skip to main content


Title: The Transport Properties of Quasi–One-Dimensional Ba3Co2O6(CO3)0.7
We have performed combined elastic neutron diffuse, electrical transport, specific heat, and thermal conductivity measurements on the quasi–one-dimensional Ba 3 Co 2 O 6 (CO 3 ) 0.7 single crystal to characterize its transport properties. A modulated superstructure of polyatomic CO 3 2− is formed, which not only interferes the electronic properties of this compound, but also reduces the thermal conductivity along the c-axis. Furthermore, a large magnetic entropy is observed to be contributed to the heat conduction. Our investigations reveal the influence of both structural and magnetic effects on its transport properties and suggest a theoretical improvement on the thermoelectric materials by building up superlattice with conducting ionic group.  more » « less
Award ID(s):
2003117
NSF-PAR ID:
10322740
Author(s) / Creator(s):
; ; ; ; ; ; ; ; ; ; ; ; ;
Date Published:
Journal Name:
Frontiers in Physics
Volume:
9
ISSN:
2296-424X
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Purpose AlSi10Mg alloy is commonly used in laser powder bed fusion due to its printability, relatively high thermal conductivity, low density and good mechanical properties. However, the thermal conductivity of as-built materials as a function of processing (energy density, laser power, laser scanning speed, support structure) and build orientation, are not well explored in the literature. This study aims to elucidate the relationship between processing, microstructure, and thermal conductivity. Design/methodology/approach The thermal conductivity of laser powder bed fusion (L-PBF) AlSi10Mg samples are investigated by the flash diffusivity and frequency domain thermoreflectance (FDTR) techniques. Thermal conductivities are linked to the microstructure of L-PBF AlSi10Mg, which changes with processing conditions. The through-plane exceeded the in-plane thermal conductivity for all energy densities. A co-located thermal conductivity map by frequency domain thermoreflectance (FDTR) and crystallographic grain orientation map by electron backscattered diffraction (EBSD) was used to investigate the effect of microstructure on thermal conductivity. Findings The highest through-plane thermal conductivity (136 ± 2 W/m-K) was achieved at 59 J/mm 3 and exceeded the values reported previously. The in-plane thermal conductivity peaked at 117 ± 2 W/m-K at 50 J/mm 3 . The trend of thermal conductivity reducing with energy density at similar porosity was primarily due to the reduced grain size producing more Al-Si interfaces that pose thermal resistance. At these interfaces, thermal energy must convert from electrons in the aluminum to phonons in the silicon. The co-located thermal conductivity and crystallographic grain orientation maps confirmed that larger colonies of columnar grains have higher thermal conductivity compared to smaller columnar grains. Practical implications The thermal properties of AlSi10Mg are crucial to heat transfer applications including additively manufactured heatsinks, cold plates, vapor chambers, heat pipes, enclosures and heat exchangers. Additionally, thermal-based nondestructive testing methods require these properties for applications such as defect detection and simulation of L-PBF processes. Industrial standards for L-PBF processes and components can use the data for thermal applications. Originality/value To the best of the authors’ knowledge, this paper is the first to make coupled thermal conductivity maps that were matched to microstructure for L-PBF AlSi10Mg aluminum alloy. This was achieved by a unique in-house thermal conductivity mapping setup and relating the data to local SEM EBSD maps. This provides the first conclusive proof that larger grain sizes can achieve higher thermal conductivity for this processing method and material system. This study also shows that control of the solidification can result in higher thermal conductivity. It was also the first to find that the build substrate (with or without support) has a large effect on thermal conductivity. 
    more » « less
  2. ZrSe3 with a quasi-one-dimensional (quasi-1D) crystal structure belongs to the transition metal trichalcogenides (TMTCs) family. Owing to its unique optical, electrical, and optoelectrical properties, ZrSe3 is promising for applications in field effect transistors, photodetectors, and thermoelectrics. Compared with extensive studies of the above-mentioned physical properties, the thermal properties of ZrSe3 have not been experimentally investigated. Here, we report the crystal growth and thermal and optical properties of ZrSe3. Millimeter-sized single crystalline ZrSe3 flakes were prepared using a chemical vapor transport method. These flakes could be exfoliated into microribbons by liquid-phase exfoliation. The transmission electron microscope studies suggested that the obtained microribbons were single crystals along the chain axis. ZrSe3 exhibited a specific heat of 0.311 J g−1 K−1 at 300 K, close to the calculated value of the Dulong–Petit limit. The fitting of low-temperature specific heat led to a Debye temperature of 110 K and an average sound velocity of 2122 m s−1. The thermal conductivity of a polycrystalline ZrSe3 sample exhibited a maximum value of 10.4 ± 1.9 W m−1 K−1 at 40 K. The thermal conductivity decreased above 40 K and reached a room-temperature value of 5.4 ± 1.3 W m−1 K−1. The Debye model fitting of the solid thermal conductivity agreed well with the experimental data below 200 K but showed a deviation at high temperatures, indicating that optical phonons could substantially contribute to thermal transport at high temperatures. The calculated phonon mean free path decreased with temperatures between 2 and 21 K. The mean free path at 2 K approached 3 μm, which was similar to the grain size of the polycrystalline sample. This work provides useful insights into the preparation and thermal properties of quasi-1D ZrSe3. 
