Elastic constants of biogenic calcium carbonate.

Living organisms form complex mineralized composite architectures that perform a variety of essential functions. These materials are commonly utilized for load-bearing purposes such as structural stability and mechanical strength in combination with high toughness and deformability, which are well demonstrated in various highly mineralized molluscan shell ultrastructures. Here, the mineral components provide the general stiffness to the composites, and the organic interfaces play a key role in providing these biogenic architectures with mechanical superiority. Although numerous studies employed state-of-the-art methods to measure and/or model and/or simulate the mechanical behavior of molluscan shells, our understanding of their performance is limited. This is partially due to the lack of the most fundamental knowledge of their mechanical characteristics, particularly, the anisotropic elastic properties of the mineral components and of the tissues they form. In fact, elastic constants of biogenic calcium carbonate, one of the most common biominerals in nature, is unknown for any organism. In this work, we employ the ultrasonic pulse-echo method to report the elasticity tensor of two common ultrastructural motifs in molluscan shells: the prismatic and the nacreous architectures made of biogenic calcite and aragonite, respectively. The outcome of this research not only provides information necessary for fundamental understanding of biological materials formation and performance, but also yields textbook knowledge on biogenic calcium carbonate required for future structural/crystallographic, theoretical and computational studies.

Amorphous-Like Ultralow Thermal Transport in Crystalline Argyrodite Cu7PS6.

Due to their amorphous-like ultralow lattice thermal conductivity both below and above the superionic phase transition, crystalline Cu- and Ag-based superionic argyrodites have garnered widespread attention as promising thermoelectric materials. However, despite their intriguing properties, quantifying their lattice thermal conductivities and a comprehensive understanding of the microscopic dynamics that drive these extraordinary properties are still lacking. Here, an integrated experimental and theoretical approach is adopted to reveal the presence of Cu-dominated low-energy optical phonons in the Cu-based argyrodite Cu7PS6. These phonons yield strong acoustic-optical phonon scattering through avoided crossing, enabling ultralow lattice thermal conductivity. The Unified Theory of thermal transport is employed to analyze heat conduction and successfully reproduce the experimental amorphous-like ultralow lattice thermal conductivities, ranging from 0.43 to 0.58 W m-1 K-1, in the temperature range of 100-400 K. The study reveals that the amorphous-like ultralow thermal conductivity of Cu7PS6 stems from a significantly dominant wave-like conduction mechanism. Moreover, the simulations elucidate the wave-like thermal transport mainly results from the contribution of Cu-associated low-energy overlapping optical phonons. This study highlights the crucial role of low-energy and overlapping optical modes in facilitating amorphous-like ultralow thermal transport, providing a thorough understanding of the underlying complex dynamics of argyrodites.

Vacancy-mediated anomalous phononic and electronic transport in defective half-Heusler ZrNiBi.

Studies of vacancy-mediated anomalous transport properties have flourished in diverse fields since these properties endow solid materials with fascinating photoelectric, ferroelectric, and spin-electric behaviors. Although phononic and electronic transport underpin the physical origin of thermoelectrics, vacancy has only played a stereotyped role as a scattering center. Here we reveal the multifunctionality of vacancy in tailoring the transport properties of an emerging thermoelectric material, defective n-type ZrNiBi. The phonon kinetic process is mediated in both propagating velocity and relaxation time: vacancy-induced local soft bonds lower the phonon velocity while acoustic-optical phonon coupling, anisotropic vibrations, and point-defect scattering induced by vacancy shorten the relaxation time. Consequently, defective ZrNiBi exhibits the lowest lattice thermal conductivity among the half-Heusler family. In addition, a vacancy-induced flat band features prominently in its electronic band structure, which is not only desirable for electron-sufficient thermoelectric materials but also interesting for driving other novel physical phenomena. Finally, better thermoelectric performance is established in a ZrNiBi-based compound. Our findings not only demonstrate a promising thermoelectric material but also promote the fascinating vacancy-mediated anomalous transport properties for multidisciplinary explorations.

Macroscopic Disk Rotation by Means of Surface Acoustic Waves.

