Ravi Kumar N V

Porous ceria for high temperature catalytic applications demands structural integrity concomitant with sinter resistance and improved gas permeability. The current state of the art hinges on complex synthesis methodologies which are not only expensive but also lack flexibility in pore tailorability. Hence, the development of porous scaffolds through low-cost processes without compromising on the functionality is in order. Herein, we demonstrate porous ceria with an open porosity of 88% developed through camphene assisted freeze casting for the first time. Microstructural evolution with different building blocks–micrometre-sized particles and short fibres were also studied. Preliminary catalytic activity obtained via temperature programmed reduction exemplified similar profiles showing no effect of the initial building blocks on the activity.

We investigate the impact of different numbers of positive and negative examples on machine learning for sapphire crystals defects prediction. We obtain the models of crystal growth parameters influence on the sapphire crystal growth. For example, these models allow predicting the defects that occur due to local overcooling of crucible walls in the thermal node leading to the accelerated crystal growth. We also develop the prediction models for obtaining the crystal weight, blocks, cracks, bubbles formation, and total defect characteristics. The models were trained on all data sets and later tested for generalization on testing sets, which did not overlap the training set. During training and testing, we find the recall and precision of prediction, and analyze the correlation among the features. The results have shown that the precision of the neural network method for predicting defects formed by local overcooling of the crucible reached 0.94.

The paper studies the high-temperature structure of a chaotic potential (CP) induced in heterojunctions of the group III nitrides by the electrostatic field of charged dislocations. The CP amplitude in the junction plane has been obtained taking into account the spatial dispersion of a dielectric response of two-dimensional electron gas. The dependence of the CP properties on the parameters of the system was found. In particular, the magnitude of the CP amplitude exceeds that of the thermal energy, if the two-dimensional non-degenerate gas given in III-nitride heterojunctions and the dislocation densities being up to and over 1010 cm–2

Palladium-containing silicon oxycarbide (SiPdOC) ceramics were synthesized using polymethylsilsesquioxane modified with palladium acetate as a single-source precursor. Thus, pyrolysis in argon at 1100 °C led to nanocomposites consisting of Pd2Si nanocrystallites dispersed in an amorphous SiOC matrix. Exposure of SiPdOC to higher temperatures resulted in the precipitation of PdSi in addition to Pd2Si. The temperature-dependent evolution of the phase composition and microstructure in SiPdOC were analyzed using XRD and TEM respectively and rationalized by a ThermoCalc-based thermodynamic assessment showing the feasibility of the possible reactions. The formation of PdSi was perceived because of the shift in the Pd-Si atomic composition towards the higher Si side, caused by the diffusion of Si present in the matrix into the Pd-Si melt, formed upon the heat-treatment above the melting point (1390 °C) of Pd2Si. Further, Raman spectroscopic investigation indicated that Pd catalytically enhanced the graphitization of the free carbon in SiPdOC ceramics.

Polymer-derived processing of ceramics (PDC) is an efficient technique to prepare porous nanocomposites with precise control over their phase composition and in relation to the Si-based ceramic matrix containing free carbon. The microstructure of these nanocomposites can be fine-tuned at the molecular scale for obtaining necessary properties by tailoring the chemical configuration of the preceramic polymer. In the present work, vanadium-based nanocomposites were synthesized as oxygen reduction reaction (ORR) catalysts with the objective of elucidating the effect of microstructure changes on catalytic efficiency. For this purpose, a single-source precursor (SSP) was synthesized by crosslinking phenyl- and hydrido-substituted polysiloxane and vanadium acetylacetonate followed by pyrolysis at 1100 °C. The resulting solid was composed of sparsely distributed nanodomains of vanadium carbide (VC) crystals precipitated within an amorphous silicon oxycarbide (−Si-O-C−) matrix. High-temperature treatment of the pyrolyzed samples beyond 1300 °C induced the crystallization of β-SiC as well as VC. Furthermore, Raman spectroscopy confirmed the segregation of sp2-hybridized, turbostratic free carbon. The samples exposed to 1300 °C revealed a specific surface area of 239 m2/g. The electrocatalytic activity of the sample heat-treated at 1300 °C showed the best performance with respect to the ORR performance with onset potential (Eo) and half-wave potential (E1/2) values of 0.81 and 0.72 V, respectively. In addition, improved kinetics with a Tafel slope of 57 mV/dec and enhanced current density in the diffusion-controlled region (Id) of 3.7 mA/cm2 were observed for this sample. The increase in Eo was attributed to the optimal interfacial characteristics between the VC and SiOC matrix with better embedment of VC with free carbon through V-C bonds. The higher E1/2 and faster kinetics are because of the higher electronic conductivity caused by the free carbon effectively connecting metallic VC crystallites. Besides, the higher specific surface area of this sample enhanced Id

The dielectric behavior of spark plasma sintered SiC(O)/HfCxN1-x nanocomposites synthesized through polymer derived ceramic route was investigated in the frequency range of 1 kHz to 1 MHz at room temperature. The nanostructural features revealed HfCxN1-x nanocrystals encapsulated in a nanometric thin layer of carbon dispersed uniformly in a SiC(O) matrix with segregated free carbon. The nanocomposites exhibited colossal permittivity values in the order of 103 at 1 kHz which reduced to 646 at 1 MHz. The interfacial polarization mechanism existing between complex nanostructural interfaces and the percolation of HfCxN1-x nanocrystals are believed to be responsible for the high permittivity values observed in the measured frequency range. The AC conductivity exemplified a frequency independent behavior at lower frequencies while at higher frequencies, the conductivity exhibited frequency dependence, indicating the existence of hopping type mechanism.

