Reactive flash sintering of powders of four constituents into a single phase of a complex oxide in a few seconds below 700°C

Recent work on reactive flash sintering of powders of two oxides, bismuth and of iron oxide, into pure single phase bismuth ferrite, which was accomplished in a few seconds at low furnace temperatures, is expanded to four constituents, alumina, lithia, zirconia, and lanthana, to produce reasonably dense polycrystals of a predominantly single phase, cubic LLZO(Al). Transformation and sintering occur concurrently at a furnace temperature near 700°C, in ambient atmosphere, in just a few seconds. The process may simplify the preparation of complex ceramics with new chemistries and dopants, which are predicted from ab intio calculations to have special attributes, not only because the powders sinter quickly at low temperatures, but also because the need for stoichiometric powders as starting materials is obviated.     

Quantifying adherence of oxide scales on steels exposed to high temperature and pressure steam

Oxide scale exfoliation is a major concern in fossil fuel power generation because it can cause tube blockages and erode valves and steam turbine components downstream. There is still considerable scientific and commercial interest to improve the mechanistic understanding of oxide failures by developing models to predict exfoliation and the extent of tube blockage as a function of operating conditions and component geometries. Tensile testing inside a scanning electron microscope was conducted on ferritic–martensitic and austenitic steel specimens with the steam side (Fe,Cr)-rich oxides grown after exposures for up to 1000 h in steam with ~100 ppb O₂ at 276 bar and 550°C. Multiple oxide layer cracks and delamination events were observed and analyzed in detail during the tests. Results from the testing agreed well with earlier observations that had identified the failure location at the outer–inner oxide layer for all tested materials. Calculated adhesion energies identified the outer–inner oxide interface of alloy 347HFG as the weakest interface.     

Reactive flash sintering: MgO and α-Al2O3 transform and sinter into single-phase polycrystals of MgAl2O4

We show that flash experiments with three phase mixed-powders of yttria-stabilized zirconia (8YSZ), MgO, and α-Al₂O₃ not only produce polycrystals of high density, but also the transformation of magnesia and alumina into single-phase spinel. The presence of zirconia facilitates the onset of the flash. The sintering experiments in the laboratory were extended to live experiments at the National Synchrotron Light Source II at Brookhaven National Laboratory in order to measure the time-dependent evolution of single-phase spinel. The phase transformation occurred in <3 seconds during Stage II. Later, during Stage III the cubic zirconia transformed partly into the monoclinic phase, which reverted back to the cubic phase when the flash was extinguished by turning off the current to the specimen. The results underpin a recent report on the synthesis of single-phase bismuth ferrite from constituent oxides in reactive flash experiments, raising the specter of flash as a method for synthesis as well as sintering of complex oxide ceramics. The role of zirconia in catalyzing the flash in the present study is discussed.     

Conjugation of curcumin with PVP capped gold nanoparticles for improving bioavailability

Curcumin, a natural polyphenolic compound, has astounding therapeutic applications but lacks in bioavailability mainly due to its poor solubility in water. Polyvinyl pyrrolidone (PVP) which is a proven drug carrier has been used to facilitate the conjugation of curcumin with gold nanoparticles and to improve the solubility of curcumin in water. In this conjugate diaryl heptanoid chromophore group of curcumin which is a much needed group in biomedical applications remains intact as observed from FTIR and UV–vis spectroscopy analysis. The work shows good promise for such conjugates as therapeutic-cum-imaging materials in biomedical field.     

α-Alumina and spinel react into single-phase high-alumina spinel in <3 seconds during flash sintering

