Enhanced thermoelectric properties of In-filled Co4Sb12 by dispersion of reduced graphene oxide.

Uniform dispersion of nanosized secondary phases in bulk thermoelectric materials has proven to be an effective strategy to reduce the lattice part of thermal conductivity and improve the thermoelectric efficiency. In this work, reduced graphene oxide (rGO) was uniformly dispersed in the In0.5Co4Sb12 bulk material by ultrasonication. The formation of impurity phases of InSb and CoSb2 in the In-filled Co4Sb12 is inevitable, as observed from XRD and EPMA analyses. The Raman spectra of the nanocomposites showed broad peaks suggesting phonon softening and additional peaks corresponding to rGO. Electron transport was not affected by rGO addition, resulting in little change in the electrical resistivity and Seebeck coefficient. The lattice thermal conductivity of the bulk material was significantly reduced by the addition of a small amount of rGO, primarily attributed to the interface scattering of phonons. Hence, the highest zT of ∼1.53 at 773 K was achieved for the In0.5Co4Sb12/0.25 vol% rGO composite in the temperature range from 723 K to 773 K.

Strength-Ductility Synergy in High Entropy Alloys by Tuning the Thermo-Mechanical Process Parameters: A Comprehensive Review.

The strength-ductility trade-off is an eminent factor in deciding the mechanical performance of a material with regard to specific applications. The strength-ductility synergy is generally inadequate in as-synthesized high entropy alloys (HEAs); however, it can be tailored owing to its tunable microstructure and phase stability. Thermo-mechanical processing (TMP) allows the microstructure to be tailored to achieve desired strength-ductility combination. The additional attribute is evolution of texture, which also significantly influences the mechanical properties. This review presents a critical insight into the role of TMP to achieve superior strength-ductility symbiosis at room temperature in single-phase (FCC, BCC) and multiphase HEA. The role of overall processing strategy of HEAs encompassing rolling and subsequent annealing in relation to the evolution of microstructure and texture in have been discussed. Recently practiced severe plastic deformation processes have also shown promise in improving the strength-ductility combination. The relevance of these processes in the processing of HEAs has also been analysed. At the end, futuristic approaches have been elaborated to enable efficient as well as hassle-free process towards achieving the proficiency of strength-ductility in HEAs.

Preferential phonon scattering and low energy carrier filtering by interfaces of in situ formed InSb nanoprecipitates and GaSb nanoinclusions for enhanced thermoelectric performance of In0.2Co4Sb12.

Filling the voids of cage forming compounds with loosely bound electropositive elements and by incorporating nano-sized secondary phases are promising approaches to enhance the thermoelectric figure of merit of these materials. Hence, in this work, by combining these two approaches-inserting In into the voids of skutterudite Co4Sb12 as well as dispersing nanoparticles (GaSb)-we have synthesized various samples via ball-milling and spark plasma sintering. InSb as the secondary phase of the matrix, mixed with GaSb, forms the solid solution Ga1-xInxSb. Nanocrystalline grains together with a few larger grains (10-30 µm) are found to be spread in In0.2Co4Sb12. The former is comprised of either InSb, GaSb or Ga1-xInxSb. Because of their identical space group and similar lattice parameters, InSb, GaSb and Ga1-xInxSb could not be detected separately in EBSD. High resolution transmission electron microscopy (HRTEM) was used to resolve different phases, which showed GaSb grains of size ∼10-30 nm and InSb grains of size ∼30-100 nm. Scattering of charge carriers at the interfaces of InSb, GaSb and Ga1-xInxSb as well as the matrix phases increased both the electrical resistivity and Seebeck coefficient. The multi-scale size distribution of grains, of both the matrix phase and the secondary phases, scattered phonons within a broad wavelength range, resulting in very low lattice thermal conductivities. As a result, an enhanced figure of merit of 1.4 was achieved for the (GaSb)0.1 + In0.2Co4Sb12 nanocomposite at 773 K.

Enhanced Thermoelectric Performance in the Ba0.3Co4Sb12/InSb Nanocomposite Originating from the Minimum Possible Lattice Thermal Conductivity.

