Long-term durability of discarded cork-based composites obtained by geopolymerization.

Geopolymers are amorphous aluminosilicate inorganic polymers synthesized by alkaline activation characterized by a lower carbon footprint, greater durability, and excellent mechanical properties compared to traditional concrete, making them promising building materials for sustainable construction. To develop sustainable lightweight geopolymer-based building materials useful as fire resistant thermal insulation materials, we added 5 and 10 wt% of discarded cork dust, a readily available industrial by-product, to metakaolin before and after the alkaline activation with sodium hydroxide 8 M and sodium silicate solutions. We followed the chemical, microstructural, antibacterial, and physical properties of the resulting composites for up to 90 days in order to monitor their long-term durability. The presence of cork does not interfere with the geopolymerization process and in fact reduces the density of the composites to values around 2.5 g/cm3, especially when added after alkaline activation. The composites resulted in chemically stable matrices (less than 10 ppm of cations release) and filler (no hazardous compounds released) with a bacterial viability of around 80%. This study provides valuable insights into the tailoring of discarded cork-based composites obtained by geopolymerization with a porosity between 32 and 48% and a mechanical resistance to compression from 15 to 5 MPa, respectively, suggesting their potential as durable interior panels with low environmental impact and desirable performance.

Natural iron-aluminosilicate as potential solid precursor for supplementary cementitious materials: A comparative study with other aluminosilicates.

The objective of this study was to investigate the impact of the geographic and climatic conditions on laterites properties and on geopolymerization based-laterite. Four different laterite deposits in the four geographical zones of Cameroon were studied. This included the center, north, south and west corners of Cameroon, having chemical composition of SiO2 + Al2O3 + Fe2O3 = 88.94, 87.6, 89.13 and 78.97%, respectively. The center and south laterites from the black forest, with high pluviometry and relative humidity, show significant amounts of Fe2O3. While the west laterite from grass field - mountainous areas and the north-laterite from plain arid and semi-arid climate still show lower iron concentrations. The IR absorption bands of the different laterites appear between 1007 and 1047 cm-1; characteristic bands of aluminosilicate. The BET (Brunauer-Emmett-Teller) Specific surface area values are comprised in the range of [21.9, 24.1 m2/g] for non-calcined laterite and between [45.6 and 123.5 m2/g] for laterites calcined at 550 °C and 575 °C. The main particle size values are 5.71, 6.37, 7.43 and 8.45 µm for center-laterite, west-laterite, north laterite and south-laterite, respectively. Although, they differ in the degree of laterization, all the laterites present almost total conversion to geopolymers, due to the presence of amorphous kaolinite and reactive goethite. However, the iron content has significant impact on the globular microstructure. The particle size of laterites, their high values of BET surface area and their significant reactivity make them promising substitutes to metakaolin and other supplementary cementitious materials.

Environmental and Biological Impact of Fly Ash and Metakaolin-Based Alkali-Activated Foams Obtained at 70°C and Fired at 1,000°C.

Alkali-activated foams (AAFs) are inorganic porous materials that can be obtained at temperatures well below 100°C with the use of inorganic wastes as aluminosilicate precursors. In this case, fly ash derived from a Slovenian power plant has been investigated. Despite the environmental benefits per se, due to saving of energy and virgin materials, when using waste materials, it is of extreme importance to also evaluate the potential leaching of heavy metal cations from the alkali-activated foams. This article presents an environmental study of a porous geopolymer derived from this particular fly ash, with respect to the leachability of potentially hazardous elements, its environmental toxicity as determined by biological testing, and the environmental impact of its production. In particular, attention was focused to investigate whether or not 1,000°C-fired alkali-activated fly ash and metakaolin-based foams, cured at 70°C, are environmentally friendlier options compared to unfired ones, and attempts to explain the rationale of the results were done. Eventually, the firing process at 1,000°C, apart from improving technical performance, could reinforce heavy metal cation entrapment within the aluminosilicate matrix. Since technical performance was also modified by addition of different types of activators (K-based or Na-based), as well as by partial replacement of fly ash with metakaolin, a life cycle assessment (LCA) analysis was performed to quantify the effect of these additions and processes (curing at 70°C and firing at 1,000°C) in terms of global warming potential. Selected samples were also evaluated in terms of leaching of potentially deleterious elements as well as for the immobilization effect of firing. The leaching test indicated that none of the alkali-activated material is classified as hazardous, not even the as-received fly ash as component of new AAF. All of the alkali-activated foams do meet the requirements for an inertness. The highest impact on bacterial colonies was found in samples that did not undergo firing procedures, i.e., those that were cured at 70°C, which induced the reduction of bacterial Enterococcus faecalis viability. The second family of bacteria tested, Escherichia coli, appeared more resistant to the alkaline environment (pH = 10-12) generated by the unfired AAMs. Cell viability recorded the lowest value for unfired alkali-activated materials produced from fly ash and K-based activators. Its reticulation is only partial, with the leachate solution appearing to be characterized with the most alkaline pH and with the highest ionic conductivity, i.e., highest number of soluble ions. By LCA, it has been shown that 1) changing K-based activators to Na-based activators increases environmental impact of the alkali-activated foams by 1%-4% in terms of most of the impact categories (taking into account the production stage). However, in terms of impact on abiotic depletion of elements and impact on ozone layer depletion, the increase is relatively more significant (11% and 18%, respectively); 2) replacing some parts of fly ash with metakaolin also results in relatively higher environmental footprint (increase of around 1%-4%, while the impact on abiotic depletion of elements increases by 14%); and finally, 3) firing at 1,000°C contributes significantly to the environmental footprint of alkali-activated foams. In such a case, the footprint increases by around one third, compared to the footprint of alkali-activated foams produced at 70°C. A combination of LCA and leaching/toxicity behavior analysis presents relevant combinations, which can provide information about long-term environmental impact of newly developed waste-based materials.