Tantalum oxynitride (TaOxN1−x) fibers were synthesized and evaluated for their electrocatalytic hydrogen activity using an in-house developed centrifugal spinning setup. By tailoring the composition of the spinning solution and optimizing collector distance and rotation speed of the spinneret, bead-free TaOxN1−x fibers with a diameter of 800 nm were obtained. The fibers were structurally characterized through phase and elemental analysis, confirming the formation of monoclinic TaOxN1−x with clear splitting of the X-ray photoelectron spectroscopy peaks indicating Ta was in +5 oxidation state. The resulting oxynitride fibers exhibited superior electrocatalytic performance with low overpotentials (250 mV) to generate 10 mA/cm2 compared to Ta2O5 oxide fibers. Interestingly, the enhanced activity of oxynitride fibers was observed to be suppressed in basic medium due to the high oxophilicity of tantalum ions and a negative Gibbs adsorption-free energy, leading to poisoning of the active sites. This work demonstrates a facile pathway for the fabrication of high-performance electrocatalysts, based on TaOxN1−x fibers, from a cost-effective and energy-efficient centrifugal spinning technique.

In this work, titania-silicon oxycarbide nanocomposites synthesized via the polymer derived ceramics route have been sintered into crack-free monoliths using spark plasma sintering and their mechanical properties as well as their apparent density have been characterized. The x-ray diffractogram clearly showed the stabilization of anatase phase of size less than 10 nm size in an amorphous silicon oxycarbide matrix at 1200 °C. The hardness and elastic modulus determined using nanoindentation were found to be 9 GPa and 82 GPa, respectively, and the fracture toughness calculated using indentation crack length method was found to be 2.34 MPa m1/2. In addition to this, ball-on-three ball technique was used to evaluate the biaxial flexural strength and fractographic studies were carried out to understand the fracture mechanisms.

Amorphous silicon oxycarbides are known to be an effective anode material for lithium-ion batteries. Despite their exceptional properties and high charge capacities, however, their practical uses are limited by their significant first-cycle loss, considerable hysteresis, and low cyclic ability. Comparatively, SiOC/metal oxide materials have demonstrated increased rate capability and cyclic stability. This study utilized a liquid precursor-derived ceramic method to modify SiOC with titanium (IV) butoxide precursor to synthesize SiOC/TiOxCy. X-ray diffractograms confirmed the amorphous nature of SiOC/TiOxCy. The elemental composition and bonding properties were investigated using X-ray photoelectron spectroscopy, and electron microscopy was used to explore morphological features. In the first cycle, the reversible capacity of pyrolyzed SiOC/TiOxCy was 520 mAh g−1, which then increased to 736 mAh g−1 for the 1200°C annealed SiOC/TiOxCy due to the increased free carbon network and TiC conductive phases. The irreversible capacity of the first cycle was 568 mAh g−1, which was lower than the annealed SiOC irreversible capacity of 695 mAh g−1. Interestingly, the rate stability of the pyrolyzed SiOC/TiOxCy performed more stability than the annealed sample. Localized carbothermal reactions between amorphous SiOC/TiOxCy and free carbon at annealing temperatures resulted in loss of structure stability.

TiNb2O7/carbon nanocomposites synthesized through a simple, surfactant assisted precursor route is reported as a promising alternative anode material for lithium-ion batteries (LIBs). The carbon component of the nanocomposites is derived from an inexpensive and sustainable keratin rich biological source. The reinforcement of carbon in TiNb2O7 facilitated the formation of non-stoichiometric (Ti0.712Nb0.288)O2 crystalline phase, in addition to the stoichiometric TiNb2O7 phase. It also yielded a high specific surface area (~90 ​m2 ​g−1) and reduced crystallite size (~4 ​nm). Electrochemical results exemplified high reversible capacity of 356 mAh g−1 at 0.1 ​C and remarkable rate capability of ~26 mAh g−1 at ultra-high current rate of 32C. TiNb2O7/carbon nanocomposites also demonstrated remarkable cyclic stability with large capacity retention of 85% even after 50 cycles at 1 ​C. The experimental data attests the potential of TiNb2O7/keratin derived carbon nanocomposites as economically and environmentally viable promising anode material for LIBs.