The thermoelectric efficiency of skutterudite materials can be improved by lowering the lattice thermal conductivity via the uniform dispersion of a nanosized second phase in the matrix of filled Co4Sb12. In this work, nanocomposites of Ba0.3Co4Sb12 and InSb were synthesized using ball-milling and spark plasma sintering. The thermoelectric transport properties were studied from 4.2 to 773 K. The InSb nanoparticles of ∼20 nm were found to be dispersed in the Ba0.3Co4Sb12 grains with a few larger grains of about 10 µm due to the agglomeration of the InSb nanoparticles. The +2 oxidation state of Ba in Co4Sb12 resulted in a low electrical resistivity, ρ, value of the matrix. The enhancement of the Seebeck coefficient, S, and the electrical resistivity values of Ba0.3Co4Sb12 with the addition of InSb can be credited to the energy-filtering effect of electrons with low energy at the interfaces. The power factor of the composites could not be enhanced compared to the matrix because of the very high ρ value. A minimum possible lattice thermal conductivity (0.45 W/m·K at 773 K) was achieved due to the combined effect of rattling of Ba atoms in the voids and enhanced phonon scattering at the interfaces induced by nanosized InSb particles. As a result, the (InSb)0.15 + Ba0.3Co4Sb12 composite exhibited improved thermoelectric properties with the highest zT of 1.4 at 773 K and improved mechanical properties with a higher hardness, higher Young's modulus, and lower brittleness.

Effect of Sn Substitution on the Thermoelectric Properties of Synthetic Tetrahedrite.

The present study reports the effect of Sn substitution on the structural and thermoelectric properties of synthetic tetrahedrite (Cu12Sb4S13) system. The samples were prepared with the intended compositions of Cu12Sb4- xSn xS13 ( x = 0.25, 0.35, 0.5, 1) and sintered using spark plasma sintering. A detailed structural characterization of the samples revealed tetrahedrite phase as the main phase with Sn substituting at both Cu and Sb sites instead of only Sb site. The theoretical calculations using density functional theory revealed that Sn at Cu(1) 12d or Cu(2) 12e site moves the Fermi level ( EF) toward the band gap, whereas Sn at Sb 8c site introduces hybridized hole states near EF. Consequently, a relatively high optimum power factor of 1.3 mW/mK2 was achieved by the x = 0.35 sample. The Sn-substituted samples exhibited a significant decrease in the total thermal conductivity (κT) compared to the pristine composition (Cu12Sb4S13), primarily because of reduced electronic thermal conductivity. Due to an optimum power factor (1.3 mW/mK2) and reduced thermal conductivity (0.9 W/mK), a maximum zT of 0.96 at 673 K was achieved for x = 0.35 sample, which is nearly 40% increment compared to that of the pristine (Cu12Sb4S13) sample.

Ti2NiCoSnSb - a new half-Heusler type high-entropy alloy showing simultaneous increase in Seebeck coefficient and electrical conductivity for thermoelectric applications.

A new single phase high entropy alloy, Ti2NiCoSnSb with half-Heusler (HH) structure is synthesized for the first time by vacuum arc melting (VAM) followed by ball-milling (BM). The BM step is necessary to obtain the single phase. Local electrode atom probe (LEAP) analysis showed that the elements are homogeneously and randomly distributed in the HH phase without any clustering tendency. When the BM was carried out for 1 hour on the VAM alloy, microcrystalline alloy is obtained with traces of Sn as secondary phase. When BM was carried out for 5 h, single HH phase formation is realized in nanocrystalline form. However, when the BM samples were subjected to Spark plasma sintering (SPS), secondary phases were formed by the decomposition of primary phase. Nanostructuring leads to simultaneous increase in S and σ with increasing temperature. The micro (1 h BM-SPS) and nanocrystalline (5 h BM-SPS) alloys exhibited a power factor (S2σ) of 0.57 and 1.02 mWm-1K-2, respectively, at 860 K. The microcrystalline sample had a total thermal conductivity similar to bulk TiNiSn sample. The nanocrystalline alloy exhibited a ZT of 0.047 at 860 K. The microcrystalline alloy showed a ZT to 0.144 at 860 K, in comparison to the nanocrystalline alloy.

Thermoelectric properties of Co4Sb12 with Bi2Te3 nanoinclusions.

