Experimental Testing of the Theoretically Predicted Magnetic Properties for Kagomé Compounds in the Li–Fe–Ge System
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Mantravadi, Aishwarya [Department of Chemistry; Io↗
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Fundamental Insights from a Single-Crystal Sodium Iridate Battery
Electrochemically driven chemical transformations play the key role in controlling storage of energy in chemical bonds and subsequent conversion to power electric vehicles and consumer electronics. The promise of coupling anionic oxygen redox with cationic redox to achieve a substantial increase in capacities has inspired research in a wide range of electrode materials. A key challenge is that these studies have focused on polycrystalline materials, where it is hard to perform precise structural determinations, especially related to the location of light atoms. Here a different approach is utilized and a highly ordered single crystal, Na 2-x IrO 3 is harnessed, to explore the role of defects and structural transformations in layered transition metal oxide materials on redox-activity, capacity, reversibility, and stability. Within a combined experimental and theoretical framework, it is demonstrated that 1) it is possible to cycle Na 2-x IrO 3 , offering proof of principle for single-crystal based batteries 2) structural phase transitions coincide with Ir 4+ /Ir 5+ redox couple with no evident contribution from anionic redox 3) strong irreversibility and capacity fade observed during cycling correlates with the Na + migration resulting in progressive growth of an electrochemically inert O 3 -type NaIrO 3 phase.
25 ENERGY STORAGE↗
FeSi 4 P 4 and CoSi 3 P 3 : Hidden Gems of Ternary Tetrel Pnictides with Outstanding Nonlinear Optical Properties
Metal silicon phosphides have shown promise as nonlinear optical materials. To be practically useful and cheap, earth-abundant 3d transition metals are preferred over their scarcer and more expensive 4d and 5d counterparts. Here, we developed a synthetic method to produce polycrystalline bulk powders and millimeter-sized single crystals of ternary compounds FeSi 4 P 4 and CoSi 3 P 3 . Both studied compounds have noncentrosymmetric and chiral crystal structures with ordered Si/P arrangements as was confirmed by single-crystal X-ray diffraction and solid-state NMR. Despite the presence of the transition metal, FeSi 4 P 4 and CoSi 3 P 3 are semiconductors with direct band gaps of 1.3 and 1.6 eV, respectively, indicating low-spin d 6 electronic configuration for octahedral Fe 2+ and Co 3+ . Relative to reported sulfide materials, FeSi 4 P 4 and CoSi 3 P 3 small band gap semiconductors demonstrate an outstanding combination of second-harmonic generation (SHG) activity and laser damage threshold (LDT). Both studied materials are phase-matchable with a 2.09 μm laser and not only exhibit 2.5–3.0 times stronger SHG signal than that of the state-of-the-art AgGaS 2 standard but also demonstrate an LDT response of 2.3–2.5 times higher than that of AgGaS 2 (at 1.09 μm laser with a pulse width of 10 ns)-which is unprecedented for small band gap semiconductors.
36 MATERIALS SCIENCE↗
Creep behavior of electron-beam-melted rhenium
Comparison of creep-rupture properties of electron beam-melted polycrystalline and powder- metallurgy rhenium sheets at 2200 to 4200 F and 4 to 40 ksi
Raffo, P. L.↗
Effects of Extended Aqueous Processing on Structure, Chemistry, and Performance of Polycrystalline LiNi x Mn y Co z O 2 Cathode Powders
The prospect of aqueous processing of LiNi x Mn y Co z O 2 (NMC) cathodes has significant appeal to battery manufacturers for the reduction in materials cost, toxicological risk, and environmental impact compared to conventional N -methyl-2-pyrrolidone (NMP)-based processing. However, the effects of aqueous processing of NMC powders at industrial timescales are not well studied, with prior studies mostly focusing on relatively brief water washing processes. Here, we investigate the bulk and surface impacts of extended aqueous processing of polycrystalline NMC powders with different compositions. We demonstrate that at timescales of several hours, polycrystalline NMC is susceptible to intergranular fracture, with the severity of fracture scaling with the NMC nickel content. While bulk crystallinity and composition are unchanged, surface sensitive techniques such as X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) indicate that the exposure of water leads to a level of delithiation, nickel reduction, and reconstruction from the layered to rock-salt structure at the surface of individual grains. Dynamic single NMC microparticle compression testing suggests that the resulting mechanical stresses weaken the integrity of the polycrystalline particle and increases susceptibility of intergranular fracture. The initially degraded surfaces along with the increased surface area lead to faster capacity fade and impedance growth during electrochemical cycling. From this work, it is demonstrated that NMC powders require surface or grain boundary modifications to make industrial-scale aqueous cathode processing viable, especially for next-generation nickel-rich NMC chemistries.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
High Temperature Mechanical Behavior of Polycrystalline Alumina from Mixed Nanometer and Micrometer Powders
Sintered aluminum oxide materials were formed using commercial methods from mechanically mixed powders of nano-and micrometer alumina. The powders were consolidated at 1500 and 1600 C with 3.2 and 7.2 ksi applied stress in argon. The conventional micrometer sized powders failed to consolidate. While 100 percent nanometer-sized alumina and its mixture with the micrometer powders achieved less than 99 percent density. Preliminary high temperature creep behavior indicates no super-plastic strains. However high strains (less than 0.65 percent) were generated in the nanometer powder, due to cracks and linked voids initiated by cavitation.
