Geopolymer foams: An overview of recent advancements

Geopolymer foams (highly porous materials) have emerged as one of the most exciting materials over the past few years due to their remarkable properties, low cost and green synthesis protocol, enabling their use in various high added-value applications. Review papers on porous geopolymers are uncommon, and the emphasis has been given to materials processing and properties, while the applications were only briefly addressed. This review aims to fill this gap by presenting a comprehensive literature survey and critical analysis of the most recent and exciting research carried out on geopolymer foams. Up to now, these bulk-type (not powders) materials have been mainly considered as thermal and acoustic insulators. However, besides addressing their use as building material, this review also shows that their use in less investigated, but environmentally and economically relevant applications (e.g. bulk-type adsorbents, pH buffering agents and catalysts), is feasible and might ensure performance and technical advantages over their powdered counterparts. The limitations, challenges and future prospects associated with the different applications are presented. This review shows the remarkable potential of geopolymer foams in high added-value applications, far beyond their historical use as Portland cement replacement, which may encourage the widespread technological use of these materials

Highly efficient lead extraction from aqueous solutions using inorganic polymer foams derived from biomass fly ash and metakaolin

This work reports a simple and safe, but powerful, route to depollute lead-containing aqueous solutions. Inorganic polymer foams (cm-size) were used as bulk-type adsorbents. The influence of the specimens' porosity and activator molarity on the foams' physical properties and on their lead extraction ability was studied. Then, the best performing samples were deeply evaluated as lead adsorbents by studying the impact of pH, lead concentration, contact time, ionic strength and solution volume. Lead sorption kinetics is strongly affected by the pollutant concentration, pH and the solution ionic strength. Under the most favourable conditions the foams showed an impressive removal capacity (105.9 mg/g at pH 5, 23 °C, C0 = 800 ppm, deionised water), surpassing all other reported values on the use of bulk-type inorganic polymers. The foams’ lead uptake is 2.3 times higher than the previous best performing bulk-type specimens (mm-size spheres), and sorption is 12.5–15 times faster. The foams can be easily regenerated using mild acidic conditions, and then reused as adsorbent, suggesting that the main adsorption mechanism is ion exchange

Late Holocene palynology and palaeovegetation of tephra-bearing mires at Papamoa and Waihi Beach, western Bay of Plenty, North Island, New Zealand.

The vegetation history of two mires associated with Holocene dunes near the western Bay of Plenty coast, North Island, New Zealand, is deduced from pollen analysis of two cores. Correlation of airfall tephra layers in the peats, and radiocarbon dates, indicate that the mires at Papamoa and Waihi Beach are c. 4600 and c. 2900 conventional radiocarbon years old, respectively. Tephras used to constrain the chronology of the pollen record include Rotomahana (1886 AD), Kaharoa (700 yr B.P.), Taupo (Unit Y; 1850 yr B.P.), Whakaipo (Unit V; 2700 yr B.P.), Stent (Unit Q; 4000 yr B.P.), Hinemaiaia (Unit K; 4600 yr B.P.), and reworked Whakatane (c. 4800 yr B.P.) at Papamoa, and Kaharoa and Taupo at Waihi Beach. Peat accumulation rates at Papamoa from 4600 - 1850 yr B.P. range from 0.94 to 2.64 mm/yr (mean 1.37 mm/yr). At Waihi Beach, from 2900 yr B.P. - present day, they range from 0.11 to 0.21 mm/yr (mean 0.20 mm/yr). Peat accumulation at both sites was slowest from 1850 to 700 yr B.P., suggesting a drier overall climate during this interval. At both sites, the earliest organic sediments, which are underlain by marine or estuarine sands, yield pollen spectra indicating salt marsh or estuarine environments. Coastal vegetation communities declined at both sites, as sea level gradually fell or the coast prograded, and were eventually superseded by a low moor bog at Papamoa, and a mesotrophic swamp forest at Waihi Beach. These differences, and the marked variation in peat accumulation rates, probably reflect local hydrology and are unlikely to have been climatically controlled. The main regional vegetation during this period was mixed northern conifer-angiosperm forest. Kauri (Agathis australis) formed a minor component of these forests, but populations of this tree have apparently not expanded during the late Holocene at these sites, which are near its present southern limit. Occasional shortlived forest disturbances are detectable in these records, in particular immediately following the deposition of Taupo Tephra. However, evidence for forest clearance during the human era is blurred by the downward dislocation of modern adventi ve pollen at these sites, preventing the clear differentiation of the Polynesian and European eras

Re-identification of c. 15 700 cal yr BP tephra bed at Kaipo Bog, eastern North Island: implications for dispersal of Rotorua and Puketarata tephra beds.

