Metal-ceramic/ceramic nanostructured layered composites for solid oxide fuel cells by spark plasma sintering.

In this work, bi-layered Fe-Ni-Co-YSZ/YSZ nanostructured composites for solid oxide fuel cells were obtained using the spark plasma sintering (SPS) technique. The microstructures of the anode and electrolyte were controlled by optimization of SPS consolidation parameters. The resulting bilayers have a full dense YSZ electrolyte and porous Fe-Ni-Co/YSZ anode as well as crack-free and well-bonded anode/electrolyte interface. On the other hand, SPS under non-optimized processing parameters cannot yield the desired results. The high resistance to thermal stresses of the fabricated half-cells was achieved with Fe-Ni-Co/YSZ anode. The developed anode showed higher thermal compatibility with YSZ electrolyte than usual Ni/YSZ cermet. Thus, with the successful combination of SPS parameters and anode material, we have obtained bi-layers for SOFCs with required microstructure and thermal compatibility.

Spark plasma sintered Ni-YSZ/YSZ bi-layers for solid oxide fuel cell.

Ni-YSZ/YSZ bi-layers for SOFCs were fabricated by spark plasma sintering (SPS). Optimization of SPS parameters of YSZ and NiO/YSZ powders was performed in order to fabricate anode and electrolyte with desired microstructures. The effect of sintering conditions on microstructure and electrical properties of YSZ was studied. The influence of processing parameters and amount of pore-forming agent on the microstructures of Ni/YSZ cermets was also investigated. It was shown that the amount of pore-former and in situ reduction of nickel oxide had a substantial effect on microstructure of the cermets. The in situ reduced anode demonstrates sufficiently homogeneous distribution of Ni and YSZ making a conduction path for electrons and ions. Ni-YSZ/YSZ bi-layers with crack-free and well-bonded anode/electrolyte interface were obtained. Furthermore, warping was not observed for the produced bi-layers.

Densification kinetics of nanocrystalline zirconia powder using microwave and spark plasma sintering--a comparative study.

Two-stage densification process of nanosized 3 mol% yttria-stabilized zirconia (3Y-SZ) polycrystalline compacts during consolidation via microwave and spark-plasma sintering have been observed. The values of activation energies obtained for microwave and spark-plasma sintering 260-275 kJ x mol(-1) are quite similar to that of conventional sintering of zirconia, suggesting that densification during initial stage is controlled by the grain-boundary diffusion mechanism. The sintering behavior during microwave sintering was significantly affected by preliminary pressing conditions, as the surface diffusion mechanism (230 kJ x mol(-1)) is active in case of cold-isostatic pressing procedure was applied.

High hardness BaCb-(BxOy/BN) composites with 3D mesh-like fine grain-boundary structure by reactive spark plasma sintering.

Boron carbide B4C powders were subject to reactive spark plasma sintering (also known as field assisted sintering, pulsed current sintering or plasma assisted sintering) under nitrogen atmosphere. For an optimum hexagonal BN (h-BN) content estimated from X-ray diffraction measurements at approximately 0.4 wt%, the as-prepared BaCb-(BxOy/BN) ceramic shows values of Berkovich and Vickers hardness of 56.7 +/- 3.1 GPa and 39.3 +/- 7.6 GPa, respectively. These values are higher than for the vacuum SPS processed B4C pristine sample and the h-BN -mechanically-added samples. XRD and electronic microscopy data suggest that in the samples produced by reactive SPS in N2 atmosphere, and containing an estimated amount of 0.3-1.5% h-BN, the crystallite size of the boron carbide grains is decreasing with the increasing amount of N2, while for the newly formed lamellar h-BN the crystallite size is almost constant (approximately 30-50 nm). BN is located at the grain boundaries between the boron carbide grains and it is wrapped and intercalated by a thin layer of boron oxide. BxOy/BN forms a fine and continuous 3D mesh-like structure that is a possible reason for good mechanical properties.

Non-catalytic facile synthesis of superhard phase of boron carbide (B13C2) nanoflakes and nanoparticles.

