Engineering topics

Shastri, Sarvjit

Publications and source records attributed to Shastri, Sarvjit.

8 records

DOE OSTI2023

Chemical compression and ferroic orders in La substituted BiFe O 3

Chemical compression effects on the ferroic orders in La substituted BiFeO 3 are studied by atomic pair distribution function analysis and structure modeling. While rhombohedral BiFeO 3 exhibits ferroelectricity and antiferromagnetism (AF) with a cycloidal Fe spin arrangement leading to zero magnetization, La substituted BiFeO 3 exhibits a reduced lattice polarization, strengthened AF order, and an apparently suppressed spin cycloid leading to nonzero magnetization. Furthermore, the observed changes in the ferroic orders arise from the chemical compression induced changes in the octahedral rotation and ferroelectric displacement of Bi atoms, which appear as lattice degrees of freedom entangling the electronic and magnetic orders in BiFeO 3 .

36 MATERIALS SCIENCE↗

DOE OSTI2023

Enhanced Thermoelectric Properties of Heavy-fermion Compounds $\text{Yb}_x\text{Ce}_y\text{Sm}_z\text{Ir}_2\text{Zn}_{20}$ $(x+y+z=1)$

Herein, thermoelectric materials hold tremendous promise for advances in fundamental science and practical ap- plications, particularly for robust electricity generation in extreme and remote environments. Despite this, for most materials the energy conversion efficiency is limited by the proportionality between the electrical and thermal conductivities and small values of the Seebeck coefficient for metals. It was previously reported that the heavy-fermion compound $\text{YbIr}_2$ $\text{Zn}_{20}$ exhibits large Seebeck coefficient and thermoelectric figure of merit $ZT$ at 35 K. This behavior is primarily associated with strong hybridization between the $f$- and conduction electron states. Here, we seek to improve the thermoelectric properties through chemical substitution on the Yb site using Ce and Sm. By surveying different levels of substitution, we find that the thermoelectric properties vary strongly with the $f$-element ratio. This confirms that electronic hybridization dominates the thermoelectric properties and clarifies directions for optimizing these materials for applications. We also investigate the impact of the disorder on the thermal conductivity, where we find only weak variation with lanthanide content.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Lattice symmetry breaking transition and critical size limit for ferroic orders in nanophase BiFeO3

Finite size effects on the ferroic orders in BiFeO 3 are studied by atomic pair distribution function analysis and magnetic measurements. While bulk rhombohedral BiFeO 3 exhibits ferroelectricity and antiferromagnetism with a cycloidal magnetic moment arrangement leading to zero magnetization and weak magnetoelectric coupling, BiFeO 3 nanoparticles with a size smaller than the spin cycloid period of 62 nm preserve their polar rhombohedral structure and develop ferromagnetism, thus exhibiting coexisting polarization and nonzero magnetization that enhances the magnetoelectric coupling. When the nanoparticles become smaller than 17 nm, however, their crystal lattice expands and becomes nonpolar cubic. They also become superparamagnetic and thus simultaneously cease exhibiting both ferroelectricity and ferromagnetism. Our findings shed light on the interaction between the lattice structure and ferroic orders in nanophase perovskites and also provide a rare example of a lattice symmetry breaking phase transition that determines their critical size.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2020

Hierarchy among the crystal lattice, charge density wave, and superconducting orders in transition metal dichalcogenides

Using high-energy x-ray scattering and large-scale three-dimensional (3D) structure modeling, in this study we investigate the relationship between the crystal lattice, charge density wave (CDW), and superconducting (SC) orders in transition metal dichalcogenides (TMDs). In particular, we systematically substitute Te for Se in Ta-Se-Te solid solutions, determine changes in their crystal lattice, and relate them to changes in the CDW transition temperature, $T_{CDW}$, and SC critical temperature, $T_c$ . We find that strong lattice distortions such as buckling of Ta layers are detrimental to the CDW and SC orders. The presence of a perfect lattice order in two dimensions is a prerequisite to the emergence of CDWs but insufficient to achieve a SC ordered state. For the SC order to emerge, the Ta sublattice should also appear periodic in 3D. Local chemical disorder may promote the SC order, and the perfectness of Ta coordination polyhedra is a factor contributing to its strength. A hierarchical relationship among the crystal lattice, CDW, and SC orders thus appears to exist in TMDs in a sense that different degrees of crystal lattice order-disorder promote and maintain the CDW and SC orders to a different extent, offering an opportunity to control the latter through modifying the former by rational design. Our findings are a step towards a better understanding of the correlation between lattice and electronic degrees of freedom in TMDs. We also demonstrate an efficient experimental approach to study them in fine detail.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2020

Exotic bonding interactions and coexistence of chemically distinct periodic lattice distortions in the charge density wave compound TaTe2

