Comparison of low and high pressure infiltration regimes on the density and highly porous microstructure of ceria ecoceramics made from sustainable cork templates

Cork templates were used to produce lightweight bulk biomimetic ecoceramic (environmentally conscious ceramic) monoliths. Bulk/monolithic ceramics are vital for many applications, i.e. energy materials and fuel cells. Using simple and flexible, aqueous green-chemistry procedures, for the first time the influence of infiltration regime, number of infiltration cycles and sintering temperature on ecoceramic density and microstructure was studied. This lightweight three-dimensionally ordered macroporous (3DOM) CeO2 preserved the hexagonal cellular structure of cork, but unlike the wood, the rear cell walls were open, greatly increasing open porosity. Higher sintering temperatures (1600 instead of 1000 °C) were required to produce cm size monolithic ecoceramics mechanically strong enough to be handled. The infiltration regime and number of infiltration cycles affected density and porosity. Lower infiltration pressure led to higher porosity ecoceramics (3.3–5.7%), which may favour catalytic performance, showing the possibility of tailoring porosity and specific surface area by modifying the number of infiltration cycles

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

Biomimetic cork-based CeO2 ecoceramics for hydrogen generation using concentrated solar energy

Naturally occurring and sustainable materials can be used as a template to create biomimetic/biomorphic ceramics, known as Ecoceramics (environmentally conscious ceramics). In this work, cork was chosen as template to produce novel ceria (CeO2) ecoceramics, for applications in water splitting for H2 production via direct concentrated solar thermochemical fuel production (TCFP). The cork powder was pyrolised at 900 °C and the resulting carbon skeleton was infiltrated with an aqueous CeO2 precursor, and then heated at 1000 °C for 2 h to produce the ecoceramic. The cellular structure of the cork was maintained, with hexagonal cell dimensions of 20-30 μm in diameter, but the grains were nanoscale at ≤100 nm. XRD data confirmed that CeO2 was the only crystalline phase obtained. An important feature was that, while the rectangular side walls were maintained to hold the three-dimensionally ordered macroporous (3DOM) cellular cork structure, the rear hexagonal walls were pierced repeatedly through the structure, unlike in the original cork structure, which will allow gasses such as H2 to permeate well into the structure, greatly increasing the reactive area available for catalysis. The next step will be to test the capabilities of both the regular, porous 3DOM structure and the nanoscale grains for thermochemical water splitting to produce hydrogen under direct concentrated solar energy

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

Nanostructured titanium dioxide coatings prepared by Aerosol Assisted Chemical Vapour Deposition (AACVD)

Titanium dioxide is a compound of great interest, due to its functional properties; one of its most important uses is as a photocatalyst. TiO2 coatings can be deposited using different techniques. Aerosol Assisted Chemical Vapour Deposition (AACVD) is particularly interesting, as high temperature or pressure are not necessary to generate the gaseous precursors. Furthermore, by carefully choosing the deposition conditions (i.e. deposition temperature, solvent), it is possible to obtain deposits with different morphology and, consequently, different functional properties. In this paper we present the synthesis of titanium dioxide coatings with AACVD using complexes between titanium isopropoxide (TIPP) and acetyl acetone (acac) as precursors. Deposition experiments were performed using different ratios of TIPP to acac, to assess the effect on the composition of the coatings, their morphology and photocatalytic activity. Results showed that the use of acac led to nanostructured titanium dioxide (nanoparticles of about 10−25 nm diameter). Raman analysis showed the presence of both anatase and rutile phases. XPS analysis indicated the presence of residual carbonaceous species in the coatings; despite this, they displayed photocatalytic properties similar or superior to AACVD films without carbon. Photocatalytic tests, performed measuring the Formal Quantum Efficiency (FQE) and the Formal Quantum Yield (FQY) in the degradation of resazurin, showed that a acac:TIPP ratio equal to 1 led to the material with the highest performance, as the FQE value was about three times higher than that for the coating prepared with TIPP alone. Overall the complexes between TIPP and acac are promising precursors for the AACVD technique, leading to nanostructured coatings with enhanced performance

Magnetic wood-based biomorphic Sr3Co2Fe24O41 Z-type hexaferrite ecoceramics made from cork templates

Ecoceramics (environmentally conscious ceramics) are biomimetic/biomorphic ceramics, which use a naturally occurring and sustainable material as a template for their unique morphology and structure. Usually woods (or lignocellulosics) are used, due to the inherent cellular nature of their microstructures. The wood is pyrolised and the resulting carbon skeleton impregnated with a fluid, and this is then heated to combust the carbon template and convert the fluid precursor into a ceramic, while maintaining the structure of the original natural template. For the first time, ecoceramics have been made from cork, a totally sustainable wood that is harvested without harming the tree. Also for the first time, ecoceramics have been made of soft magnetic Z-type hexaferrites, in this case the room temperature multiferroic strontium Z ferrite Sr3Co2Fe24O41 (SrZ). Cork powder was pyrolised at 1000°C, infiltrated with an aqueous sol-gel SrZ precursor, and then heated at 1200°C/2h to produce the ecoceramic. The cellular structure of the cork was maintained, with a small reduction in the hexagonal cell dimension to 10μm diameter, but the cell walls remained 1-2μm thick, of a similar magnitude to the hexaferrite grain size. Both magnetic and XRD data agreed that there was a small portion of the SrW phase present in these ecoceramics as well, and the magnetic loop showed a magnetically soft ecoceramic with Ms=59.5 A m2 kg -1 (at 3T), and a low Hc of 16 kA m-1

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

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

Sequential piezoresponse force microscopy and the 'small-data' problem

The term big-data in the context of materials science not only stands for the volume, but also for the heterogeneous nature of the characterization data-sets. This is a common problem in combinatorial searches in materials science, as well as chemistry. However, these data-sets may well be 'small' in terms of limited step-size of the measurement variables. Due to this limitation, application of higher-order statistics is not effective, and the choice of a suitable unsupervised learning method is restricted to those utilizing lower-order statistics. As an interesting case study, we present here variable magnetic-field Piezoresponse Force Microscopy (PFM) study of composite multiferroics, where due to experimental limitations the magnetic field dependence of piezoresponse is registered with a coarse step-size. An efficient extraction of this dependence, which corresponds to the local magnetoelectric effect, forms the central problem of this work. We evaluate the performance of Principal Component Analysis (PCA) as a simple unsupervised learning technique, by pre-labeling possible patterns in the data using Density Based Clustering (DBSCAN). Based on this combinational analysis, we highlight how PCA using non-central second-moment can be useful in such cases for extracting information about the local material response and the corresponding spatial distribution

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