Boron Carbide is one the hardest and lightest material that is also relatively easier to synthesis as compared to other superhard ceramics like cubic boron nitride and diamond. However, the brittle nature of monolithic advanced ceramics material hinders its use in various engineering applications. Thus, strategies that can toughen the material are of fundamental and technological importance. One approach is to use nanostructure materials as building blocks, and organize them into a complex hierarchical structure, which could potentially enhance its mechanical properties to exceed that of the monolithic form. In this paper, we demonstrated a simple approach to synthesize one- and two-dimension nanostructure boron carbide by simply changing the mixing ratio of the initial compound to influence the saturation condition of the process at a relatively low temperature of 1500 degrees C with no catalyst involved in the growing process. Characterization of the resulting nano-structures shows B13C2, which is a superhard phase of boron carbide as its hardness is almost twice as hard as the commonly known B4C. Using ab-initio density functional theory study on the elastic properties of both B12C3 and B13C2, the high hardness of B13C2 is consistent to our calculation results, where bulk modulus of B13C2 is higher than that of B4C. High resolution transmission electron microscopy of the nanoflakes also reveals high density of twinning defects which could potentially inhibit the crack propagation, leading to toughening of the materials.

Tough yttria-stabilized zirconia ceramic by low-temperature spark plasma sintering of long-term stored nanopowders.

Weakly agglomerated 1.75 and 3 mol% yttria stabilized zirconia nanopowders were used in this study after six years of storage in vacuum-processed plastic containers. The proper storage conditions of the Y-TZP nanopowders avoided the hard agglomeration. Untreated and bead-milled nanopowders were used to obtain dense ceramics by slip casting and subsequent low-temperature sintering. Fully dense nanostructured 1.75Y-TZP and 3Y-YZP ceramics with and without doping of 1 wt% Al2O3 were produced by an optimized spark plasma sintering (SPS) technique at the temperatures of 1050-1150 degrees C at a pressure of 100 MPa. The SPS has revealed the clear advantage of consolidation of the weakly agglomerated nanopowders without preliminary deagglomeration. The Vickers hardness of both the low-temperature and spark plasma sintered samples was found to lie in the range of 10.98-13.71 GPa. A maximum fracture toughness of 15.7 MPa m(1/2) (average 14.23 MPa m(1/2)) was achieved by SPS of the 1.75Y-TZP ceramic doped with 1 wt% Al2O3 whereas the toughness of the 3Y-TZP ceramics with and without alumina doping was found to vary between 3.55 and 5.5 MPa m(1/2).

'Beautiful' unconventional synthesis and processing technologies of superconductors and some other materials.

Superconducting materials have contributed significantly to the development of modern materials science and engineering. Specific technological solutions for their synthesis and processing helped in understanding the principles and approaches to the design, fabrication and application of many other materials. In this review, we explore the bidirectional relationship between the general and particular synthesis concepts. The analysis is mostly based on our studies where some unconventional technologies were applied to different superconductors and some other materials. These technologies include spray-frozen freeze-drying, fast pyrolysis, field-assisted sintering (or spark plasma sintering), nanoblasting, processing in high magnetic fields, methods of control of supersaturation and migration during film growth, and mechanical treatments of composite wires. The analysis provides future research directions and some key elements to define the concept of 'beautiful' technology in materials science. It also reconfirms the key position and importance of superconductors in the development of new materials and unconventional synthesis approaches.

Zirconia nanoceramic via redispersion of highly agglomerated nanopowder and spark plasma sintering.

