Ceramics, Volume 1, Issue 2 (December 2018) – 13 articles

Calcium phosphate powder was synthesized at room temperature from aqueous solutions of ammonium hydrophosphate and calcium acetate without pH adjusting at constant Ca/P molar ratio 1.5. Phase composition of the as-synthesized powder depended on the precursors concentration: At 2.0 M of calcium acetate in the starting solution, poorly crystallized hydroxyapatite was formed, 0.125 M solution of calcium acetate afforded brushite, and the powders synthesized from 0.25–1.0 M calcium acetate solutions were mixtures of the mentioned phases. Firing at 1100 °C led to complete elimination of the reaction by-products, yet the phase composition of the annealed compacted samples was the following: When 2.0 M solution of calcium acetate was used, the obtained ceramics consisted of β-Ca₃(PO₄)₂, whereas at 0.125 to 1.0 M of calcium acetate, the ceramics was a mixture of β-Ca₃(PO₄)₂ and β-Ca₂P₂O₇. Synthesized calcium phosphate powders can be used as the powdered precursors for biocompatible bioresorbable composite ceramics production. Full article

Improving optical fiber amplifiers requires the elaboration and use of new materials and new compositions. In this sense, we prepared erbium-doped optical fiber samples that were co-doped with magnesium or lanthanum by gradual-time solution doping. Doping concentrations and thermal processes induce the formation of nanoparticles. The effect of lanthanum and magnesium contents on the width of the spontaneous emission of the ${}^4$ I ${}_{13/2}$ level of Er ${}^{3+}$ was characterized in the nanoparticle-rich fiber samples. For that purpose, the width was characterized by the effective linewidth and the full-width at half-maximum (FWHM). The results indicate the robustness of the effective linewidth to strong variations in the intensity profiles of the ${}^4$ I ${}_{13/2}$ spontaneous emission. Increasing the doping concentrations of both magnesium and lanthanum increases the FWHM and the effective linewidth, along with optical losses. Results show that the fabrication of nanoparticle-rich optical fibers through lanthanum or magnesium doping induces an FHWM broadening of 54% and 64%, respectively, or an effective linewidth broadening of 59% (for both elements) while maintaining a transparency that is compatible with fiber laser and amplifier applications. Full article

Various porous materials have been used as adsorbents for water remediation. Among them, metal-organic framework (MOF) particles have been explored intensively, due to their size-controlled micropores and high surface areas. MOF nanoparticles are often used because of high external surface area and easy access to the micropores. However, recovering MOF nanoparticles, usually by filtration or centrifugation, is time-consuming and is difficult to scale up. We report here the preparation of porous MOF/polymer monoliths by freeze casting for water remediation. Chitosan and UiO-66 (Universitetet i Oslo) nanoparticles (including different surface functional groups) are used to prepare such monoliths. In order to improve the mechanical stability and the tendency of disintegrating in water, the freeze-dried UiO-66/chitosan monoliths are further treated by heating, washing with aqueous NaOH solution, or chemical crosslinking with glutaraldehyde. All these treated monoliths are used for adsorption of a herbicide methylchlorophenoxypropionic acid (MCPP) from aqueous solution. Particularly, the crosslinked chitosan/UiO-66 monolith achieves an adsorption capacity of 47.67 mg g⁻¹, with a 60 ppm MCPP solution. It is superior to that presented by the sole UiO-66 nanoparticles, exhibiting over a 30% increase in the adsorption capacity. The monoliths can be easily removed using tweezers, providing facile recyclability, which is advantageous for upscaling. The recycled monolith upheld approximately 75% of the adsorption capacity compared to the original monolith after three reuse cycles. Full article

Compositions of (ZrO₂)_0.92(Y₂O₃)_0.08 (zirconia: 8 mol % yttria—8YSZ) and (CeO₂)_0.8(Sm₂O₃)_0.2 (ceria: 20 mol % samaria—SDC20) ceramic powders were prepared by attrition milling to form an equimolar powder mixture, followed by uniaxial and isostatic pressing. The pellets were quenched to room temperature from 1200 °C, 1300 °C, 1400 °C and 1500 °C to freeze the defects configuration attained at those temperatures. X-ray diffraction analyses, performed in all quenched pellets, show the evolution of the two (8YSZ and SDC20) cubic fluorite structural phases to a single phase at 1500 °C, identified by Rietveld analysis as a tetragonal phase. Impedance spectroscopy analyses were carried out in pellets either quenched or slowly cooled from 1500 °C. Heating the quenched pellets to 1000 °C decreases the electrical resistivity while it increases in the slowly cooled pellets; the decrease is ascribed to annealing of defects created by lattice micro-tensions during quenching while the increase to partial destabilization of the tetragonal phase. Full article

