Zintl Chemistry for Designing High Efficiency Thermoelectric Materials

Zintl phases and related compounds are promising thermoelectric materials; for instance, high zT has been found in Yb_(14)MnSb_(11), clathrates, and the filled skutterudites. The rich solid-state chemistry of Zintl phases enables numerous possibilities for chemical substitutions and structural modifications that allow the fundamental transport parameters (carrier concentration, mobility, effective mass, and lattice thermal conductivity) to be modified for improved thermoelectric performance. For example, free carrier concentration is determined by the valence imbalance using Zintl chemistry, thereby enabling the rational optimization of zT. The low thermal conductivity values obtained in Zintl thermoelectrics arise from a diverse range of sources, including point defect scattering and the low velocity of optical phonon modes. Despite their complex structures and chemistry, the transport properties of many modern thermoelectrics can be understood using traditional models for heavily doped semiconductors

Transport properties of the layered Zintl compound SrZnSb_2

Transport properties of the layered Zintl compound SrZnSb_2 have been characterized from room temperature to 725 K on polycrystalline samples. SrZnSb_2 samples were found to be p-type with a Hall carrier concentration of 5×10^(20) cm^(−3) at room temperature, and a small Seebeck coefficient and electrical resistivity are observed. A single band model predicts that, even with optimal doping, significant thermoelectric performance will not be achieved in SrZnSb_2. A relatively low lattice thermal conductivity is observed, κ_L~1.2 W m^(−1) K^(−1), at room temperature. The thermal transport of SrZnSb_2 is compared to that of the layered Zintl compounds AZn2Sb_2 (A=Ca,Yb,Sr,Eu), which have smaller unit cells and larger lattice thermal conductivity, κ_L~2 W m^(−1) K^(−1), at 300K. Ultrasonic measurements, in combination with kinetic theory and the estimated κ_L values, suggest that the lower κ_L of SrZnSb_2 is primarily the result of a reduction in the volumetric specific heat of the acoustic phonons due to the increased number of atoms per unit cell. Therefore, this work recommends that unit cell size should be considered when selecting Zintl compounds for potential thermoelectric application

Thermoelectric properties of p-type LiZnSb: Assessment of ab initio calculations

In response to theoretical calculations on the thermoelectric performance of LiZnSb, we report the pertinent transport properties between room temperature and 523 K. Nominal LiZnSb samples are found to be p-type, with a carrier concentration in the range (4–7)×10^(20) cm^(−3). The thermoelectric figure of merit (zT) is found to be 0.02–0.08 at 523 K. Analysis of material transport parameters and previously reported ab initio calculations demonstrates that even with optimal doping, p-type LiZnSb is unlikely to achieve zT>0.2 at 523 K. The accuracy of the high zT estimate (zT>2) for n-type compositions from ab initio calculations is discussed within the current synthetic limits

Valence band study of thermoelectric Zintl-phase SrZn_2Sb_2 and YbZn_2Sb_2: X-ray photoelectron spectroscopy and density functional theory

The electronic structure of SrZn_2Sb_2 and YbZn_2Sb_2 is investigated using density functional theory and high-resolution x-ray photoemission spectroscopy. Both traditional Perdew-Burke-Ernzerhof and state-of-the-art hybrid Heyd-Scuseria-Ernzerhof functionals have been employed to highlight the importance of proper treatment of exchange-dependent Zn  3d states, Yb 4f states, and band gaps. The role of spin-orbit corrections in light of first-principles transport calculations are discussed and previous claims of Yb^(3+) valence are investigated with the assistance of photoelectron as well as scanning and transmission electron microscopy

Power Dependent Lineshape Corrections for Quantitative Spectroscopy

The Voigt profile - a convolution of a Gaussian and a Lorentzian - accurately describes the absorption lines of atomic and molecular gases at low probe powers. Fitting such to experimental spectra yields both the Lorentzian natural linewidth and the Gaussian Doppler broadening. However, as the probe power increases saturation effects introduce spurious power dependence into the fitted Doppler width. Using a simple atomic model, we calculate power-dependent corrections to the Voigt profile, which are parametrized by the Gaussian Doppler width, the Lorentzian natural linewidth, and the optical depth. We show numerically and experimentally that including the correction term substantially reduces the spurious power dependence in the fitted Gaussian width.Comment: 4 pages, 3 figure

