Mechanochemical Synthesis and Thermoelectric Properties of Magnesium Silicide and Related Alloys

The present invention provides a method of making a substantially phase pure compound including a cation and an anion. The compound is made by mixing in a ball-milling device a first amount of the anion with a first amount of the cation that is less than the stoichiometric amount of the cation, so that substantially all of the first amount of the cation is consumed. The compound is further made by mixing in a ball-milling device a second amount of the cation that is less than the stoichiometric amount of the cation with the mixture remaining in the device. The mixing is continued until substantially all of the second amount of the cation and any unreacted portion of anion X are consumed to afford the substantially phase pure compound

Thermoelectric properties of the Yb_9Mn_(4.2-x)Zn_xSb_9 solid solutions

Yb_9Mn_(4.2)Sb_9 has been shown to have extremely low thermal conductivity and a high thermoelectric figure of merit attributed to its complex crystal structure and disordered interstitial sites. Motivated by previous work which shows that isoelectronic substitution of Mn by Zn leads to higher mobility by reducing spin disorder scattering, this study investigates the thermoelectric properties of the solid solution, Yb_9Mn_(4.2−x)Zn_xSb_9 (x = 0, 1, 2, 3 and 4.2). Measurements of the Hall mobility at high temperatures (up to 1000 K) show that the mobility can be increased by more than a factor of 3 by substituting Zn into Mn sites. This increase is explained by the reduction of the valence band effective mass with increasing Zn, leading to a slightly improved thermoelectric quality factor relative to Yb_9Mn_(4.2)Sb_9. However, increasing the Zn-content also increases the p-type carrier concentration, leading to metallic behavior with low Seebeck coefficients and high electrical conductivity. Varying the filling of the interstitial site in Yb_9Zn_(4+y)Sb_9 (y = 0.2, 0.3, 0.4 and 0.5) was attempted, but the carrier concentration (~10^(21) cm^(−3) at 300 K) and Seebeck coefficients remained constant, suggesting that the phase width of Yb_9Zn_(4+y)Sb_9 is quite narrow

Rapid Solid-State Metathesis Routes to Nanostructured Silicon-Germainum

Methods for producing nanostructured silicon and silicon-germanium via solid state metathesis (SSM). The method of forming nanostructured silicon comprises the steps of combining a stoichiometric mixture of silicon tetraiodide (SiI4) and an alkaline earth metal silicide into a homogeneous powder, and initating the reaction between the silicon tetraiodide (SiI4) with the alkaline earth metal silicide. The method of forming nanostructured silicon-germanium comprises the steps of combining a stoichiometric mixture of silicon tetraiodide (SiI4) and a germanium based precursor into a homogeneous powder, and initiating the reaction between the silicon tetraiodide (SiI4) with the germanium based precursors

Ultra-Light Ultra-Strong Proppants

The present invention provides a method of preparing a proppant material by heating a reaction mixture comprising a plurality of oxides in a reactive atmosphere to a temperature above the melting point of the reaction mixture to form a melt, and then allowing the melt to solidify in a mold in the form of spherical particles. The present invention also provides a method of preparing a proppant material by heating a reaction mixture comprising a plurality of oxides and one or more additives in a reactive atmosphere to a temperature below the melting point of the reaction mixture to form a powder including one or more reaction products, and then processing the powder to form spherical particles. The present invention also provides a proppant material including spherical particles characterized by a specific gravity of about 1.0 to 3.0 and a crush strength of at least about 10,000 psi

High temperature thermoelectric properties of Zn-doped Eu_5In_2Sb_6

The complex bonding environment of many ternary Zintl phases, which often results in low thermal conductivity, makes them strong contenders as thermoelectric materials. Here, we extend the investigation of A_5In_2Sb_6 Zintl compounds with the Ca_5Ga_2As_6 crystal structure to the only known rare-earth analogue: Eu_5In_2Sb_6. Zn-doped samples with compositions of Eu_5In_(2−x)ZnxSb_6 (x = 0, 0.025, 0.05, 0.1, 0.2) were synthesized via ball milling followed by hot pressing. Eu_5In_2Sb_6 showed significant improvements in air stability relative to its alkaline earth metal analogues. Eu5In2Sb6 exhibits semiconducting behavior with possible two band behavior suggested by increasing band mass as a function of Zn content, and two distinct transitions observed in optical absorption measurements (at 0.15 and 0.27 eV). The p-type Hall mobility of Eu_5In_2Sb_6 was found to be much larger than that of the alkaline earth containing A_5In_2Sb_6 phases (A = Sr, Ca) consistent with the reduced hole effective mass (1.1 me). Zn doping was successful in optimizing the carrier concentration, leading to a zT of up to 0.4 at ∼660 K, which is comparable to that of Zn-doped Sr_5In_2Sb_6

Mechanochemical synthesis and high temperature thermoelectric properties of calcium-doped lanthanum telluride La_(3−x)Ca_xTe_4

