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All sources NASA NTRS DOE OSTI

DOE OSTI2022

Superconductivity and phase diagrams of CaK(Fe 1- x Mn x ) 4 As 4 single crystals

In order to study the effects of Mn substitution on the superconducting and magnetic ground state of CaKFe 4 As 4 (T c = 35 K), members of the CaK (Fe 1–x Mn x ) 4 As 4 series have been synthesized by high-temperature solution growth in single-crystalline form and characterized by elemental analysis, thermodynamic, and transport measurements. These measurements show that the superconducting transition temperature decreases monotonically and is finally suppressed below 1.8 K as x is increased from 0 to 0.036. For x values greater than 0.016, signatures of a magnetic transition can be detected in both thermodynamic and transport measurements in which kinklike features allow for the determination of the transition temperature T* that increases as Mn substitution increases. Here, a temperature-composition (T–x) phase diagram is constructed, revealing a half-dome of superconductivity with the magnetic transition temperature T* appearing near 26 K for x ~ 0.017 and rising slowly up to 33 K for x ~ 0.036. In addition to the creation of the T–x phase diagram for CaK(Fe 1–x Mn x ) 4 As 4 , specific-heat data are used to track the jump in specific heat at T c ; the CaK(Fe 1–x Mn x ) 4 As 4 data do not follow the scaling of ΔC p with $T$$^{3}_{c}$ as many of the other Fe-based superconducting systems do. These data suggest that, as magnetic pair breaking is present, the jump in C p for a given T c is reduced. Elastoresistivity coefficients 2m 66 and m 11 – m 12 as a function of temperature are also measured. 2m 66 and m 11 – m 12 are qualitatively similar to CaK(Fe 1–x Ni x ) 4 As 4 . This may indicate that the magnetic order in Mn-substituted system may be still the same as CaK(Fe 1–x Mn x ) 4 As 4 . Superconductivity of CaK(Fe 1–x Mn x ) 4 As 4 is also studied as a function of magnetic field. A clear change in H' c2 (T)/T c , where H' c2 (T) is dH' c2 (T)/dT, at x ~ 0.015 is observed and probably is related to change of the Fermi surface due to magnetic order. Coherence lengths and the London penetration depths are also calculated based on H c1 and H c2 data. Coherence lengths as the function of x also show the changes near x = 0.015, again consistent with Fermi-surface changes associated with the magnetic ordering seen for higher-x values.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

NASA NTRS2010

AIRS Water Vapor and Cloud Products Validate and Explain Recent Short Term Decreases in Global and Tropical OLR as Observed by CERES

A strong equatorial SST cooling occurred from 160E westward to 120W during the period of September 2002 through August 2010, surrounded by a weaker warming ring to the west. This is the result of a transition from a strong El Nino in late 2002 to a strong La Nina in 2008. Late 2009 is characterized by the beginning of another El Nino. Average rates of change (ARC's) in 500mb specific humidity and cloud cover are in phase with those in the Sea surface temperature (SST). In the El Nino and surrounding region causing outgoing longwave radiation (OLR), to decrease significantly near the dateline and increase in the vicinity of Indonesia. Tropical OLR ARC's in these two areas cancel each other to first order. The negative zonal mean tropical OLR ARC from a drop in equatorial OLR in region 1 from 140W to 40E. This results from increasing water vapor and cloud cover in this area during La Nina with the reverse holding during El Nino.

Susskind, Joel↗

DOE OSTI2025

Magnetocaloric effect in Mn-rich Heusler-derived alloys for room temperature-based applications

Magnetic refrigeration-based technologies rely on the magnetocaloric properties of materials and are crucial for improving energy efficiency and for supporting clean environments. However, materials possessing significant magnetocaloric properties that can be used for room temperature-based applications are still lacking. Heusler alloys (such as Mn–Ni–Ga) show giant magnetocaloric effects, which can be further improved by tuning their composition. Herein, we optimized the ratio of Ni to Ga to achieve an alloy with unique magnetocaloric properties. Here, the alloy demonstrated a substantial magnetocaloric effect, attributed to its narrow temperature range for structural and magnetic phase transitions (near room temperature with minimal hysteresis). Structural phase changes were also observed through high-resolution transmission electron microscopy. Optimum entropy changes, calculated from isothermal magnetization curves (4 Tesla magnetic field), were found to be 24.50 J kg −1 K −1 , which is higher than that of state-of-the-art alloys. Experimental demonstration of the magnetocaloric effect (refrigeration cycle) was also carried out using a thermal imaging camera. Furthermore, first-principles calculations were conducted to validate the experimental findings, specifically focusing on the compositional effects on the structural transitions and magnetic properties of the investigated MNG alloys.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Amorphous-crystalline transition-driven synthesis of Co single-atom catalysts on MoO 3 for enhanced hydrogen evolution in acidic and alkaline media

