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

Enhanced thermoelectric properties of the Zintl phase BaGa_2Sb_2 via doping with Na or K

Na- or K-doped samples of Ba_(1−x)(Na, K)xGa_2Sb_2 were prepared by ball-milling followed by hot-pressing. The topological analysis of the electron density of BaGa_2Sb_2 implies a polar covalent nature of the Sb–Ga bonds in which the Sb atoms receive the electrons transferred from Ba rather than the Ga atoms. Successful doping of BaGa_2Sb_2 with Na or K was confirmed with combined microprobe and X-ray diffraction analysis. Alkali metal doping of BaGa_2Sb_2 increased the p-type charge carrier concentration to almost the predicted optimum values (∼10^(20) h^+ cm^(−3)) needed to achieve high thermoelectric performance. With increasing alkali metal concentration, electronic transport was shifted from non-degenerate semiconducting behaviour observed for BaGa_2Sb_2 to degenerate one for Na- or K-doped compounds. Overall, the thermoelectric figure of merit, zT, values reached up to ∼0.65 at 750 K, considerably higher than the undoped sample (zT ∼ 0.1 at 600 K), and a slight improvement relative to previously reported Zn-doped samples (∼0.6 at 800 K)

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

Thermoelectric Enhancement in BaGa_2Sb_2 by Zn Doping

The Zintl phase BaGa_2Sb_2 has a unique crystal structure in which large tunnels formed by ethane-like dimeric [Sb_3Ga−GaSb_3] units are filled with Ba atoms. BaGa_2Sb_2 was obtained in high purity from ball-milling followed by hot pressing. It shows semiconducting behavior, in agreement with the valence precise Zintl counting and band structure calculations, with a band gap ∼0.4 eV. The thermal conductivity of BaGa_2Sb_2 is found to be relatively low (0.95 W/K m at 550 K), which is an inherent property of compounds with complex crystal structures. As BaGa_2Sb_2 has a low carrier concentration (∼2 × 10^18 h^+/cm^3) at room temperature, the charge carrier tuning was performed by substituting trivalent Ga with divalent Zn. Zn-doped samples display heavily doped p-type semiconducting behavior with carrier concentrations in the range (5−8) × 10^19 h^+/cm^3. Correspondingly, the zT values were increased by a factor of 6 by doping compared to the undoped sample, reaching a value of ∼0.6 at 800 K. Zn-doped BaGa_2Sb_2 can thus be considered as a promising new thermoelectric material for intermediate-temperature applications

Impact of Neutron Irradiation on the Thermoelectric Properties of Rare Earth‐Based Thermoelectric Materials

The impact of neutron irradiation on the thermoelectric (TE) properties of n‐type La 3‐x Te 4 , p‐type Yb 14 MnSb 11 , and n‐ and p‐type filled skutterudites is reported and discussed. During operation in Radioisotope Thermoelectric Generators (RTGs), these TE materials are expected to experience a certain degree of radiation over time, specifically, fission neutrons. This could affect their TE properties and thus the performance of the generators over time. In this study three samples of each of the above materials were exposed to 18 years worth of neutron radiation near room temperature at the Ohio State University Research Reactor (OSURR). Their electrical resistivity, carrier mobility, carrier concentration, thermal conductivity, Hall coefficient, and Seebeck coefficient were measured before and after radiation exposure at room temperature. Post‐irradiation the properties are measured twice. The first measurements were conducted on the samples as received after irradiation. The samples were then polished to remove any surface discoloration or oxidation films. The above properties were tested again to determine if the initial surface characteristics played an influence on the TE properties. The room temperature TE properties indicate that the neutron exposure had limited impact on the Seebeck and resistivity (less than 10% deviation). Results agree with previous investigations that established the minimal impact of neutron exposure on other similar TE materials. High‐temperature TE property measurements, including thermal conductivity, will also be performed on the samples to confirm the initial room temperature results

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