skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.

Explore Research Products in the PAR
It may take a few hours for recently added research products to appear in PAR search results.


Title: A machine learning based computational approach for prediction of cation distribution in spinel crystal
In this study, a machine learning based computational approach has been developed to investigate the cation distribution in spinel crystals. The computational approach integrates the construction of datasets consisting of the energies calculated from density functional theory, the training of machine learning models to derive the relationship between system energy and structural features, and atomistic Monte Carlo simulations to sample the thermodynamic equilibrium structures of spinel crystals. It is found that the support vector machine model yields excellent performance in energy predictions based on spinel crystal structures. Furthermore, the developed computational approach has been applied to predict the cation distribution in single spinel MgAl2O4 and MgFe2O4 and double spinel MgAl2-aFeaO4. Agreeing with the available experimental data, the computational approach correctly predicts that the equilibrium degree of inversion of MgAl2O4 increases with temperature, whereas the degree of inversion of MgFe2O4 decreases with temperature. Additionally, it is predicted that the equilibrium occupancy of Mg cations at the tetrahedral and octahedral sites in MgAl2-aFeaO4 could be tuned as a function of chemical composition. Therefore, this study presents a reliable computational approach that can be extended to study the variation of cation distribution with processing temperature and chemical composition in a wide range of complex multi-cation spinel oxides with numerous applications.  more » « less
Award ID(s):
1760916
PAR ID:
10548878
Author(s) / Creator(s):
; ;
Publisher / Repository:
AIP Publishing
Date Published:
Journal Name:
The Journal of Chemical Physics
Volume:
158
Issue:
19
ISSN:
0021-9606
Page Range / eLocation ID:
194102
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. ; ; ; ; ; ; ; (, APL Materials)
    We present an exploration of a family of compositionally complex cubic spinel ferrites featuring combinations of Mg, Fe, Co, Ni, Cu, Mn, and Zn cations, systematically investigating the average and local atomic structures, chemical short-range order, magnetic spin configurations, and magnetic properties. All compositions result in ferrimagnetic average structures with extremely similar local bonding environments; however, the samples display varying degrees of cation inversion and, therefore, differing apparent bulk magnetization. Additionally, first-order reversal curve analysis of the magnetic reversal behavior indicates varying degrees of magnetic ordering and interactions, including potentially local frustration. Finally, reverse Monte Carlo modeling of the spin orientation demonstrates a relationship between the degree of cation inversion and the spin collinearity. Collectively, these observations correlate with differences in synthesis procedures. This work provides a framework for understanding magnetic behavior reported for “high-entropy spinels,” revealing many are likely compositionally complex oxides with differing degrees of chemical short-range order—not meeting the community established criteria for high or medium entropy compounds. Moreover, this work highlights the importance of reporting complete sample processing histories and investigating local to long-range atomic arrangements when evaluating potential entropic mixing effects and assumed property correlations in high entropy materials. 
    more » « less
  2. ; ; ; ; ; ; ; (, Journal of the American Ceramic Society)
    In situ X-ray diffraction measurements at the Advanced Photon Source show that alpha-Al2O3 and MgAl2O4 react nearly instantaneously and completely, and nearly completely to form single-phase high-alumina spinel during voltage-to-current type of flash sintering experiments. The initial sample was constituted from powders of alpha-Al2O3, MgAl2O4 spinel, and cubic 8 mol% Y2O3-stabilized ZrO2 (8YSZ) mixed in equal volume fractions, the spinel to alumina molar ratio being 1:1.5. Specimen temperature was measured by thermal expansion of the platinum standard. These measurements correlated well with a black-body radiation model, using appropriate values for the emissivity of the constituents. Temperatures of 1600-1736 degrees C were reached during the flash, which promoted the formation of alumina-rich spinel. In a second set of experiments, the flash was induced in a current-rate method where the current flowing through the specimen is controlled and increased at a constant rate. In these experiments, we observed the formation of two different compositions of spinel, MgO center dot 3Al(2)O(3) and MgO center dot 1.5Al(2)O(3), which evolved into a single composition of MgO center dot 2.5Al(2)O(3) as the current continued to increase. In summary, flash sintering is an expedient way to create single-phase, alumina-rich spinel. 