Single atom catalysts (SACs) dispersed in metal oxide supports offer not only maximized catalyst utilization but also extended modulation capabilities through interactions between the SA and its support. However, achieving facile preparation and ensuring electrochemical durability of such SACs, particularly for hydrogen evolution reaction (HER) applications, remain formidable challenges. Here, our study addresses these issues by employing an amorphous-to-crystalline phase transition in MoO 3 to synthesize a cobalt (Co) SA catalyst. This method facilitates the production of highly selective SA catalysts at low temperatures and ensures their enhanced stability in HER applications. The Co SA MoO 3 catalyst exhibits superior performance in HER, operating effectively in both acidic and alkaline environments. Significantly, it maintains stable HER activity across these diverse electrolytic conditions. Our Density Functional Theory (DFT) calculations provide insights into the exceptional HER performance of Co SA MoO 3 . These calculations reveal that the strong affinity for hydrogen and water, facilitated by the modulation of the p-band orbitals at specific oxygen sites adjacent to the Co SA, establishes a thermoneutral pathway for HER. This study represents a pivotal advancement, showcasing a highly practical and robust single-atom catalyst, marking a significant stride towards sustainable energy solutions.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Ball Milling-Enabled Fe 2.4+ to Fe 3+ Redox Reaction in Prussian Blue Materials for Long-Life Aqueous Sodium-Ion Batteries

Aqueous Na-ion batteries using Prussian blue materials have inherent advantages on safety, material sustainability, and economic cost. However, it is challenging to obtain long term cycling stability because many redox reactions have poor intrinsic stability in water. In this report we demonstrate reversible Fe 2.4+ to Fe 3+ redox reaction of Prussian blue electrodes cycled in 17 m NaClO 4 water-in-salt electrolyte. The cubic phase c-Na 1.17 Fe[Fe(CN) 6 ]·0.35H 2 O) derived from monoclinic Prussian blue (m-Na 1.88 Fe[Fe(CN) 6 ]·0.7H 2 O) through ball milling delivers excellent cycling stability of >18,000 cycles with >90% capacity retention at 10C rate. The specific capacity is ~75 mAh/g and ~67 mAh/g at 1C and 10C rate, respectively. Systematic characterizations including electron microscopy, X-ray diffraction, Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy have verified the phase transition and iron oxidation state evolution, revealing the mechanism that enables the material’s high rate and long durability as the battery cathode.

25 ENERGY STORAGE↗

DOE OSTI2024

Deconvolution of X-ray natural and magnetic circular dichroism in chiral Dy-ferroborate

Structural chirality and magnetism, when intertwined, can have profound implications on materials properties. Using X-ray imaging and spectroscopic measurements that leverage the natural and magnetic circular dichroic effects present in magnetized chiral crystal structures, we probe the interplay between chirality and magnetism across the field-induced spin-flop transition of Dy ferroborate, DyFe 3 (BO 3 ) 4 . Deconvolution of natural and magnetic circular dichroic signals at the Fe K and Dy L 2,3 absorption edges of the non-centrosymmetric structure was enabled by use of tunable temperature and magnetic field, providing access to element-specific magnetic information across the spin-flop transition. The magnetic response of Fe and Dy sublattices was found to be independent of domain chirality. The chiral domains were robust against both the (chirality preserving) R32 to P3 1 21/P3 2 21 structural phase transition at 280 K, and application of magnetic field up to 4 Tesla. A third flavor of X-ray dichroism, magneto-chiral dichroism, was not detected within the accuracy of our measurements. The absence of significant Fe magnetization along the screw, c-axis for the magnetic field strength used in this study, together with non-linear coupling of magnetic field to electric polarization across the spin-flop transition, may hinder observation of magneto-chiral dichroic effects in this system.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