    more » « less
  3. Diamine-appended variants of the metal–organic framework M2(dobpdc) (M = Mg, Mn, Fe, Co, Zn; dobpdc4– = 4,4′-dioxidobiphenyl-3,3′-dicarboxylate) exhibit exceptional CO2 capture properties owing to a unique cooperative adsorption mechanism, and thus hold promise for use in the development of energy- and cost-efficient CO2 separations. Understanding the nature of thermal transport in these materials is essential for such practical applications, however, as temperature rises resulting from exothermic CO2 uptake could potentially offset the energy savings offered by such cooperative adsorbents. Here, molecular dynamics (MD) simulations are employed in investigating thermal transport in bare and e-2-appended Zn2(dobpdc) (e-2 = N-ethylethylenediamine), both with and without CO2 as a guest. In the absence of CO2, the appended diamines function to enhance thermal conductivity in the ab-plane of e-2–Zn2(dobpdc) relative to the bare framework, as a result of noncovalent interactions between adjacent diamines that provide additional heat transfer pathways across the pore channel. Upon introduction of CO2, the thermal conductivity along the pore channel (the c-axis) increases due to the cooperative formation of metal-bound ammonium carbamates, which serve to create additional heat transfer pathways. In contrast, the thermal conductivity of the bare framework remains unchanged in the presence of zinc-bound CO2 but decreases in the presence of additional adsorbed CO2. 
    more » « less
  4. Kagome compounds have garnered attention in the past few years for their intriguing magnetic properties arising from spin frustration dictated by the geometry of the Kagome sublattice. In this paper, we highlight the success of the unconventional hydride route for the fast and easy synthesis of the Kagome compound KV6Sb6. High-temperature in situ powder x-ray diffraction (PXRD) studies proved to be useful in hinting at the existence of KV6Sb6, identifying its synthesis conditions, and understanding the reaction mechanism. The crystal structure for KV6Sb6 was determined from high-resolution PXRD data. The compound has a layered structure [R¯3m,a=5.5318(9)Å, c=34.23(3)Å, V=907.0(8)Å3, Z=3 at room temperature] and features a Kagome bilayer of V atoms. KV6Sb6 is isostructural to the previously reported RbV6Sb6 and CsV6Sb6 compounds. KV6Sb6 is thermally stable in vacuum up to 1173 K, as evident from the high-temperature in situ PXRD and differential scanning calorimetric analysis. Investigation of magnetic properties for KV6Sb6 between 2 and 300 K reveals temperature-independent paramagnetism and an absence of superconductivity, like the Rb and Cs analogs. Furthermore, we compare the magnetic properties of KV3Sb5, another ternary Kagome compound, synthesized via two different methods: the hydride route and the traditional route from elements. Low-temperature transport property measurements of KV6Sb6 indicate metallic behavior and an intrinsically low thermal conductivity of 1.0WK−1m−1 at 300 K. The layered structure of KV6Sb6 makes it an attractive candidate for deintercalation and doping studies to tune both magnetic and transport properties, laying a foundation for further studies. 
    more » « less
  5. Side chain alkyl groups have become the standard for incorporating solubilizing groups into conjugated polymers. However, the variety of alkyl groups available and their location on the polymer’s backbone can contribute to the packing of the polymer chains in many different ways, resulting in many different morphologies in the polymer that can affect its properties and performances. In this paper, we investigate the effects on the conductivity of nine phenothiazine-containing polyaniline derivatives (P1−P9) with alkyl or aryl side chains on the phenothiazine core while also varying the number of methyl groups on the p-phenylenediamine unit. 1H nuclear magnetic resonance spectroscopy, ultraviolet−visible spectroscopy, differential scanning calorimetry, scanning electron microscopy, atomic force microscopy, and wide-angle X-ray scattering (WAXS) were all used to study the polymers’ structures, physical and thermal properties, and morphologies. The t-butylphenyl substituent on the phenothiazine core seems to provide more rigidity in the polymer’s backbone resulting in higher Tg for series 3, while series 2 containing the 2-hexyldecyl-substituted polymers had the lowest Tg, which is attributed to the large volume of the side chain, that limits interchain interactions. Consequently, series 2 had the lowest conductivity. However, the strongest effect on the conductivity was seen from the tetramethyl groups on the PPDA unit, which resulted in the lowest conductivity in each series due to torsional strain (twisting) in the polymer’s backbone. The WAXS data suggest mostly amorphous films; thus, the conductivity in these materials seems to be dominated by a multiscale charge transport phenomenon that occurs in amorphous conjugated materials. Our results will aid in the understanding of side chain engineering of PANI derivatives for their optimum performances. 
    more » « less