Devendraprakash Gautam

Thermolytic synthesis of graphitic boron carbon nitride from an ionic liquid precursor: mechanism, structure analysis and electronic properties

Recent work has shown the potential of ionic liquids (ILs) as a precursor for porous networks and nitrogen doped carbon materials. The combination of liquid state and negligible vapour pressure represents almost ideal precursor properties and simplifies the processing drastically. Here, we extend this work to get a deeper insight into the solid formation mechanism and to synthesize a mixed boron carbon nitride species by the thermolysis of N,N′-ethylmethylimidazolium tetracyanoborate (EMIM-TCB), a well-known boron- and nitrogen-containing IL. In contrast to other molecule pyrolysis routes boron carbon nitride shows the average composition “BC3N” and like other IL-derived materials turns out to be distorted graphitic, but thermally and chemically very stable, and possesses favourable electrical properties. The detailed mechanistic investigation using TG-IR, FT-IR, solid-state NMR, Raman, WAXS, EELS, XPS and HRTEM also contributes to the general understanding of IL-based material formation mechanisms.

Thermoelectric properties of pulsed current sintered nanocrystalline Al-doped ZnO by chemical vapour synthesis

ZnO is a promising n-type oxide thermoelectric material, which is stable in air at elevated temperatures. In the present study, we report the bottom-up approach to create Al-doped ZnO nanocomposites from nanopowders, which are prepared by chemical vapour synthesis. With our synthesis route, we are able to create highly doped Al-containing ZnO nanocomposites that exhibit bulk-like electrical conductivity. Moreover, the impact of the microstructure of the nanocomposites on their thermal conductivity is enormous, with a value of 1.0 W m−1 K−1 for 1% Al–ZnO at room temperature, which is one of the lowest values reported, to date, on ZnO nanocomposites. The optimization of the Al-doping and microstructure with respect to the transport properties of bulk Al–ZnO nanocomposites leads to a zT value of about 0.24 at 950 K, underlining the potential of our technique.

The effect of Peltier heat during current activated densification

It is shown that current-activated pressure-assisted densification (CAPAD) is sensitive to the Peltier effect. Under CAPAD, the Peltier effect leads to a significant redistribution of heat within the sample during the densification. The densification of highly p-doped silicon nanoparticles during CAPAD and the properties of the obtained samples are investigated experimentally and by computer simulation. Both, simulation and experiments, indicate clearly a higher temperature on the cathode side and a decreasing temperature from the center to the outer shell. Furthermore, computer simulations provide additional insights into the temperature profile which explain the anisotropic properties of the measured sample.It is shown that current-activated pressure-assisted densification (CAPAD) is sensitive to the Peltier effect. Under CAPAD, the Peltier effect leads to a significant redistribution of heat within the sample during the densification. The densification of highly p-doped silicon nanoparticles during CAPAD and the properties of the obtained samples are investigated experimentally and by computer simulation. Both, simulation and experiments, indicate clearly a higher temperature on the cathode side and a decreasing temperature from the center to the outer shell. Furthermore, computer simulations provide additional insights into the temperature profile which explain the anisotropic properties of the measured sample.

Stable zinc oxide nanoparticle dispersions in ionic liquids

The influence of the hydrophilicity and length of the cation alkyl chain in imidazolium-based ionic liquids on the dispersability of ZnO nanoparticles by ultrasound treatment was studied by dynamic light scattering and advanced rheology. ZnO nanopowder synthesized by chemical vapor synthesis was used in parallel with one commercially available material. Before preparation of the dispersion, the nanoparticles characteristics were determined by transmission electron microscopy, X-ray diffraction, nitrogen adsorption with BET analysis, and FT-IR spectroscopy. Hydrophilic ionic liquids dispersed all studied nanopowders better and in the series of hydrophilic ionic liquids, an improvement of the dispersion quality with increasing length of the alkyl chain of the cation was observed. Especially, for ionic liquids with short alkyl chain, additional factors like nanoparticle concentration in the dispersion and the period of the ultrasonic treatment had significant influence on the dispersion quality. Additionally, nanopowder characteristics (crystallite shape and size as well as the agglomeration level) influenced the dispersion quality. The results indicate that the studied ionic liquids are promising candidates for absorber media at the end of the gas phase synthesis reactor allowing the direct preparation of non-agglomerated nanoparticle dispersions without supplementary addition of dispersants and stabilizers.

Synthesis and Characterization of Hafnium Carbide Based Ceramics

Hafnium carbide powder was synthesized by sol-gel polycondensation of hafnium chloride with citric acid. The starting materials were dissolved in water and mixed homogeneously on a hot plate until a precomposite gel was formed. Pyrolysis of the obtained gel resulted in formation of monoclinic hafnia and amorphous carbon, which after subsequent heat treatment transformed into hafnium carbide. Materials were analyzed by means of X-ray diffraction and electron microscopy investigations. The results showed that the obtained carbide powder was composed of nearly equiaxed particles of narrow size distribution. The obtained hafnium carbide powder was densified via spark plasma sintering (SPS) at 1950 oC using molybdenun silicide as sintering additive. Microstructure and mechanical properties of the obtained hafnium carbide ceramics were investigated.

The influence of sintering conditions on the phase purity of bulk EuTiO3 and Eu0.5Ba0.5TiO3 ceramics

EuTiO3 and Eu0.5Ba0.5TiO3 ceramics were synthesized using mechanochemical activation of oxide precursors and then calcined. The uniaxially as well as isostatically pressed samples were sintered in different kinds of reducing atmospheres, namely Ar + (7–10)%H2, respectively, 99.99%H2 in the case of pressureless sintering or in vacuum (enriched by CO vapors) in the case of pressure-assisted spark plasma sintering (SPS). The samples prepared by SPS contained the pyrochlore phase as the second phase. In contrast with SPS, pressureless sintered samples were phase pure, although thermodynamics calculations showed that CO atmosphere in SPS is more reducing than pure hydrogen. This is explained by short sintering times in SPS that do not allow establishment of the thermodynamic equilibrium. The proper choice of sintering temperature, time, and atmosphere enabled preparation of dense and phase pure samples of Eu x Ba1− x TiO3 ceramics suitable for the evaluation of “true” physical properties (e.g., infrared reflectivity), or for experimental confirmation of specific functionalities proposed from theory.