NASA NTRS2005

X-Ray and Radio Studies of Black Hole X-Ray Transients During Outburst Decay

Black hole (BH) and black hole candidate (BHC) transients are X-ray binary systems that typically undergo bright outbursts that last a couple months with recurrence times of years to decades. For this ADP project, we are studying BH/BHC systems during the decaying phases of their outbursts using the Rossi X-ray Taming Explorer (RXTE), the Chandra X-ray Observatory, and multi-wavelength facilities. These systems usually undergo state transitions as they decay, and our observations are designed to catch the state transitions. The specific goals of this proposal include: 1. To determine the evolution of the characteristic frequencies present in the power spectrum (such as quasi-periodic oscillations, QPOs) during state transitions in order to place constraints on the accretion geometry; 2. To contemporaneously measure X-ray spectral and timing properties along with flux measurements in the radio band to determine the relationship between the accretion disk and radio jets; 3. To extend our studies of X-ray properties of BHCs to very low accretion rates using RXTE and Chandra. The work performed under this proposal has been highly successful, allowing the PI to lead, direct, or assist in the preparation of 7 related publications in refereed journals and 6 other conference presentations or reports. These items are listed below, and the abstracts for the refereed publications have also been included. Especially notable results include our detailed measurements of the characteristic frequencies and spectral parameters of BH/BHCs after the transition to the hard state (see All A3, and A5) and at low flux levels (see A4). Our measurements provide one of the strongest lines of evidence to date that the inner edge of the optically thick accretion disk gradually recedes from the black hole at low flux levels. In addition, we have succeeded in obtaining excellent multi-wavelength coverage of a BH system as its compact jet turned on (see Al). Our results show, somewhat unexpectedly, that the radio jet does not turn on until the hard X-ray emission is well past its peak hard state level, strongly constraining theoretical models for hard X-ray production and the spectrum emitted by the jet. Finally, the X-ray/radio results in A2 led us to propose a general picture about the relationship between jet production and X-ray spectral states .

Tomsick, John A.↗

NASA NTRS2014

Assimilation of Dual-Polarimetric Radar Observations with WRF GSI

Dual-polarimetric (dual-pol) radar typically transmits both horizontally and vertically polarized radio wave pulses. From the two different reflected power returns, more accurate estimate of liquid and solid cloud and precipitation can be provided. The upgrade of the traditional NWS WSR-88D radar to include dual-pol capabilities will soon be completed for the entire NEXRAD network. Therefore, the use of dual-pol radar network will have a broad impact in both research and operational communities. The assimilation of dual-pol radar data is especially challenging as few guidelines have been provided by previous research. It is our goal to examine how to best use dual-pol radar data to improve forecast of severe storm and forecast initialization. In recent years, the Development Testbed Center (DTC) has released the community Gridpoint Statistical Interpolation (GSI) DA system for the Weather Research and Forecasting (WRF) model. The community GSI system runs in independently environment, yet works functionally equivalent to operational centers. With collaboration with the NASA Short-term Prediction Research and Transition (SPoRT) Center, this study explores regional assimilation of the dual-pol radar variables from the WSR-88D radars for real case storms. Our presentation will highlight our recent effort on incorporating the horizontal reflectivity (ZH), differential reflectivity (ZDR), specific differential phase (KDP), and radial velocity (VR) data for initializing convective storms, with a significant focus being on an improved representation of hydrometeor fields. In addition, discussion will be provided on the development of enhanced assimilation procedures in the GSI system with respect to dual-pol variables. Beyond the dual-pol variable assimilation procedure developing within a GSI framework, highresolution (≤1 km) WRF model simulations and storm scale data assimilation experiments will be examined, emphasizing both model initialization and short-term forecast of precipitation fields and processes. Further details of the methodology of data assimilation, the impact of different dual-pol variables, the influence on precipitation forecast will be presented at the conference.

