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At least 217 records · Page 12
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Structural Complexity and Tuned Thermoelectric Properties of a Polymorph of the Zintl Phase Ca 2 CdSb 2 with a Non-centrosymmetric Monoclinic Structure

The Zintl phase Ca 2 CdSb 2 was found to be dimorphic. Besides the orthorhombic Ca 2 CdSb 2 (-o), here we report on the synthesis, the structural characterization, and the thermoelectric transport properties of its monoclinic form, Ca 2 CdSb 2 (-m), and its Lu-doped variant Ca 2–x Lu x CdSb 2 (x ≈ 0.02). The monoclinic structure exhibits complex structural characteristics and constitutes a new structure type with the non-centrosymmetric space group Cm (Z = 30). The electrical resistivity ρ(T) measured on single crystals of both phases portrays a transition from a semiconductor to a degenerate p-type semiconductor upon doping with Lu and with an attendant change in the Hall carrier concentration nH from 7.15 × 10 18 to 2.30 × 10 19 cm –3 at 300 K. The Seebeck coefficient S(T) of both phases are comparable and indicate a hole-dominated carrier transport mechanism with magnitudes of 133 and 116 μV/K at 600 K for Ca 2 CdSb 2 (-m) and Ca 2–x Lu x CdSb 2 , respectively. The convoluted atomic bonding with an attendant large unit cell volume of ~4365 Å 3 drives a putative low thermal conductivity in these materials resulting in a power factor PF of 1.63 μW/cm K 2 and an estimated thermoelectric figure of merit zT of ~0.5 for Ca 2–x Lu x CdSb 2 at 600 K. Furthermore, differential scanning calorimetry results reveal the stability of these phases up to about 960 K, making them candidates for moderate temperature thermoelectric materials.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Dependence of Uranium Oxide Polymorphism on Plasma Synthesis Conditions

Here, we synthesized uranium oxide nanoparticles using a plasma flow reactor (PFR) and studied the effects of three different experimental parameters on the resulting morphologies and speciation of the particles: (1) collection duration, (2) collection substrate temperature, and (3) radial collection position due to radial temperature gradients in the PFR. We also induced three distinct temperature histories along the axis of the plasma flow reactor by varying the gas flow rates downstream of the plasma torch. Transmission electron microscopy (TEM) analyses of collected particles showed two phases of uranium oxides (fcc-UO 2 and α-UO 3 ). The chemical compositions of the resulting uranium oxide particles were not altered by the three parameters investigated in this work but varied based on the temperature history induced. Preheating of the collection substrate led to deposition of fewer particles, which is attributed to a reduction in thermophoretic force caused by the reduced temperature gradient for preheated substrates. The relative amounts of UO 2 to UO 3 and particle size varied depending on the cooling history employed during synthesis.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2025

Directing Polymorphism of Colloid Crystals Using Conformational Entropy of Polymer Chains

Controlling the polytypes of close-packed structures of spherical colloids is still a challenging problem despite their wide occurrence. Here, in this work, we show that systematic engineering of the polytype structures of close-packed colloids is possible by using the conformational entropy of polymer chains confined in the interstitial space of colloid crystals. Our interstitial space analysis shows that the hexagonal close-packed (HCP) structures offer larger local interstitial space domains, and the structure director chains in favor of HCP counteract the entropic advantages of the face-centered cubic (FCC) lattices. Using model block copolymer colloids and the known lattice entropy of FCC, a proportionality parameter, β CP = 1.91 × 10 –3 ± 3.67 × 10 –4 , for quantifying the conformational entropy contribution toward HCP structures is extracted. This work demonstrates that the interstitial space of colloid crystals serves as a new structure engineering tool for the self-assembly of colloids.

36 MATERIALS SCIENCE↗