In situ X-ray diffraction measurements at the Advanced Photon Source show that α-Al₂O₃ and MgAl₂O₄ react nearly instantaneously and completely, and nearly completely to form single-phase high-alumina spinel during voltage-to-current type of flash sintering experiments. The initial sample was constituted from powders of α-Al₂O₃, MgAl₂O₄ spinel, and cubic 8 mol% Y₂O₃-stabilized ZrO₂ (8YSZ) mixed in equal volume fractions, the spinel to alumina molar ratio being 1:1.5. Specimen temperature was measured by thermal expansion of the platinum standard. These measurements correlated well with a black-body radiation model, using appropriate values for the emissivity of the constituents. Temperatures of 1600-1736°C were reached during the flash, which promoted the formation of alumina-rich spinel. In a second set of experiments, the flash was induced in a current-rate method where the current flowing through the specimen is controlled and increased at a constant rate. In these experiments, we observed the formation of two different compositions of spinel, MgO•3Al₂O₃ and MgO•1.5Al₂O₃, which evolved into a single composition of MgO•2.5Al₂O₃ as the current continued to increase. In summary, flash sintering is an expedient way to create single-phase, alumina-rich spinel.     

Viscous Potential Flow Analysis of Kelvin–Helmholtz Instability of a Cylindrical Flow with Heat and Mass Transfer

A linear analysis of Kelvin–Helmholtz instability of a cylindrical interface has been carried out when there is heat and mass transfer across the interface, using viscous potential flow theory. Both fluids are considered as incompressible, viscous, and thermally conducting with different kinematic viscosities. Both axisymmetric as well as asymmetric disturbances are considered. Stability criterion is given by a critical value of relative velocity and stability is discussed theoretically as well as numerically. Various graphs with respect to physical parameters such as wave number, viscosity ratio, heat transfer coefficients, Reynolds number, etc., have been drawn and the effect of various parameters have been described. A comparison with the linear stability analysis of inviscid fluids (Lee [10]) has been made and it is observed that viscosity has a stabilizing effect on the stability of the system. © 2013 Wiley Periodicals, Inc. Heat Trans Asian Res, 43(6): 489–503, 2014; Published online 3 October 2013 in Wiley Online Library ( wileyonlinelibrary.com/journal/htj ). DOI 10.1002/htj.21092     

Oxidation Kinetics of an Amorphous Silicon Carbonitride Ceramic

The oxidation kinetics of amorphous silicon carbonitride (SiCN) was measured at 1350°C in ambient air. Two types of specimens were studied: one in the form of thin disks, the other as a powder. Both specimens contained open nanoscale porosity. The disk specimens exhibited weight gain that saturated exponentially with time, analogous to the oxidation behavior of reaction-bonded Si₃N₄. The saturation value of the weight gain increased linearly with specimen volume, suggesting the nanoscale pore surfaces oxidized uniformly throughout the specimen. This interpretation was confirmed by high-resolution electron microscopy and secondary ion mass spectroscopy. Experiments with the powders (having a particle size much larger than the scale of the nanopores) were also consistent with measurements of the disks. However, the powder specimens, having a high surface-to-volume ratio, continued to show measurable weight gain due to oxidation of the exterior surface. The wide range of values for the surface-to-volume ratio, which included all specimens, permitted a separation of the rate of oxidation of the free surface and the oxidation of the internal surfaces of the nanopores. Surface oxidation data were used to obtain the rate constant for parabolic growth of the oxidation scale. The values for the rate constant obtained for SiCN lay at the lower end of the spectrum of oxidation rates reported in the literature for several Si₃N₄ and SiC materials. Convergence in the behavior of SiCN and CVD-SiC is ascribed to the purity of both materials. Conversely, it is proposed that the high rates of oxidation of sintered polycrystalline silicon carbides and nitrides, as well as the high degree of variability of these rates, might be related to the impurities introduced by the sintering aids.     

Effects of SEBS-g-MA copolymer on non-isothermal crystallization kinetics of polypropylene

The non-isothermal crystallization kinetics of pure PP and PP/SEBS-g-MA blends up to volume fraction, Φ _d (0–0.50) was studied by differential scanning calorimetry at four different cooling rates. Crystallization parameters were analyzed by Ozawa and Liu models. The Ozawa model fits in the PP/SEBS-g-MA blends and indicates the effect of SEBS-g-MA copolymer on the crystallization process of polypropylene. Augis–Bennet model has been used to calculate activation energy, ?E, during non-isothermal crystallization process. The value of ?E decreased with SEBS-g-MA due to flexibility of SEBS-g-MA by which movements of chains of PP become easier.