morphology and the granulometry of the sol-gel derived bioactive glass powders.publishe

Enhanced bioactivity of a rapidly-dried sol-gel derived quaternary bioglass

Novel quaternary (67Si-24Ca-10Na-8P) glass powders were successfully synthesised by sol-gel followed by two alternative drying schedules, conventional drying (CD) and an innovative fast drying (FD) process (200 times quicker). The glasses were thermally stabilised at 550 °C, and then characterised by different complementary techniques. The samples showed very similar silica network structures, with the FD one having slightly lower degree of polymerisation than the CD sample. This less polymerised, more open, network structure exhibited an improved bioactivity in simulated body fluid (SBF), probably also due to the apparent presence of poorly crystalline HAp in the stabilised glass powder. In contrast, the CD glass exhibited an unwanted secondary crystalline silica phase. Both glasses showed excellent biomineralisation upon immersion in SBF, being more pronounced in the case of FD with clear evidence of HAp formation after 4 h, while equivalent signs in the CD samples were only noticed after longer immersion periods between 8 h and 1 week.publishe

Robocasting of Cu2+ & La3+ 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 Cu2+ or La3+. The parent HSSGG composition within the system SiO2-CaO-Na2O-P2O5 [67% Si - 24% Ca - 5% Na - 4% P (mol%)] was doped with 5 wt% Cu2+ or La3+ (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 Cu2+ or La3+. 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 La3+) 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.publishe

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.publishe

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

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

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

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

BIONANOSCULP, an ongoing project in biotechnology applications for preventive conservation of outdoor sculptures

The objective of this paper is the presentation of the research strategies adopted and results of the ongoing BIONANOSCULP research project that is aiming to develop solutions in the area of sustainable nanomaterials, which are non-invasive and high-performance in their preventive conservation approach. An integrated methodology was designed as a holistic strategy to the characterisation of the microbiota present on the surface of public outdoor sculptures. Gathering objective data in the characterization of the surface microbiota of public outdoor sculptures is important, in order to design strategies for the preventive conservation of these objects that make use of biotechnology innovative coatings. Such is one of the objectives of the project BIONANOSCULP. Methodologies applied include conservation reports, surface sampling methodologies using gels, 3D modeling, SEM, flow cytometry and metagenomics. The project is already significantly contributing to create a bridge between the experts from different areas: the skills of biotechnologists, microbiologists, materials scientists, art historians and conservators-restorers to assess the state of conservation, biodeterioration and biocontamination of a selected number of sculptures, and to design the appropriate materials to pursue preventive conservation through coatings with anti-microbial activities