The superstructure of TaTe 2 is examined by total high-energy x-ray scattering and large-scale structure modeling over a broad temperature range. At room temperature, it features double zigzag chains of Ta atoms exhibiting metallic bonding. The chains are sandwiched between planes of weakly interacting Te atoms. Below 170 K, the chains appear broken to “butterflylike” clusters and single zigzag chains of covalently bonded Te atoms emerge while Ta-Te interactions remain largely ionic. This is a rare example of a charge density wave compound stabilized by bonding that is a mix of covalent, ionic, and metallic character giving rise to chemically distinct periodic lattice distortions. We argue that the formation of periodic lattice distortions in the Te sublattice in addition to those in the Ta sublattice favors charge delocalization, which may explain the unusually diminished resistivity and increased magnetic susceptibility exhibited by the low-temperature charge density wave phase of TaTe 2 . The effect may be common for 5d transition metal chalcogenides containing Te because of the extended electronic orbitals of the constituent atoms.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2020

Genesis of the periodic lattice distortions in the charge density wave state of 2 H- TaSe 2

Using high-energy x-ray diffraction and large-scale three-dimensonal structure modeling, we reveal the evolution of local lattice distortions in the archetypal charge density wave (CDW) system 2 H- TaSe 2 as it is cooled from its normal state above room temperature down to temperature where Ta atoms form a long-range ordered superstructure. In particular, we find that the structure is formed via a gradual in-plane clustering of Ta atoms exhibiting unusually short bonding distances already near room temperature, and not via a cooperative distortion of Ta atomic planes taking place at the critical ordering temperature. Our findings clarify the debated local symmetry and magnitude of the periodic lattice distortions in the CDW state of 2 H- TaSe 2 , and emphasize the role of locally correlated lattice distortions as a precursor of CDWs in low-dimensional solids. Further, we demonstrate an efficient experimental approach to study them.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Morphing Mn core @Pt shell nanoparticles: Effects of core structure on the ORR performance of Pt shell

Currently, the catalysts performance for the oxygen reduction reaction (ORR) is limited by two major factors, their price and the scaling relationship, i.e. constant offset, between the binding energy of reactants and reaction intermediates. Here we show that both limitations may be eased by using nanoparticle catalysts composed of a core of earth-abundant Mn and Pt shell of two atomic layers. We report the unusual atomic-structure of Mn core renders the distribution of coordination numbers and related atomic-level stresses on the Pt shell very broad in com- parison to pure Pt particles. This increases the chances of nearby sites on the shell to affect each other’s activity such that the dissociative absorption of molecular oxygen is facilitated without correspondingly increasing the binding strength of reaction intermediates, thereby promoting the ORR kinetics. Our findings introduce the concept of structural flexibility of the 3d-metal core and 5d-Pt shell as a strategy for catalysis performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2019

Origin of High Activity and Durability of Twisty Nanowire Alloy Catalysts under Oxygen Reduction and Fuel Cell Operating Conditions

The ability to control the surface composition and morphology of alloy catalysts is critical for achieving high activity and durability of catalysts for oxygen reduction reaction (ORR) and fuel cells. Here, this report describes an efficient surfactant-free synthesis route for producing a twisty nanowire (TNW) shaped platinum–iron (PtFe) alloy catalyst (denoted as PtFe TNWs) with controllable bimetallic compositions. PtFe TNWs with an optimal initial composition of ~24% Pt are shown to exhibit the highest mass activity (3.4 A/mg Pt , ~20 times higher than that of commercial Pt catalyst) and the highest durability (<2% loss of activity after 40000 cycles and <30% loss after 120000 cycles) among all PtFe-based nanocatalysts under ORR or fuel cell operating conditions reported so far. Using ex situ and in situ synchrotron X-ray diffraction coupled with atomic pair distribution function (PDF) analysis and 3D modeling, the PtFe TNWs are shown to exhibit mixed face-centered cubic (fcc)-body-centered cubic (bcc) alloy structure and a significant lattice strain. A striking finding is that the activity strongly depends on the composition of the as-synthesized catalysts and this dependence remains unchanged despite the evolution of the composition of the different catalysts and their lattice constants under ORR or fuel cell operating conditions. Notably, dealloying under fuel cell operating condition starts at phase-segregated domain sites leading to a final fcc alloy structure with subtle differences in surface morphology. Due to a subsequent realloying and the morphology of TNWs, the surface lattice strain observed with the as-synthesized catalysts is largely preserved. This strain and the particular facets exhibited by the TNWs are believed to be responsible for the observed activity and durability enhancements. These findings provide new insights into the correlation between the structure, activity, and durability of nanoalloy catalysts and are expected to energize the ongoing effort to develop highly active and durable low-Pt-content nanowire catalysts by controlling their alloy structure and morphology.

25 ENERGY STORAGE↗