Shaped porous ceramics have proven to be the most adapted materials for several industrial applications, both at low and high temperatures. Recent research has been focused on developing shaping techniques, allowing for a better control over the total porosity and the pores characteristics. In this study, macroporous alumina foams were fabricated by gel-casting using pre-expanded polymeric microspheres with average sizes of 40 μm, 20 μm, and 12 μm as sacrificial templates. The gel-casting method, as well as the drying, debinding, and presintering conditions were investigated and optimized to process mechanically strong and highly porous alumina scaffolds. Furthermore, a reliable model relating the amount of pre-expanded polymeric microspheres and the total porosity of the presintered foams was developed and validated by mercury intrusion porosimetry measurements. The electron microscopy investigation of the presintered foams revealed that the size distribution and the shape of the pores could be tailored by controlling the particle size distribution and the shape of the wet pre-expanded microspheres. Highly uniform and mechanically stable alumina foams with bimodal porosity ranging from 65.7 to 80.2 vol. % were processed, achieving compressive strengths from 3.3 MPa to 43.6 MPa. Given the relatively open pore structure, the pore size distribution, the presintered mechanical strength, and the high porosity achieved, the produced alumina foams could potentially be used as support structures for separation, catalytic, and filtration applications. Full article

Macroporous composite foams consisting of β-tricalcium phosphate (β-TCP) and titanium nitride (TiN) have been prepared by a facile emulsion route involving sintering at elevated temperatures after shaping. Commercially available hydroxyapatite and titanium particles are used as the starting material; to which, the surface of the particles has been modified by preferential adsorption of hexadecylamine to change from hydrophilic to hydrophobic character in water. This renders stable air-in-water emulsions from the particle-filled suspensions by simple mechanical frothing. Sintered β-TCP/TiN foams with a porosity of 65–70%, pore size of 20–2000 nm, and three-point rupture strength of 25–43 kPa have been obtained. Electrical resistance has been found to reduce pronouncedly when the initial titanium loading exceeds 15 vol.% for the composite foams sintered at 1000 °C under reducing nitrogen-hydrogen atmosphere. Full article

Lead-free piezoelectric 0.95(Na_0.49K_0.49Li_0.02)(Nb_0.8Ta_0.2)O₃–0.05CaZrO₃ with 2 wt % MnO₂ addition was prepared using mechanochemically-assisted solid-state synthesis. Upon mechanochemical activation of the mixture of reagents partial amorphization occurs which contributes to a significantly lower temperature of completion of the solid-state reaction, ~600 °C as opposed to ~700 °C for the conventional solid-state synthesis as determined by thermal analysis. The ceramic specimens prepared by the mechanochemically-assisted route exhibit improved compositional homogeneity and slightly enhanced piezoelectric properties, achieved in a considerably shorter processing time compared to the conventional solid-state synthesis route, which was studied as a reference. Full article

We evaluated the influence of aging on mechanical properties of 8% yttria-doped zirconia (8YSZ) from room temperature to 1200 K. The temperature dependence of the dynamic Young’s and shear moduli of 8YSZ with and without the aging treatment was investigated by using a resonance method. The dynamic Young’s and shear moduli of 8YSZ without the aging treatment decreased by 33% below 700 K and gradually increased at higher temperatures with increasing temperature. On the other hand, those with the aging treatments decreased by around 20% below 600 K while did not significantly change above 600 K with increasing temperature. These demonstrated the effect of aging on the dynamic Young’s and shear moduli of 8YSZ was most remarkable at intermediate temperatures (600~1000 K). Although it was suggested that the existence ratio of the metastable tetragonal phase was increased during the aging treatment, it is likely that the influence of this phase transition on the dynamic Young’s and shear moduli was not significant. It seemed that the difference in the dynamic Young’s and shear moduli of 8YSZ with and without the aging treatment at intermediate temperatures was due to the local ordering of the oxygen vacancies. Full article