    more » « less
  3. ; ; ; ; ; ; ; (, Applied Physics Letters)
    The thermal conductivities of (100) γ-Ga2O3 films deposited on (100) MgAl2O4 substrates with various thicknesses were measured using frequency-domain thermoreflectance. The measured thermal conductivities of γ-Ga2O3 films are lower than the thermal conductivities of (2¯ 01) β-Ga2O3 films of comparable thickness, which suggests that γ-phase inclusions in the doped or alloyed β-phase may affect its thermal conductivity. The thermal conductivity of γ-Ga2O3 increases from 2.3−0.5+0.9 to 3.5±0.7 W/m K for films with thicknesses of 75–404 nm, which demonstrates a prominent size effect on thermal conductivity. The thermal conductivity of γ-Ga2O3 also shows a slight increase as temperature increases from 293 to 400 K. This increase in thermal conductivity occurs when defect and boundary scattering suppress signatures of temperature-dependent Umklapp scattering. γ-Ga2O3 has a cation-defective spinel structure with at least two gallium vacancies in every unit cell, which are the likely source of defect scattering. 
    more » « less
  4. ; (, Journal of Applied Physics)
    Prussian blue analogs (PBAs) are an important material class for aqueous electrochemical separations and energy storage owing to their ability to reversibly intercalate monovalent cations. However, incorporating interstitial [Formula: see text] molecules in the ab initio study of PBAs is technically challenging, though essential to understanding the interactions between interstitial water, interstitial cations, and the framework lattice that affect intercalation potential and cation intercalation selectivity. Accordingly, we introduce and use a method that combines the efficiency of machine-learning models with the accuracy of ab initio calculations to elucidate mechanisms of (1) lattice expansion upon intercalation of cations of different sizes, (2) selectivity bias toward intercalating hydrophobic cations of large size, and (3) semiconductor–conductor transitions from anhydrous to hydrated lattices. We analyze the PBA nickel hexacyanoferrate [[Formula: see text]] due to its structural stability and electrochemical activity in aqueous electrolytes. Here, grand potential analysis is used to determine the equilibrium degree of hydration for a given intercalated cation (Na[Formula: see text], K[Formula: see text], or Cs[Formula: see text]) and [Formula: see text] oxidation state based on pressure-equilibrated structures determined with the aid of machine learning and simulated annealing. The results imply new directions for the rational design of future cation-intercalation electrode materials that optimize performance in various electrochemical applications, and they demonstrate the importance of choosing an appropriate calculation framework to predict the properties of PBA lattices accurately. 
    more » « less
  5. ; (, Polymers)
    Porous polymer-derived membranes are useful for applications ranging from filtration and separation technologies to energy storage and conversion. Combining block copolymer (BCP) self-assembly with the industrially scalable, non-equilibrium phase inversion technique (SNIPS) yields membranes comprising periodically ordered top surface structures supported by asymmetric, hierarchical substructures that together overcome performance tradeoffs typically faced by materials derived from equilibrium approaches. This review first reports on recent advances in understanding the top surface structural evolution of a model SNIPS-derived system during standard membrane formation. Subsequently, the application of SNIPS to multicomponent systems is described, enabling pore size modulation, chemical modification, and transformation to non-polymeric materials classes without compromising the structural features that define SNIPS membranes. Perspectives on future directions of both single-component and multicomponent membrane materials are provided. This points to a rich and fertile ground for the study of fundamental as well as applied problems using non-equilibrium-derived asymmetric porous materials with tunable chemistry, composition, and structure. 
    more » « less
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Save / Share this Record
  • Send to Email