Mechanical Compatibility between Mg3(Sb,Bi)2 and MgAgSb in Thermoelectric Modules.

Thermoelectric (TE) modules are exposed to temperature gradients and repeated thermal cycles during their operation; therefore, mechanically robust n- and p-type legs are required to ensure their structural integrity. The difference in the coefficients of thermal expansion (CTEs) of the two legs of a TE module can cause stress buildup and the deterioration of performance with frequent thermal cycles. Recently, n-type Mg3Sb2 and p-type MgAgSb have become two promising components of low-temperature TE modules because of to their high TE performance, nontoxicity, and abundance. However, the CTEs of n-Mg3Sb2 and p-MgAgSb differ by approximately 10%. Furthermore, the oxidation resistances of these materials at increased temperatures are unclear. This work manipulates the thermal expansion of Mg3Sb2 by alloying it with Mg3Bi2. The addition of Bi to Mg3Sb2 reduces the coefficient of linear thermal expansion from 22.6 × 10-6 to 21.2 × 10-6 K-1 for Mg3Sb1.5Bi0.5, which is in excellent agreement with that of MgAgSb (21 × 10-6 K-1). Furthermore, thermogravimetric data indicate that both Mg3Sb1.5Bi0.5 and MgAgSb are stable in air and Ar at temperatures below ∼570 K. The results suggest the compatibility and robustness of Mg3Sb1.5Bi0.5 and MgAgSb as a pair of thermoelectric legs for low-temperature TE modules.

Boosting Thermoelectric Performance in Epitaxial GeTe Film/Si by Domain Engineering and Point Defect Control.

This study demonstrates a simultaneous realization of ultralow thermal conductivity and high thermoelectric power factor in epitaxial GeTe thin films/Si substrates by a combination of the interface introduction by domain engineering and the suppression of Ge vacancy generation by point defect control. We formed epitaxial Te-poor GeTe thin films having low-angle grain boundaries with a misorientation angle close to 0° or twin interfaces with a misorientation angle close to 180°. The control of interfaces and point defects gave rise to ultralow lattice thermal conductivity of ∼0.7 ± 0.2 W m-1 K-1. This value was the same in the order of magnitude as the theoretical minimum lattice thermal conductivity of ∼0.5 W m-1 K-1 calculated by the Cahill-Pohl model. At the same time, the GeTe thin films exhibited a high thermoelectric power factor because of the suppression of Ge vacancy generation and a small contribution of grain boundary carrier scattering. The outstanding combined technique of domain engineering and point defect control can be a great approach for developing high-performance thermoelectric films.

Validating ground-based aerodynamic levitation surface tension measurements through a study on Al2O3.

The surface tension of a molten sample can be evaluated based on its resonant frequency with various levitation techniques. Under a 1-G condition, the use of levitation forces to counteract gravity will cause the levitated sample's resonant frequency to differ from that under microgravity. A mathematical relationship to correct for this deviation is not available for a sample levitated with aerodynamic levitation (ADL), which raises issues on the validity of surface tension measurements done with ADL. In this study, we compared the surface tension of molten Al2O3 obtained using the front tracking (FT) simulation method, the drop-bounce method with ADL, and the oscillating drop method with ADL. The drop-bounce method simulates microgravity by allowing the sample to free-fall over a period of tens of milliseconds. Based on the results of this comparison, we determined that the surface tension of molten materials measured with ground-based ADL with the oscillating drop method, calculated using the resonant frequency of the l=2 m=0 mode, only shows a small deviation from that obtained under microgravity.

Multiple-gas cooling method for constant-pressure heat capacity measurement of liquid metals using aerodynamic levitator.

Until now, heat capacity measurements performed with levitation techniques have required accurate knowledge of the sample's emissivity beforehand. For a sample levitated using an aerodynamic levitator, it experiences both radiative and forced convective heat loss. The sample's emissivity only allows for the calculation of the radiative heat loss term, and a model has yet to be developed to accurately describe the total combined heat loss for aerodynamic levitation (ADL). In this study, we will introduce a novel multiple-gas cooling method for heat capacity measurement for ADL where two types of inert levitation gases (Ar and Kr) with different thermal conductivities were used to generate two cooling curves for the same sample. For samples being cooled at different cooling rates, the total heat loss is the same. The radiative heat loss was expressed using Stefan-Boltzmann's law, and the convective heat loss using Ranz-Marshall's equation. The two independent parameters (i.e., emissivity and heat capacity) of one given sample could then be solved using the two independent cooling curves. The heat capacities of gold, copper, nickel, iron, and palladium around the melting point were measured using this method. The multiple-gas cooling method for heat capacity measurement introduced in this study is the first heat capacity measurement method available for ADL and can be performed for materials with unknown emissivity. This newly developed method is important for the study of the thermophysical properties of high-temperature liquids, especially molten oxides with low electrical conductivity.