Optical and structural properties of glasses and glass-ceramics (GC) obtained by different heat-treatment of Tb and Tb-Yb doped sol-gel derived 30ZrO₂-70SiO₂ materials were investigated. A glass was formed after treatment at 700 °C whereas devitrification of the media after the treatment at 1000 and 1100 °C, led to the formation of GC containing up to three different crystalline phases, namely, tetragonal ZrO₂, Yb-disilicate and cristobalite. The modification of the optical properties through the heat treatment was caused by redistribution of the rare earth elements (REE) among the different phases: both Tb and Yb entered the t-ZrO₂ lattice, Yb can also be present in the form of a Yb₂Si₂O₇ crystal. Devitrification led to an increase in Tb→Yb energy transfer efficiency as compared to the glass, though it was higher in the samples heat-treated at 1000 °C than in those treated at 1100 °C. The most intensive Yb³⁺ luminescence, induced by the energy transfer from the Tb³⁺ ion, was observed at the interface between t-ZrO₂ and the glassy phases, due to the high concentration of REE in this area caused by the inability of ZrO₂ to accept larger amounts of the REE. The mechanisms of the Tb→Yb energy transfer vary between different phases of the GC. The results obtained in this study are important for the development of spectral down-converters for potential solar energy applications based on Tb-Yb co-doped glass-ceramics. Full article

We investigated copper electrodes deposited onto a BaZr_0.7Ce_0.2Y_0.1O_3-δ (BZCY72) proton-conducting membrane via a novel electroless plating method, which resulted in significantly improved performance when compared to a traditional painted copper electrode. The increased performance was examined with a multiscale multitechnique characterization method including time-of-flight secondary-ion mass spectroscopy (TOF-SIMS), transmission electron microscopy (TEM), scanning spreading-resistance microscopy (SSRM), and atom-probe tomography (APT). Through this method, we observed that a palladium catalyst layer alloys with the copper electrode. We also explored the nature of a non-coking-induced carbon-rich phase that may be involved with the improved performance of the electrode. Full article

In this work, nanostructured (La_0.6Sr_0.4)_0.99CoO₃ (LSC)-Ce_0.8Gd_0.2O_1.9 (CGO) core-shell particles were prepared by precipitating CGO nanoparticles on the surface of LSC particles under hydrothermal conditions. The as-prepared core-shell particles were sintered by spark plasma sintering (SPS) and conventional sintering, and the microstructure evolution and densification behavior were studied. Dense microstructures were reached using both sintering methods at relatively low temperatures. In the case of SPS, the core-shell architecture was partially maintained and nano-structured CGO grains were formed, while conventional sintering led to the formation of larger CGO grains. This work covers a detailed characterization of (a) the individual LSC-CGO core-shell particles and (b) the composites after densification. Full article

Tubular oxygen transport membranes (OTMs) that can be directly integrated in high temperature processes have a large potential to reduce CO₂ emissions. However, the challenging processing of these multilayered tubes, combined with strict material stability requirements, has so far hindered such a direct integration. We have investigated if a porous support based on (Y₂O₃)_0.03(ZrO₂)_0.97 (3YSZ) with a dense composite oxygen membrane consisting of (Y₂O₃)_0.01(Sc₂O₃)_0.10(ZrO₂)_0.89 (10Sc1YSZ) as an ionic conductor and LaCr_0.85Cu_0.10Ni_0.05O_3−δ (LCCN) as an electronic conductor could be fabricated as a tubular component, since these materials would provide outstanding chemical and mechanical stability. Tubular components were made by extrusion, dip coating, and co-sintering, and their chemical and mechanical integrity was evaluated. Sufficient gas permeability (≥10⁻¹⁴ m²) and mechanical strength (≥50 MPa) were achieved with extruded 3YSZ porous support tubes. The high co-sintering temperature required to densify the 10ScYSZ/LCCN membrane on the porous support, however, causes challenges related to the evaporation of chromium from the membrane. This chemical degradation caused loss of the LCCN electronic conducting phase and the formation of secondary lanthanum zirconate compounds and fractures. LCCN is therefore not suitable as the electronic conductor in a tubular OTM, unless means to lower the sintering temperature and reduce the chromium evaporation are found that are applicable to the large-scale fabrication of tubular components. Full article

The evaluation of the piezoelectric properties of ferroelectric ceramics generally has a high level of uncertainty, due to incomplete poling, porosity, domain wall clamping and other effects. In addition, the poling process is often difficult and dangerous, due to the risk of breaking or damaging the sample. A method is described for the evaluation of the potential intrinsic piezoelectric response that a ceramic would have after full poling, without poling it. The method relies on the fact that any material undergoes an elastic softening below the ferroelectric transition temperature, whose magnitude can be expressed in terms of the intrinsic piezoelectric and dielectric coefficients of the material. Such a softening is equivalent to an electromechanical coupling factor averaged over all the components, due to the unpoled state of the sample, and can be deduced from a single temperature scan of an elastic modulus of a ceramic sample, spanning the ferroelectric and paraelectric states. The strengths, limits and possible applications of the method are discussed. Full article