Li, Xuanli↗

NASA NTRS2014

Assimilation of Dual-Polarimetric Radar Observations with WRF GSI

Li, Xuanli↗

NASA NTRSDate not supplied

Flow Regime Transitions and Pressure Drop in Gas-Liquid Flows through Packed Beds in Microgravity

The Packed Bed Reactor Experiment (PBRE) focused on the hydrodynamics of gas-liquid flow in porous media, specifically on flow regime transition and pressure drop correlation. The reactor included a cylindrical test section of 60 cm in length, 5 cm in diameter and filled with 2 mm spherical glass beads. Liquid water and Nitrogen gas were flowed into a centrifugal phase separator after exiting the test section. Five absolute pressure transducers and two high-speed video cameras spanned the test section to measure the pressure drop and capture flow regime behavior. Video observations, analysis of pressure traces, and pressure drop data were used to identify flow patterns. It was found that the slope of pressure gradient data when plotted versus the gas or liquid Reynolds numbers changed when the flow regime changed. This observation was used to identify the flow regime boundaries. At high liquid flow rates (high interaction regime), dispersed bubble and pulse flow regimes were detected. At low liquid flow rates (low interaction regime), large bubble and gas channeling regimes were observed. The transition from the big bubble regime to the gas channeling regime occurred at a critical gas flow rate independent of the liquid flow rate. Similarly, the transition from the low interaction to the high interaction regime occurred at a critical liquid flow rate. For these different flow regimes, different two-phase flow friction factors and pressure gradient correlations were fitted as a function of the gas and liquid modified Reynolds numbers and Suratman number. It was found that in all the flow regimes the capillary contribution to the pressure drop is significant and can be as high as 90% of the total pressure drop.

Brian Motil↗

DOE OSTI2024

Designed metal-insulator transition in low-symmetry magnetic intermetallics

Compounds exhibiting half-metallic character and metal-insulator transitions draw considerable attention in condensed-matter and materials physics due to their potential use in spintronics. Here we show that specific electron doping plays a crucial role in tailoring thermodynamic, structural, electronic, and magnetic properties of materials derived from low-symmetry magnetic intermetallics, exemplified on triclinic Mn 4 Al 11 . Upon chemical doping of Al by Ge, we predict improved phase stability and adherence to a generalized “18-n rule” governing closed-shell configurations in intermetallic with narrow bandgaps. Validating experiments include measurements of phase stability and electronic transport properties of electron-doped Mn 4 Al 10 Ge that crystallizes in the Mn 4 Al 11 -type structure, confirming the bandgap opening as predicted by chemical analysis and density-functional theory. Here we also demonstrate theoretically that hydrostatic pressure enhances the predicted half-metallic gap in the up-spin channel, which leads to a ferrimagnetic-to-ferromagnetic transition driven by Mn-Mn charge ordering in the Mn 4 Al 11 parent. We have also discussed the generality of our approach in predicting the design of other classes of intermetallics including half and full Heusler compounds.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2021

Reimagining the $e_g$ 1 Electronic State in Oxygen Evolution Catalysis: Oxidation-State-Modulated Superlattices as a New Type of Heterostructure for Maximizing Catalysis

We report that the discovery of solid-phase, inexpensive transition-metal-based water oxidation catalysts is a central goal for renewable energy, and has led to a general consensus that a partially populated metal e g d-electronic state is desirable, leading to favorable catalysis for certain elements in specific oxidation states. In manganese systems, the key species is manganese(III), whose high-spin d 4 electronic configuration places an unpaired electron in the e g orbital, which is postulated to contribute to electronic and structural features that support catalysis. Based on density functional theory calculations, it is predicted that electron transfer would be facilitated by a catalyst with alternating low- and high-Mn III -content sheets, which positions neighboring band edges in closer energetic proximity. The preparation of such catalysts is demonstrated for the first time and it is shown that the catalytic activity is maximized in these systems over more uniform, but more Mn III -rich systems. The best catalyst possesses alternating high-and low-average oxidation state sheets with interlayer Cs + ions, and has an overpotential of 450 mV at 10 mA, which represents an improvement of 250 mV over the best unmodified synthetic potassium birnessites. Using scanning tunneling spectroscopy, bandgap modulations consistent with the theoretically predicted band edge shifts are detected.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Superior electrochemical performance and reduced heat generation in 3D printed vs. 2D tape-casted NMC622 electrodes