Biosynthesis of bismuth selenide nanoparticles using chalcogen-metabolizing bacteria.

Cost and energy reductions in the production process of bismuth chalcogenide (BC) semiconductor materials are essential to make thermoelectric generators comprised of BCs profitable and CO2 neutral over their life cycle. In this study, as an eco-friendly production method, bismuth selenide (Bi2Se3) nanoparticles were synthesized using the following five strains of chalcogen-metabolizing bacteria: Pseudomonas stutzeri NT-I, Pseudomonas sp. RB, Stenotrophomonas maltophilia TI-1, Ochrobactrum anthropi TI-2, and O. anthropi TI-3 under aerobic conditions. All strains actively volatilized selenium (Se) by reducing selenite, possibly to organoselenides. In the growth media containing bismuth (Bi) and Se, all strains removed Bi and Se concomitantly and synthesized nanoparticles containing Bi and Se as their main components. Particles synthesized by strain NT-I had a theoretical elemental composition of Bi2Se3, whereas those synthesized by other strains contained a small amount of sulfur in addition to Bi and Se, making strain NT-I the best Bi2Se3 synthesizer among the strains used in this study. The particle sizes were 50-100 nm in diameter, which is sufficiently small for nanostructured semiconductor materials that exhibit quantum size effect. Successful synthesis of Bi2Se3 nanoparticles could be attributed to the high Se-volatilizing activities of the bacterial strains. Selenol-containing compounds as intermediates of Se-volatilizing metabolic pathways, such as methane selenol and selenocysteine, may play an important role in biosynthesis of Bi2Se3.

Density and viscosity of liquid ZrO2 measured by aerodynamic levitation technique.

Liquid ZrO2 is one of the most important materials involved in severe accident analysis of a light-water reactor. Despite its importance, the physical properties of liquid ZrO2 are scarcely reported. In particular, there are no experimental reports on the viscosity of liquid ZrO2. This is mainly due to the technical difficulties involved in the measurement of thermo-physical properties of liquid ZrO2, which has an extremely high melting point. To address this problem, an aerodynamic levitation technique was used in this study. The density of liquid ZrO2 was calculated from its mass and volume, estimated based on the recorded image of the sample. The viscosity was measured by a droplet oscillation technique. The density and viscosity of liquid ZrO2 at temperatures ranging from 2753 K to 3273 K, and 3170 K-3471 K, respectively, were successfully evaluated. The density of liquid ZrO2 was found to be 4.7 g/cm 3 at its melting point of 2988 K and decreased linearly with increasing temperature, and the viscosity of liquid ZrO2 was 13 mPa at its melting point.

Chalcopyrite ZnSnSb2: A Promising Thermoelectric Material.

Ternary compounds with a tetragonal chalcopyrite structure, such as CuGaTe2, are promising thermoelectric (TE) materials. It has been demonstrated in various chalcopyrite systems, including compounds with quaternary chalcopyrite-like structures, that the lattice parameter ratio, c/ a, being exactly 2.00 to have a pseudo-cubic structure is key to increase the degeneracy at the valence band edge and ultimately achieve high TE performance. Considering the fact that ZnSnSb2 with a chalcopyrite structure is reported to have c/ a close to 2.00, it is expected to have multiple valence bands leading to a high p-type zT. However, there are no complete investigations on the high temperature TE properties of ZnSnSb2 mainly because of the difficulty of obtaining a single-phase ZnSnSb2. In the present study, pure ZnSnSb2 samples with no impurities are synthesized successfully using a Sn flux-based method and TE properties are characterized up to 585 K. Transport properties and thermal analysis indicate that the structure of ZnSnSb2 remains chalcopyrite with no order-disorder transition and clearly show that ZnSnSb2 can be made to exhibit a high zT in the low-to-mid temperature range through further optimization.

High wettability of liquid caesium iodine with solid uranium dioxide.

In March 2011, the Fukushima Daiichi Nuclear Power Plant accident caused nuclear fuel to melt and the release of high-volatility fission products into the environment. Caesium and iodine caused environmental contamination and public exposure. Certain fission-product behaviours remain unclear. We found experimentally that liquid CsI disperses extremely favourably toward solid UO2, exhibiting a contact angle approaching zero. We further observed the presence of CsI several tens of micrometres below the surface of the solid UO2 sample, which would be caused by the infiltration of pores network by liquid CsI. Thus, volatile fission products released from molten nuclear fuels with complex internal composition and external structure migrate or evaporate to varying extents, depending on the nature of the solid-liquid interface and the fuel material surface, which becomes the pathway for the released fission products. Introducing the concept of the wettability of liquid chemical species of fission products in contact with solid fuels enabled developing accurate behavioural assessments of volatile fission products released by nuclear fuel.