A 10 mm thick, c. 15 700 calendar yr BP (c. 13 100 14C yr BP) rhyolitic tephra bed in the well-studied montane Kaipo Bog sequence of eastern North Island was previously correlated with Maroa-derived Puketarata Tephra. We revise this correlation to Okataina-derived Rotorua Tephra based on new compositional data from biotite phenocrysts and glass. The new correlation limits the known dispersal of Puketarata Tephra (sensu stricto, c. 16 800 cal yr BP) and eliminates requirements to either reassess its age or to invoke dual Puketarata eruptive events. Our data show that Rotorua Tephra comprises two glass-shard types: an early-erupted low-K2O type that was dispersed mostly to the northwest, and a high-K2O type dispersed mostly to the south and southeast, contemporary with late-stage lava extrusion. Late-stage Rotorua eruptives contain biotite that is enriched in FeO compared with biotite from Puketarata pyroclastics. The occurrence of Rotorua Tephra in Kaipo Bog (100 km from the source) substantially extends its known distribution to the southeast. Our analyses demonstrate that unrecognised syn-eruption compositional and dispersal changes can cause errors in fingerprinting tephra deposits. However, the compositional complexity, once recognised, provides additional fingerprinting criteria, and also documents magmatic and dispersal processes

Synthesis of red mud derived M-type barium hexaferrites with tuneable coercivity

Hexagonal ferrites can be employed in a multitude of applications, the most common hexaferrites are the M ferrites such as BaFe12O19 (barium hexaferrite, BaM). It is known that if Fe3+ is substituted with a combination of Ti4+/Co2+ the coercivity of BaM can be reduced to produce soft M ferrites with easily switchable magnetisation. They can be utilised as powders, films or bulk ceramics, and can be manufactured from a wide variety of synthesis methods. The production of hexaferrites usually requires commercial raw materials, but if an industrial waste can be utilised, this will help to ease waste disposal and storage costs, valorise a waste material and encourage circular economy. In this study, bauxite residue (red mud) from the production of alumina was used to synthesise M-type hexaferrites, using a simple ceramic process. BaCO3, or BaCO3+Co3O4, were added to the red mud, blended and heated at 1000 °C to produce the M-type hexaferrites. Without cobalt addition up to 81.1 wt% M ferrite was produced, and with Co addition up to 74.3 wt% M ferrite was formed. Without cobalt, the M ferrite phase closely resembled BaFe9Al3O19, and was a hard ferrite with a magnetisation of 12–19 A m2/kg for the whole powder (up to 23.6 A m2/kg for the M ferrite phase) and a coercivity of ~290 kA/m. When cobalt was added, secondary titanate phases vanished, and Ti4+/Co2+ partially substituted very soft M ferrite was formed with a low coercivity of ~16 kA/m but a higher magnetisation of 24.5 A m2/kg for the whole powder (up to 34.9 A m2/kg for the M ferrite phase). Therefore, not only can good quality magnetic materials be easily produced from this common waste material, but its magnetic properties can be tuned by varying the 2 + ions added during the process

Unravelling the Affinity of Alkali-Activated Fly Ash Cubic Foams towards Heavy Metals Sorption

In this work, alkali-activated fly ash-derived foams were produced at room temperature by direct foaming using aluminum powder. The 1 cm3 foams (cubes) were then evaluated as adsorbents to extract heavy metals from aqueous solutions. The foams’ selectivity towards lead, cadmium, zinc, and copper ions was evaluated in single, binary, and multicomponent ionic solutions. In the single ion assays, the foams showed much higher affinity towards lead, compared to the other heavy metals; at 10 ppm, the removal efficiency reached 91.9% for lead, 83.2% for cadmium, 74.6% for copper, and 64.6% for zinc. The greater selectivity for lead was also seen in the binary tests. The results showed that the presence of zinc is detrimental to cadmium and copper sorption, while for lead it mainly affects the sorption rate, but not the ultimate removal efficiency. In the multicomponent assays, the removal efficiency for all the heavy metals was lower than the values seen in the single ion tests. However, the superior affinity for lead was preserved. This study decreases the existing knowledge gap regarding the potential of alkali-activated materials to act as heavy metals adsorbents under different scenarios

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

Films of chitosan and natural modified hydroxyapatite as effective UV-protecting, biocompatible and antibacterial wound dressings

Chitosan is a natural polysaccharide widely used in biomedicine, for instance for wound dressing. Hydroxyapatite is a very bioactive calcium phosphate which, if modified with an appropriate element (iron Fe), can also have UV-absorbing properties. In this work, we report the study of films of chitosan incorporated with iron-modified hydroxyapatite of natural origin (from cod fish bones); this combination led to an innovative chitosan-based material with excellent and advanced functional properties. The films showed very high UV absorption (Ultraviolet Protection Factor (UPF) value higher than 50). This is the first time that a chitosan-based material has shown such high UV protection properties. The films also showed to be non-cytotoxic, and possessed antimicrobial activity towards both Gram-positive and negative strains. Their mechanical properties, optimised with an experimental design approach, confirmed their potential use as multifunctional wound dressing, capable of reducing bacterial infections and, at the same time, protecting from UV light

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