Combustion Synthesis and Reactive Spark Plasma Sintering of Non-Equiatomic CoAl-Based High Entropy Intermetallics.

The present work reports the direct production of a high-entropy (HE) intermetallic CoNi0.3Fe0.3Cr0.15Al material with a B2 structure from mechanically activated elemental powder mixtures. Fast and efficient combustion synthesis (CS), spark plasma sintering (SPS), and reactive SPS (RSPS) methods were used to synthesize the HE powders and bulks. The formation of the main B2 phase along with some amounts of secondary BCC and FCC phases are reported, and L12 intermetallic (CS scheme) and BCC based on Cr (CS + SPS and RSPS schemes at 1000 °C) were observed in all samples. The interaction between the components during heating to 1600 °C of the mechanically activated mixtures and CS powders has been studied. It has been shown that the formation of the CoNi0.3Fe0.3Cr0.15Al phase occurs at 1370 °C through the formation of intermediate intermetallic phases (Al9Me2, AlCo, AlNi3) and their solid solutions, which coincidences well with thermodynamic calculations and solubility diagrams. Compression tests at room and elevated temperatures showed that the alloy obtained by the RSPS method has enhanced mechanical properties (σp = 2.79 GPa, σ0.2 = 1.82 GPa, ε = 11.5% at 400 °C) that surpass many known alloys in this system. High mechanical properties at elevated temperatures are provided by the B2 ordered phase due to the presence of impurity atoms and defects in the lattice.

Graphene Nanoflake- and Carbon Nanotube-Supported Iron-Potassium 3D-Catalysts for Hydrocarbon Synthesis from Syngas.

Transformation of carbon oxides into valuable feedstocks is an important challenge nowadays. Carbon oxide hydrogenation to hydrocarbons over iron-based catalysts is one of the possible ways for this transformation to occur. Carbon supports effectively increase the dispersion of such catalysts but possess a very low bulk density, and their powders can be toxic. In this study, spark plasma sintering was used to synthesize new bulk and dense potassium promoted iron-based catalysts, supported on N-doped carbon nanomaterials, for hydrocarbon synthesis from syngas. The sintered catalysts showed high activity of up to 223 µmolCO/gFe/s at 300-340 °C and a selectivity to C5+ fraction of ~70% with a high portion of olefins. The promising catalyst performance was ascribed to the high dispersity of iron carbide particles, potassium promotion of iron carbide formation and stabilization of the active sites with nitrogen-based functionalities. As a result, a bulk N-doped carbon-supported iron catalyst with 3D structure was prepared, for the first time, by a fast method, and demonstrated high activity and selectivity in hydrocarbon synthesis. The proposed technique can be used to produce well-shaped carbon-supported catalysts for syngas conversion.