A 2.7 mol% yttria stabilizing tetragonal zirconia (2.7Y-TZP) nanopowder was synthesized and stored for five years. Humidity and unsatisfactory storage conditions gradually caused heavy agglomeration. Within a few months, 2.7Y-TZP nanopowder became useless for any technological application. A bead-milling deagglomeration technique was applied to recover the heavily agglomerated yttria-stabilized zirconia nanopowder. Low-temperature sintering and spark plasma sintering (SPS) were performed, resulting in fully dense nanostructured ceramics. Compacts formed with heavily agglomerated powder present low sinterability and poor mechanical properties. Bead-milling suspension formed compacts exhibit mechanical properties in the range of the values reported for nanostructured zirconia. This observation confirms the effectiveness of bead-milling in the deagglomeration of highly agglomerated nanopowders. The high value of Vickers hardness of 13.6 GPa demonstrates the success of the processing technique for recovering long-time-stored oxide nanopowders.

Si3N4-TiN nanocomposite by nitration of TiSi2 and consolidation by hot pressing and spark plasma sintering.

Homogeneous nanostructured Si3N4-TiN composite powder was obtained by nitration of a TiSi2 powder precursor in a nitrogen flow. Mechanoactivation of titanium disilicide increases the nitration rate and reduces the temperature of formation of the Si3N4 and TiN. The properties of hot pressing (HP) and spark plasma sintering (SPS) of the nanostructured Si3N4-TiN composite with Y2O3 and Al2O3 additives have been studied. In the case of the HP-prepared composite the processing conditions are sufficient to form a stable, equilibrated grain boundary framework. The SPS consolidation is extremely rapid, low-temperature process and the sintering temperature was 300-400 degrees C lower than that of the hot pressing temperature. As a result the grain boundary framework was underdeveloped. Post-sintering anneal of the SPS-prepared samples caused significant improvement of their mechanical properties. The SPS and HP-derived Si3N4-40 mass% TiN-6 mass% Y2O3-2 mass% Al2O3 nano-composite of 98.4% and 98.9% of relative density demonstrate the Vickers hardness values of 13.2 and 13.7 GPa, respectively. The grains of Si3N4 and TiN were much finer in the case of the SPS-derived ceramic composite. However, the better development of the grain boundary framework in the case of the higher temperature HP treatment in comparison to the SPS significantly reduced the advantage of nanocrystallinity. In both cases the fracture toughness was comparable even after the improvement of grain boundary framework during the SPS consolidation. The K(1c), of 7.83 MPax m(1/2) of the sample prepared according to the best SPS regime is also comparable to K(1c) of 8.30 MPa x m(1/2) of much coarser hot pressed ceramic with very similar relative density.

Nanoblast synthesis and consolidation of (La0.8Sr0.2)(Ga0.9Mg0.1)O(3-delta) under Spark plasma sintering conditions.

Four-cation nanograined strontium and magnesium doped lanthanum gallate (La0.8Sr0.2) (Ga0.9Mg0.1)O(3-delta) (LSGM) and its composite with 2 wt% of ceria (LSGM-Ce) were prepared. Morphologically homogeneous nanoreactors, i.e., complex intermediate metastable aggregates of desired composition were assembled by spray atomization technique, and subsequently loaded with nanoparticles of highly energetic C3H6N6O6. Rapid nanoblast calcination technique was applied and the final composition was synthesized within the preliminary localized volumes of each single nanoreactor on the first step of spark plasma treatment. Subsequent SPS consolidations of nanostructured extremely active LSGM and LSGM-Ce powders were achieved by rapid treatment under pressures of 90-110 MPa. This technique provided the heredity of the final structure of nanosize multimetal oxide, allowed the prevention of the uncontrolled agglomeration during multicomponent aggregates assembling, subsequent nanoblast calcination, and final ultra-rapid low-temperature SPS consolidation of nanostructured ceramics. LaSrGaMgCeO(3-delta) nanocrystalline powder consisting of approximately 11 nm crystallites was consolidated to LSGM-Ce nanoceramic with average grain size of approximately 14 nm by low-temperature SPS at 1250 degrees C. Our preliminary results indicate that nanostructured samples of (La0.8Sr0.2)(Ga0.9Mg0.1)O(3-delta) with 2 wt% of ceria composed of approximataley 14 nm grains can exhibit giant magnetoresistive effect in contrast to the usual paramagnetic properties measured on the samples with larger grain size.