It is shown experimentally that a flat piezoelectric disk poled perpendicular to its surface and suspended on a thin thread can be rotated about 50° by two surface acoustic waves (SAWs) intentionally excited with different amplitudes and propagating in the opposite directions. The excitation of such counter-propagating SAWs with different amplitudes is based on the nonsymmetrical interdigital transducer with different angular width electrodes located along the disk radius. The angular width of each of the two electrodes per angular period is not change along the disk radius. Such a ring unidirectional transducer realized on one of the disk surfaces is used for the excitation of SAWs. Hereby, the flat surface of the disk allows one to create any transducer pattern using conventional technology. The other disk surface can be free or covered by the silver layer.

Microwave Acoustic Attenuation in CTGS Single Crystals.

This article presents a study of special material properties of the single crystalline material Ca3TaGa3Si2O14 (CTGS = Catangasite). The comparatively highly ordered crystal structure and acceptable piezoelectric strength make it a candidate for microacoustic applications under extreme conditions. Obviously, low-loss dynamic behavior is typical for this crystal which consequently enables high-temperature use. As a particular challenge, the behavior at gigahertz frequencies is investigated here. For that, High overtone Bulk Acoustic wave Resonator (HBAR) type measurements in the range of 1-6 GHz are performed. The selection of five distinctive propagation directions for exclusively pure or quasi-longitudinal modes enables to derive the dynamic viscosities from the quality factors of HBAR results. The observed frequency dependences exhibit Akhiezer behavior as the predominant loss mechanism in the cases examined.

Discovery of TaFeSb-based half-Heuslers with high thermoelectric performance.

Discovery of thermoelectric materials has long been realized by the Edisonian trial and error approach. However, recent progress in theoretical calculations, including the ability to predict structures of unknown phases along with their thermodynamic stability and functional properties, has enabled the so-called inverse design approach. Compared to the traditional materials discovery, the inverse design approach has the potential to substantially reduce the experimental efforts needed to identify promising compounds with target functionalities. By adopting this approach, here we have discovered several unreported half-Heusler compounds. Among them, the p-type TaFeSb-based half-Heusler demonstrates a record high ZT of ~1.52 at 973 K. Additionally, an ultrahigh average ZT of ~0.93 between 300 and 973 K is achieved. Such an extraordinary thermoelectric performance is further verified by the heat-to-electricity conversion efficiency measurement and a high efficiency of ~11.4% is obtained. Our work demonstrates that the TaFeSb-based half-Heuslers are highly promising for thermoelectric power generation.

Transport and Electromechanical Properties of Ca3TaGa3Si2O14 Piezoelectric Crystals at Extreme Temperatures.

Transport mechanisms in structurally ordered piezoelectric Ca3TaGa3Si2O14 (CTGS) single crystals are studied in the temperature range of 1000-1300 °C by application of the isotope 18O as a tracer and subsequent analysis of diffusion profiles of this isotope using secondary ion mass spectrometry (SIMS). Determined oxygen self-diffusion coefficients enable calculation of oxygen ion contribution to the total conductivity, which is shown to be small. Since very low contributions of the cations have to be expected, the total conductivity must be dominated by electron transport. Ion and electron conductivities are governed by different mechanisms with activation energies (1.9±0.1) eV and (1.2±0.07) eV, respectively. Further, the electromechanical losses are studied as a function of temperature by means of impedance spectroscopy on samples with electrodes and a contactless tone-burst excitation technique. At temperatures above 650 °C the conductivity-related losses are dominant. Finally, the operation of CTGS resonators is demonstrated at cryogenic temperatures and materials piezoelectric strain constants are determined from 4.2 K to room temperature.

Discovery of ZrCoBi based half Heuslers with high thermoelectric conversion efficiency.

Thermoelectric materials are capable of converting waste heat into electricity. The dimensionless figure-of-merit (ZT), as the critical measure for the material's thermoelectric performance, plays a decisive role in the energy conversion efficiency. Half-Heusler materials, as one of the most promising candidates for thermoelectric power generation, have relatively low ZTs compared to other material systems. Here we report the discovery of p-type ZrCoBi-based half-Heuslers with a record-high ZT of ∼1.42 at 973 K and a high thermoelectric conversion efficiency of ∼9% at the temperature difference of ∼500 K. Such an outstanding thermoelectric performance originates from its unique band structure offering a high band degeneracy (Nv) of 10 in conjunction with a low thermal conductivity benefiting from the low mean sound velocity (vm ∼2800 m s-1). Our work demonstrates that ZrCoBi-based half-Heuslers are promising candidates for high-temperature thermoelectric power generation.