Quantitative atomic spectroscopy for primary thermometry

Quantitative spectroscopy has been used to measure accurately the Doppler-broadening of atomic transitions in $^{85}$Rb vapor. By using a conventional platinum resistance thermometer and the Doppler thermometry technique, we were able to determine $k_B$ with a relative uncertainty of $4.1\times 10^{-4}$, and with a deviation of $2.7\times 10^{-4}$ from the expected value. Our experiment, using an effusive vapour, departs significantly from other Doppler-broadened thermometry (DBT) techniques, which rely on weakly absorbing molecules in a diffusive regime. In these circumstances, very different systematic effects such as magnetic sensitivity and optical pumping are dominant. Using the model developed recently by Stace and Luiten, we estimate the perturbation due to optical pumping of the measured $k_B$ value was less than $4\times 10^{-6}$. The effects of optical pumping on atomic and molecular DBT experiments is mapped over a wide range of beam size and saturation intensity, indicating possible avenues for improvement. We also compare the line-broadening mechanisms, windows of operation and detection limits of some recent DBT experiments

A review of conventional and emerging process technologies for the recovery of helium from natural gas

Helium is a unique gas with a wide range of important medical, scientific and industrial applications based on helium's extremely low boiling temperature, inert and non-flammable nature and small molecular size. The only practical sources of helium are from certain natural gas (NG) fields. As world demand for helium rapidly increases, the value of NG fields that contain it even in very small amounts is likely to rise significantly if the helium can be recovered efficiently. However, recovering the helium from the NG using conventional cryogenic distillation processes is expensive and energy intensive. We review the scope for improving the efficiency of the conventional helium recovery and upgrade processes, and evaluate the potential of emerging technologies based on adsorption or membrane separations for helium upgrade and purification. Helium recovery and purification processes are comparable in many ways with systems designed for hydrogen purification and thus, many of recent technological advances for H-2 separation from CH4, N-2 and CO2 may be applicable to a helium recovery process. Furthermore, some recent patents and pilot plant studies indicate there exist several opportunities for the development of advanced materials, such as helium-selective adsorbents, and optimized process operations for the recovery of helium from NG

Saturated phase densities of (CO2 + H2O) at temperatures from (293 to 450) K and pressures up to 64 MPa

An apparatus consisting of an equilibrium cell connected to two vibrating tube densimeters and two syringe pumps was used to measure the saturated phase densities of (CO2 + H2O) at temperatures from (293 to 450) K and pressures up to 64 MPa, with estimated average standard uncertainties of 1.5 kg · m−3 for the CO2-rich phase and 1.0 kg · m−3 for the aqueous phase. The densimeters were housed in the same thermostat as the equilibrium cell and were calibrated in situ using pure water, CO2 and helium. Following mixing, samples of each saturated phase were displaced sequentially at constant pressure from the equilibrium cell into the vibrating tube densimeters connected to the top (CO2-rich phase) and bottom (aqueous phase) of the cell. The aqueous phase densities are predicted to within 3 kg · m−3 using empirical models for the phase compositions and partial molar volumes of each component. However, a recently developed multi-parameter equation of state (EOS) for this binary mixture, Gernert and Span [32], was found to under predict the measured aqueous phase density by up to 13 kg · m−3. The density of the CO2-rich phase was always within about 8 kg · m−3 of the density for pure CO2 at the same pressure and temperature; the differences were most positive near the critical density, and became negative at temperatures above about 373 K and pressures below about 10 MPa. For this phase, the multi-parameter EOS of Gernert and Span describes the measured densities to within 5 kg · m−3, whereas the computationally-efficient cubic EOS model of Spycher and Pruess (2010), commonly used in simulations of subsurface CO2 sequestration, deviates from the experimental data by a maximum of about 8 kg · m−3

Effectively Mapping Linguistic Abstractions for Message-passing Concurrency to Threads on the Java Virtual Machine

Efficient mapping of message passing concurrency (MPC) abstractions to Java Virtual Machine (JVM) threads is critical for performance, scalability, and CPU utilization; but tedious and time consuming to perform manually. In general, this mapping cannot be found in polynomial time, but we show that by exploiting the local characteristics of MPC abstractions and their communication patterns this mapping can be determined effectively. We describe our MPC abstraction to thread mapping technique, its realization in two frameworks (Panini and Akka), and its rigorous evaluation using several benchmarks from representative MPC frameworks. We also compare our technique against four default mapping techniques: thread-all, round-robin-task-all, random-task-all and work-stealing. Our evaluation shows that our mapping technique can improve the performance by 30%-60% over default mapping techniques. These improvements are due to a number of challenges addressed by our technique namely: i) balancing the computations across JVM threads, ii) reducing the communication overheads, iii) utilizing information about cache locality, and iv) mapping MPC abstractions to threads in a way that reduces the contention between JVM threads