Biomimetic calcium carbonate with hierarchical porosity produced using cork as a sustainable template agent

Calcium carbonate has many applications in different fields; its use in environment remediation is particularly considered, due to its non-toxicity and potentially high efficiency. The structure, morphology and surface features of calcium carbonate can greatly affect its performance. Hierarchical porosity, in particular, can be beneficial for several functional properties. In this study, we report the synthesis of biomorphic calcium carbonate using a sustainable template agent – waste cork powder. Pyrolysed cork powder was infiltrated by an appropriate calcium-containing salt and successively thermally treated. Selected precursors, different impregnation-solution concentrations and thermal conditions were tested. The resulting materials were characterised by XRD, Raman spectroscopy and SEM. Surface area and porosity features were studied by BET analysis, with a detailed study on the effect of synthesis on the mesoporosity of the materials, average sizes varying between 4−15 nm. The most valuable results were achieved with calcium acetate followed by pyrolysis performed for relatively short time period. This maintained the porous 3D honeycomb cork structure made of ∼20 μm hexagonal cells, while consisting of highly mesoporous single-phase CaCO3. Such samples showed the highest surface area ever reported for CaCO3 prepared using a plant-based template; moreover, it also exhibited a dual-scale hierarchical porosity as, in addition to micrometer scale cellular macroporosity, it contained a significant mesoporosity in the cell walls, with a very narrow range of 3.6–3.9 nm. These promising characteristics enable the potential employment of cork-derived CaCO3 for environment remediation.publishe

Cork-derived hierarchically porous hydroxyapatite with different stoichiometries for biomedical and environmental applications

Hierarchically porous hydroxyapatite derived from cork powder shows excellent performance in biomedicine (low cytotoxicity) and environmental remediation (high Pb2+ removal)

Innovative application for bauxite residue: red mud-based inorganic polymer spheres as pH regulators

In this study, and for the first time, red mud (RM)-based geopolymer spheres were synthesised, with varying porosity and RM content, and then their use as pH regulators was evaluated. The aluminosilicate sources of these inorganic polymers were 100% waste-based, consisting of a mixture of RM and fly ash wastes. Geopolymer spheres containing up to 60 wt.% RM were successfully produced, while higher RM contents distorted the specimens' spherical shape. Results showed that alkalis leaching from the spheres over time can be controlled by their porosity, while the RM content induces only minor changes to leaching. The RM-based spheres leached up to 0.0237 mol/dm3g of OH- ions from their structure, this being among the highest values ever reported for geopolymers. This allowed a continuous and prolonged pH buffer capacity with narrow pH decay over the 28 days (2.4 pH units), suggesting the use of the RM-based spheres as pH buffering materials in wastewater treatment and anaerobic digestion systems.publishe

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

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

In-depth investigation of the long-term strength and leaching behaviour of inorganic polymer mortars containing green liquor dregs

Green liquor dregs are the most challenging waste stream coming from the pulp and paper industry. Despite tremendous efforts, there are not currently any viable recycling alternatives for this massively produced waste (2 Mt/year), which inevitably ends up in landfills. Urgent actions must be undertaken to tackle this. In this work, a substantial amount of dregs was incorporated into eco-friendly, waste-based inorganic polymer (geopolymer) mortars as fine filler. Then, and for the first time, the long-term strength performance (up to 270 days) and heavy metals leaching behaviour of the dregs-containing mortars was evaluated. The effect of the mixture composition and dregs incorporation content on the fresh- and hardened-state properties of the mortars was also studied. Dregs were found to increase the initial and final setting time of the slurries, thus extending the open time before their in-situ application. The use of dregs as fine filler effectively enhances the compressive strength of the mortars, and decreases their water absorption levels. These eco-friendly building materials showed excellent long-term performance, as their strength continuously increases up to the 270th day (after mixture), and no signs of efflorescence formation were detected. Moreover, the heavy metals leaching levels of the mortars were well below the contamination limits in soil, which demonstrates the feasibility of this recycling methodology.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

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 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