The figure of merit (zT) of a thermoelectric material can be enhanced by incorporation of nanoinclusions into bulk material. The presence of bismuth telluride (Bi2Te3) nanoinclusions in Co4Sb12 leads to lower phonon thermal conductivity by introducing interfaces and defects; it enhances the average zT between 300-700 K. In the current study, Bi2Te3 nanoparticles were dispersed into bulk Co4Sb12 by ball-milling. The bulk was fabricated by spark plasma sintering. The presence of Bi2Te3 dispersion in Co4Sb12 was confirmed by x-ray diffraction, scanning electron microscopy, transmission electron microscopy and electron back scattered diffraction technique. Energy dispersive spectroscopy showed antimony (Sb) as an impurity phase for higher contents of Bi2Te3 in the sample. The Seebeck coefficient (S) and electrical conductivity (σ) were measured in the temperature range of 350-673 K. The negative value of S indicates that most of the charge carriers were electrons. A decrease in S and increase in σ with Bi2Te3 content are due to the increased carrier concentration, as confirmed by Hall measurement. The thermal conductivity, measured between 423-673 K, decreased due to the increased phonon scattering at interfaces. A maximum zT of 0.17 was achieved at 523 K and it did not vary much throughout the temperature range. The experimental results of composites were compared by using effective medium theories.

Radioactive isotopes reveal a non sluggish kinetics of grain boundary diffusion in high entropy alloys.

High entropy alloys (HEAs) have emerged as a new class of multicomponent materials, which have potential for high temperature applications. Phase stability and creep deformation, two key selection criteria for high temperature materials, are predominantly influenced by the diffusion of constituent elements along the grain boundaries (GBs). For the first time, GB diffusion of Ni in chemically homogeneous CoCrFeNi and CoCrFeMnNi HEAs is measured by radiotracer analysis using the 63Ni isotope. Atom probe tomography confirmed the absence of elemental segregation at GBs that allowed reliable estimation of the GB width to be about 0.5 nm. Our GB diffusion measurements prove that a mere increase in number of constituent elements does not lower the diffusion rates in HEAs, but the nature of added constituents plays a more decisive role. The GB energies in both HEAs are estimated at about 0.8-0.9 J/m2, they are found to increase significantly with temperature and the effect is more pronounced for the CoCrFeMnNi alloy.

Origin of magnetocapacitance in chemically homogeneous and inhomogeneous ferrites.

The present work mainly focuses on the magnetodielectric (MD) effect in polycrystalline Ni0.9-yCuyZn0.1Fe1.98O3.97 (y = 0, 0.1, 0.2, 0.3, 0.4, 0.5) ferrite synthesized by a solid-state reaction method. Sintered samples showed the formation of CuO-rich grain boundary segregation for y≥ 0.2. The appearance of segregation made the present material chemically inhomogeneous and electrically heterogeneous. A negative MD response was observed in homogeneous ferrite for y = 0 and 0.1 due to lattice distortion (an intrinsic effect), whereas a positive MD response occurs in chemically inhomogeneous segregated ferrite (y≥ 0.2) due the collective effects of Maxwell-Wagner (MW) polarization with intrinsic magnetoresistance (an extrinsic effect).

Effect of molybdenum and niobium on the phase formation and hardness of nanocrystalline CoCrFeNi high entropy alloys.

In the present study, influence of molybdenum and niobium additions on phase formation during mechanical alloying and spark plasma sintering of CoCrFeNi high entropy alloy was studied. Major FCC and minor BCC phase were observed after mechanical alloying of CoCrFeNi. However, major FCC and sigma phase were observed after spark plasma sintering. A maximum relative density of 95% was obtained with the hardness of 570 HV in CoCrFeNi HEA. The phase formation behavior was not significantly affected by the addition of molybdenum or niobium. However, addition of Mo to CoCrFeNi increased the hardness from 570 HV to 620 HV, and the hardness increased to 710 HV with combined addition of molybdenum and niobium. After sintering, major FCC phase with crystallite size of 60-70 nm was observed in all the compositions. Further, the microstructure and hardness retention was observed in CoCrFeNiMo0.2 with annealing temperature up to 800 degrees C.