This study compares the charge storage mechanisms, thermodynamics behavior, ion transport, and heat generation in NMC622 electrodes fabricated using a novel 3D printing process and the conventional 2D tape casting process. First, potentiometric entropy measurements revealed that the charge storage mechanisms for both types of electrodes consisted of lithium deintercalation in a homogeneous solid solution of NMC622 followed by a transition from a hexagonal (H1) phase to another hexagonal (H2) phase through a monoclinic (M) phase. Both types of electrodes had similar thermodynamics behavior with overlapping entropic potential profiles. Furthermore, operando isothermal calorimetry at high C-rates indicated that the 3D printed electrodes featured larger specific capacity and better rate performance than the 2D tape-casted electrodes. The better performance of 3D printed electrodes was attributed to their larger electrode/electrolyte interfacial surface area and electrical conductivity as well as their faster lithium ion transport. As a result, the instantaneous heat generation rates were smaller in 3D printed electrodes than in 2D tape-casted electrodes, thus resulting in lower overall specific electrical energy and thermal energy dissipation per unit charge stored. Overall, additive manufacturing techniques offer great potential in producing electrodes with superior electrochemical performance and reduced heat generation for fast charging batteries.

25 ENERGY STORAGE↗

NASA NTRS1994

Programmable Automated Welding System (PAWS): Control of welding through software and hardware

The ATD phase of the PAWS program ended in November 1992 and the follow-on ManTech program was started in September 1993. The system will be industrially hardened during the first year of this program. Follow-on years will focus upon the transition into specific end-user sites. These implementations will also expand the system into other welding processes (e.g. FCAW, GTAW, PAW). In addition, the architecture is being developed for application to other non-welding robotic processes (e.g. inspection, surface finishing). Future development is anticipated to encompass hardening for extreme environments, expanded exception handling techniques, and application to a range of manipulators.

Kline, Martin D.↗

NASA NTRS2010

Human Perception of Ambiguous Inertial Motion Cues

Human daily activities on Earth involve motions that elicit both tilt and translation components of the head (i.e. gazing and locomotion). With otolith cues alone, tilt and translation can be ambiguous since both motions can potentially displace the otolithic membrane by the same magnitude and direction. Transitions between gravity environments (i.e. Earth, microgravity and lunar) have demonstrated to alter the functions of the vestibular system and exacerbate the ambiguity between tilt and translational motion cues. Symptoms of motion sickness and spatial disorientation can impair human performances during critical mission phases. Specifically, Space Shuttle landing records show that particular cases of tilt-translation illusions have impaired the performance of seasoned commanders. This sensorimotor condition is one of many operational risks that may have dire implications on future human space exploration missions. The neural strategy with which the human central nervous system distinguishes ambiguous inertial motion cues remains the subject of intense research. A prevailing theory in the neuroscience field proposes that the human brain is able to formulate a neural internal model of ambiguous motion cues such that tilt and translation components can be perceptually decomposed in order to elicit the appropriate bodily response. The present work uses this theory, known as the GIF resolution hypothesis, as the framework for experimental hypothesis. Specifically, two novel motion paradigms are employed to validate the neural capacity of ambiguous inertial motion decomposition in ground-based human subjects. The experimental setup involves the Tilt-Translation Sled at Neuroscience Laboratory of NASA JSC. This two degree-of-freedom motion system is able to tilt subjects in the pitch plane and translate the subject along the fore-aft axis. Perception data will be gathered through subject verbal reports. Preliminary analysis of perceptual data does not indicate that the GIF resolution hypothesis is completely valid for non-rotational periodic motions. Additionally, human perception of translation is impaired without visual or spatial reference. The performance of ground-base subjects in estimating tilt after brief training is comparable with that of crewmembers without training.

Zhang, Guan-Lu↗

NASA NTRS2014

Functional Sensory-Motor Performance Following Long Term Space Flight: The First Results of "Field Test" Experiment