Polysaccharide Based Polymers Produced by Scabby Cankered Cactus Pear (Opuntia ficus-indica L.) Infected by Neofusicoccum batangarum: Composition, Structure, and Chemico-Physical Properties.

Neofusiccocum batangarum is the causal agent of scabby canker of cactus pear (Opuntia ficus-indica L.). The symptoms of this disease are characterized by crusty, perennial cankers, with a leathery, brown halo. Characteristically, a viscous polysaccharide exudate, caking on contact with air, leaks from cankers and forms strips or cerebriform masses on the surface of cactus pear cladodes. When this polysaccharide mass was partial purified, surprisingly, generated a gel. The TLC analysis and the HPLC profile of methyl 2-(polyhydroxyalkyl)-3-(o-tolylthiocarbomoyl)-thiazolidine-4R-carboxylates obtained from the mixture of monosaccharides produced by acid hydrolysis of the three EPSs examined in this research work [the polysaccharide component of the exudate (EPSC) and the EPSs extracted from asymptomatic (EPSH) and symptomatic (EPSD) cladodes] showed the presence of d-galactose, l-rhamnose, and d-glucose in a 1:1:0.5 ratio in EPSC while d-galactose, l-rhamnose, d-glucose, and d-xylose at the same ratio were observed in EPSH and EPSD. The presence of uronic acid residues in EPSC was also showed by solid state NMR and IR investigation. Furthermore, this manuscript reports the chemical-physical characterization of the gel produced by the infected cactus pear.

Chlorogenic acid/PEG-based organic-inorganic hybrids: A versatile sol-gel synthesis route for new bioactive materials.

New organic-inorganic hybrid materials were synthesized by an acid catalysed sol-gel approach, using silicon alkoxide and low molecular weight polyethylene glycol (PEG400) as inorganic and organic precursor, respectively. Chlorogenic acid (CGA), an antioxidant natural phenol compound, enriched further the organic component. Hybrids synthesized, all identical in terms of their starting materials, but differing in terms of their relative proportions, were characterized by means of Fourier Transform InfraRed (FTIR) measurements, UV-Vis spectroscopy, and UHPLC-HRMS analysis. The preservation of the intrinsic chlorogenic acid ability to scavenge, in a dose-dependent manner, radical species was investigated by directly exposing the hybrids to DPPH radical and ABTS radical cation. The relative ratio of both the natural compound and PEG heavily affected the antiradical response, suggesting that chemical interactions in the established network were able, based on components' ratio, to differently mask and/or display the CGA moieties, commonly deemed relevant for antioxidant power exerting. Cell culture MTT assay was used to assess the biocompatibility of hybrid materials towards fibroblast NIH-3 T3 cells and neuroblastoma SH-SY5Y cells. Cells tested appeared differently responsive. In particular, a marked cell viability increase was observed when hybrids with low PEG amount (6%) and high CGA (15%) were directly exposed to fibroblast cells, whose mitochondrial redox activity was negatively affected by hybrid synthesized using the highest organic component rate (both PEG and CGA). Cell viability and morphology of human neuroblastoma SH-SY5Y cells were broadly compromised regardless of organic/inorganic starting materials ratio, suggesting the ability of hybrids to exert pro-oxidant effect towards tumour cells and to selectively interfere with their growth. The hybrids, able to elicit cleverly anti- or proliferative effects, were also shown to be bioactive. In fact, a biologically active hydroxyapatite layer was observed to be formed on the surface of the smart synthesized materials. This feature, which makes them a valuable bonding interface with tissues, opens new scenario aiming at further investigating the employment of natural phenol compounds in versatile sol-gel synthesis routes.

Correction: Biodegradable nanoparticles bearing amine groups as a strategy to alter surface features, biological identity and accumulation in a lung metastasis model.

Correction for 'Biodegradable nanoparticles bearing amine groups as a strategy to alter surface features, biological identity and accumulation in a lung metastasis model' by Diletta Esposito et al., J. Mater. Chem. B, 2018, 6, 5922-5930.