Enhancement of thermoelectric efficiency of CoSb3-based skutterudites by double filling with K and Tl.

The high-temperature thermoelectric properties of thallium (Tl) and potassium (K) double-filled cobalt antimonide (CoSb3)-based skutterudites with nominal compositions TlxK0.3Co4Sb12 (x = 0.1 - 0.3) were investigated. The filling fraction of Tl in CoSb3 was enhanced by co-filling with K, which resulted in all of the samples showing the filled-skutterudite single phase. Owing to the high filling ratio, the carrier concentration in the sample with x = 0.3 was as high as 4.3 × 10(20) cm(-3) at room temperature. Furthermore, quite low lattice thermal conductivity (as low as 0.9 Wm(-1)K(-1)) was obtained for the sample with x = 0.3, probably because of strong phonon scattering by the Tl and K co-rattling effect, which resulted in a maximum zT of around one at 773 K.

Bottom-up nanostructured bulk silicon: a practical high-efficiency thermoelectric material.

The effectiveness of thermoelectric (TE) materials is quantified by the dimensionless figure of merit (zT). An ideal way to enhance zT is by scattering phonons without scattering electrons. Here we show that, using a simple bottom-up method, we can prepare bulk nanostructured Si that exhibits an exceptionally high zT of 0.6 at 1050 K, at least three times higher than that of the optimized bulk Si. The nanoscale precipitates in this material connected coherently or semi-coherently with the Si matrix, effectively scattering heat-carrying phonons without significantly influencing the material's electron transport properties, leading to the high zT.

Chalcopyrite CuGaTe(2): a high-efficiency bulk thermoelectric material.

CuGaTe(2) with a chalcopyrite structure demonstrates promising thermoelectric properties. The maximum figure of merit ZT is 1.4 at 950 K. CuGaTe(2) and related chalcopyrites are a new class of high-efficiency bulk thermoelectric material for high-temperature applications.

Synthesis and formation mechanism of hydrogenated boron clusters B(12)H(n) with controlled hydrogen content.

We present the formation of hydrogen-content-controlled B(12)H(n) (+) clusters through the decomposition and ion-molecule reactions of the decaborane (B(10)H(14)) and diborane (B(2)H(6)) molecules in an external quadrupole static attraction ion trap. The hydrogen- and boron-contents of the B(10-y)H(x) (+) cluster are controlled by charge transfer from ambient gas ions. In the process of ionization, a certain number of hydrogen and boron atoms are detached from decaborane ions by the energy caused by charge transfer. The energy caused by the ion-molecule reactions also induces H atom detachment. Ambient gas of Ar leads to the selective generation of B(10)H(6) (+). The B(10)H(6) (+) clusters react with B(2)H(6) molecules, resulting in the selective formation of B(12)H(8) (+) clusters. Ambient gas of Ne (He) leads to the generation of B(10-y)H(x) (+) clusters with x=4-10 and y=0-1 (with x=2-10 and y=0-2), resulting in the formation of B(12)H(n) (+) clusters with n=4-8 (n=2,4-8). The introduction of ambient gas also increases the production of clusters. PBE0/6-311+G(d)//B3LYP/6-31G(d)-level density functional theory calculations are conducted to investigate the structure and the mechanism of formation of B(10-y)H(x) (+) and B(12)H(n) (+) clusters.

Formation of hydrogenated boron clusters in an external quadrupole static attraction ion trap.

We report the formation of icosahedral B(12)H(8) (+) through ion-molecule reactions of the decaborane ion [B(10)H(x)(+) (x=6-14)] with diborane (B(2)H(6)) molecules in an external quadrupole static attraction ion trap. The hydrogen content n of B(12)H(n)(+) is determined by the analysis of the mass spectrum. The result reveals that B(12)H(8)(+) is the main product. Ab initio calculations indicate that B(12)H(8)(+) preferentially forms an icosahedral structure rather than a quasiplanar structure. The energies of the formation reactions of B(12)H(14)(+) and B(12)H(12)(+) between B(10)H(x)(+) (x=6,8) ions, which are considered to be involved in the formation of B(12)H(n)(+), and a B(2)H(6) molecule are calculated. The calculations of the detachment pathway of H(2) molecules and H atoms from the product ions, B(12)H(14)(+) and B(12)H(12) (+), indicate that the intermediate state has a relatively low energy, enabling the detachment reaction to proceed owing to the sufficient reaction energy. This autodetachment of H(2) accounts for the experimental result that B(12)H(8)(+) is the most abundant product, even though it does not have the lowest energy among B(12)H(n)(+).