The effect that extended-duration space flights may have on human space travelers, including exploration missions, is widely discussed at the present time. Specifically, there is an increasing amount of evidence showing that the physical capacity of cosmonauts is significantly reduced after long-duration space flights. It is evident that the most impaired functions are those that rely on gravity, particularly up right posture and gait. Because of the sensorimotor disturbances manifested in the neurology of the posture and gait space flight and postflight changes may also be observed in debilitating motion sickness. While the severity of particular symptoms varies, disturbances in spatial orientation and alterations in the accuracy of voluntary movements are persistently observed after long-duration space flights. At this time most of the currently available data are primarily descriptive and not yet suitable for predicting operational impacts of most sensorimotor decrements observed upon landing on planetary surfaces or asteroids. In particular there are no existing data on the recovery dynamics or functionality of neurological, cardiovascular or muscle performance making it difficult to model or simulate the cosmonauts' activity after landing and develop the appropriate countermeasure that will ensure the rapid and safe recovery of crewmembers immediately after landing in what could be hostile environments. However and as a starting position, the videos we have acquired during recent data collection following the long duration flights of cosmonauts and astronauts walking and performing other tasks shortly after return from space flight speak volumes about their level of deconditioning. A joint Russian-American team has developed a new study specifically to address the changes in crewmembers performance and the recovery of performance with the intent of filling the missing data gaps. The first (pilot) phase of this study includes recording body kinematics and quantifying the coordination and timing of relatively simple basic movements - transition from seated and prone positions to standing, walking, stepping over obstacles, tandem walking, muscle compliance, as well as characteristics of postural sway and orthostatic tolerance. Testing for changes in these parameters have been initiated in the medical tent at the landing site. The first set of experiments showed that during the first hour after landing, cosmonauts and astronauts were able to execute (although slower and with more effort than preflight) simple movements such as egress from a seated or prone position and also to remain standing for 3.5 minutes without exhibiting pronounced cardiovascular changes. More challenging tests, however, demonstrated a prominent reduction in coordination - the obstacle task, for example, was performed at much slower speed and with a marked overestimation of the obstacle height and tandem walking was greatly degraded suggesting significant changes in proprioception, brainstem and vestibular function. There is some speculation that the neural changes, either from the bottom-up or top down may be long lasting; requiring compensatory responses that will modify or mask the adverse responses we have observed. Furthermore, these compensatory responses may actually be beneficial, helping achieve a more rapid adaptation to both weightlessness and a return to earth.

Tomilovskaya, E. S.↗

NASA NTRS2019

Computational Fluid Dynamics Methods Used in the Development of the Space Launch System Liftoff and Transition Lineloads Databases

The objective of this paper is to document the reasoning and trade studies that supported the selection of appropriate tools for constructing aerodynamic lineload databases for the Liftoff and Transition phases of flight for launch vehicles. These decisions were made amid the maturation of an evolving workflow for generating databases on variants of the Space Launch System launch vehicle, with most being based on results from brief developmental studies performed in response to specific, unforeseen challenges that were encountered in analyzing a given configuration. This report is intended to provide a summary of the results and the decision-making processes chronologically over the design cycles of various configurations, starting with isolated free-air bodies for the Block 1 Crew, then the Block 1B Crew and Cargo configurations, and most recently the Block 1B Crew configuration in proximity to the launch tower. The results from these analyses led to the selection of the CREATE-AV Kestrel flowsolver for simulating these problems. The need to accurately capture the expected leeward-wake flow field characteristics required the use of Delayed Detached Eddy Simulation (DDES) method, for which the vorticity magnitude was employed as the solution Adaptive Mesh Refinement (AMR) function over the off-body Cartesian grid region. In addition, the Spalart-Allmaras (SA) model is used to account for the flow turbulence effects.

Ratnayake, Nalin A.↗

DOE OSTI2021

Resolving Configurational Disorder for Impurities in a Low-Entropy Phase

Hematite (α-Fe 2 O 3 ) exerts a strong control over the transport of minor but critical metals in the environment and is used in multiple industrial applications; the photocatalysis community has explored the properties of hematite nanoparticles over a wide range of transition metal dopants. Nonetheless, simplistic assumptions are used to rationalize the local coordination environment of impurities in hematite. Here, we use ab initio molecular dynamics (AIMD)-guided structural analysis to model the extended X-ray absorption fine structure (EXAFS) of Cu 2+ - and Zn 2+ -doped hematite nanoparticles. Specific defect–impurity associations were identified, and the local coordination environments of Cu and Zn both displayed considerable configurational disorder that, in aggregate, approached Jahn–Teller-like distortion for Cu but, in contrast, maintained hematite-like symmetry for Zn. This study highlights the role of defects in accommodating impurities in a nominally low-entropy phase and the limits to traditional shell-by-shell fitting of EXAFS for dopants/impurities in unprecedented bonding environments.

36 MATERIALS SCIENCE↗