The thermoelectric properties from 300–1275 K of calcium-doped La_(3−x)Te_4 are reported. La_(3−x)Te_4 is a high temperature n-type thermoelectric material with a previously reported zT_(max) 1.1 at 1273 K and x = 0.23. Computational modeling suggests the La atoms define the density of states of the conduction band for La_(3−x)Te_4. Doping with Ca^(2+) on the La^(3+) site is explored as a means of modifying the density of states to improve the power factor and to achieve a finer control over the carrier concentration. High purity, oxide-free samples are produced by ball milling of the elements and consolidation by spark plasma sintering. Calcium substitution upon the lanthanum site was confirmed by a combination of Rietveld refinements of powder X-ray diffraction data and wave dispersive spectroscopy. A zT_(max) 1.2 is reached at 1273 K for the composition La_(2.2)Ca_(0.78)Te_4 and the relative increase compared to La_(3−x)Te_4 is attributed to the finer carrier concentration

Achieving zT > 1 in Inexpensive Zintl Phase Ca_9Zn_(4+x)Sb_9 by Phase Boundary Mapping

Complex multinary compounds (ternary, quaternary, and higher) offer countless opportunities for discovering new semiconductors for applications such as photovoltaics and thermoelectrics. However, controlling doping has been a major challenge in complex semiconductors as there are many possibilities for charged intrinsic defects (e.g., vacancies, interstitials, antisite defects) whose energy depends on competing impurity phases. Even in compounds with no apparent deviation from a stoichiometric nominal composition, such defects commonly lead to free carrier concentrations in excess of 10^(20) cm^(−3). Nevertheless, by slightly altering the nominal composition, these defect concentrations can be tuned with small variation of the chemical potentials (composition) of each element. While the variation of chemical composition is undetectable, it is shown that the changes can be inferred by mapping (in nominal composition space) the boundaries where different competing impurity phases form. In the inexpensive Zintl compound Ca_9Zn_(4+x)Sb_9, the carrier concentrations can be finely tuned within three different three-phase regions by altering the nominal composition (x = 0.2–0.8), enabling the doubling of thermoelectric performance (zT). Because of the low thermal conductivity, the zT can reach as high as 1.1 at 875 K, which is one of the highest among the earth abundant p-type thermoelectrics with no ion conducting

Synthesis and Characterization of Vacancy-Doped Neodymium Telluride for Thermoelectric Applications

Thermoelectric materials exhibit a voltage under an applied thermal gradient and are the heart of radioisotope thermoelectric generators (RTGs), which are the main power system for space missions such as Voyager I, Voyager II, and the Mars Curiosity rover. However, materials currently in use enable only modest thermal-to-electrical conversion efficiencies near 6.5% at the system level, warranting the development of material systems with improved thermoelectric performance. Previous work has demonstrated large thermoelectric figures of merit for lanthanum telluride (La_(3–x)Te_4), a high-temperature n-type material, achieving a peak zT value of 1.1 at 1275 K at an optimum cation vacancy concentration. Here, we present an investigation of the thermoelectric properties of neodymium telluride (Nd_(3–x)Te_4), another rare-earth telluride with a structure similar to La_(3–x)Te_4. Density functional theory (DFT) calculations predicted a significant increase in the Seebeck coefficient over La_(3–x)Te_4 at equivalent vacancy concentrations because of an increased density of states (DOS) near the Fermi level from the 4f electrons of Nd. The high-temperature electrical resistivity, Seebeck coefficient, and thermal conductivity were measured for Nd_(3–x)Te_4 at various carrier concentrations. These measurements were compared to La_(3–x)Te_4 in order to elucidate the impact of the four 4f electrons of Nd on the transport properties of Nd_(3–x)Te_4. A zT of 1.2 was achieved at 1273 K for Nd_(2.78)Te_4, which is a 10% improvement over that of La_(2.74)Te_4

Nanostructured Bulk Silicon As An Effective Thermoelectric Material

Thermoelectric power sources have consistently demonstrated their extraordinary reliability and longevity for deep space missions and small unattended terrestrial systems. However, more efficient bulk materials and practical devices are required to improve existing technology and expand into large-scale waste heat recovery applications. Research has long focused on complex compounds that best combine the electrical properties of degenerate semiconductors with the low thermal conductivity of glassy materials. Recently it has been found that nanostructuring is an effective method to decouple electrical and thermal transport parameters. Dramatic reductions in the lattice thermal conductivity are achieved by nanostructuring bulk silicon with limited degradation in its electron mobility, leading to an unprecedented increase by a factor of 3.5 in its performance over that of the parent single-crystal material. This makes nanostructured bulk (nano-bulk) Si an effective high temperature thermoelectric material that performs at about 70% the level of state-of-the-art Si0.8Ge0.2 but without the need for expensive and rare Ge. © 2009 WILEY-VCH Verlag GmbH & Co. KGaA