Goldsby, Jon C.↗
Ultrasonic Apparatus for Pulverizing Brittle Material
The figure depicts an apparatus that pulverizes brittle material by means of a combination of ultrasonic and sonic vibration, hammering, and abrasion. The basic design of the apparatus could be specialized to be a portable version for use by a geologist in collecting powdered rock samples for analysis in the field or in a laboratory. Alternatively, a larger benchtop version could be designed for milling and mixing of precursor powders for such purposes as synthesis of ceramic and other polycrystalline materials or preparing powder samples for x-ray diffraction or x-ray fluorescence measurements to determine crystalline structures and compositions. Among the most attractive characteristics of this apparatus are its light weight and the ability to function without need for a large preload or a large power supply: It has been estimated that a portable version could have a mass <0.5 kg, would consume less than 1 W h of energy in milling a 1-cm3 volume of rock, and could operate at a preload <10 N. The basic design and principle of operation of this apparatus are similar to those of other apparatuses described in a series of prior NASA Tech Briefs articles, the two most relevant being Ultrasonic/ Sonic Drill/Corers With Integrated Sensors (NPO-20856), Vol. 25, No. 1 (January 2001), page 38 and Ultrasonic/ Sonic Mechanisms for Deep Drilling and Coring (NPO-30291), Vol. 27, No. 9 (September 2003), page 65. As before, vibrations are excited by means of a piezoelectric actuator, an ultrasonic horn, and a mass that is free to move axially over a limited range. As before, the ultrasonic harmonic motion of the horn drives the free-mass in a combination of ultrasonic harmonic and lower-frequency hammering motion. In this case, the free-mass is confined within a hollow cylinder that serves as a crushing chamber, and the free-mass serves as a crushing or milling tool. The hammering of the free-mass against a material sample at the lower end of the chamber grinds the sample into powder in a relatively short time. The restriction of the free-mass to axial motion only makes the grinding very efficient. The free-mass can be fabricated to have teeth on its lower face to enhance the grinding effect. Optionally, there can be a hole at the bottom of the chamber covered with a sieve to tailor the size distribution of the powder leaving the crushing chamber.
Sherrit, Stewart↗
Creep behavior of electron-beam-melted rhenium
Creep rupture behavior of electron beam melted polycrystalline sheet and powdered rhenium
Raffo, P. L.↗
X-ray diffraction studies of shocked lunar analogs
The X-ray diffraction experiments on shocked rock and mineral analogs of particular significance to lunar geology are described. Materials naturally shocked by meteorite impact, nuclear-shocked, or artificially shocked in a flat plate accelerator were utilized. Four areas were outlined for investigation: powder diffractometer studies of shocked single crystal silicate minerals (quartz, orthoclase, oligoclase, pyroxene), powder diffractometer studies of shocked polycrystalline monomineralic samples (dunite), Debye-Scherrer studies of single grains of shocked granodiorite, and powder diffractometer studies of shocked whole rock samples. Quantitative interpretation of peak shock pressures experienced by materials found in lunar or terrestrial impact structures is presented.
Hanss, R. E.↗
Short-range magnetic order and planar anisotropy in the topological ferrimagnet Mn 3 Si 2 Te 6
Mn 3 Si 2 Te 6 is a ferrimagnetic topological nodal-line semiconductor that exhibits unconventional colossal magnetoresistance behavior, with short-range spin fluctuations being potentially intimately linked to the emergent properties. Here we determine the short-range magnetic order and anisotropy through total neutron scattering and polarized neutron powder diffraction measurements on polycrystalline Mn 3 Si 2 Te 6 . Strong in-plane anisotropy is quantified on the Mn ions through extraction of the local site susceptibility tensor. Here, the real-space local spin structure is determined through the application of magnetic pair distribution function analysis covering a wide temperature range. Short-range order over a locally frustrated trimer of three nearest neighbors is found to exist well above the long-range ferrimagnetic transition.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Diamond Smoothing Tools
Diamond smoothing tools have been proposed for use in conjunction with diamond cutting tools that are used in many finish-machining operations. Diamond machining (including finishing) is often used, for example, in fabrication of precise metal mirrors. A diamond smoothing tool according to the proposal would have a smooth spherical surface. For a given finish machining operation, the smoothing tool would be mounted next to the cutting tool. The smoothing tool would slide on the machined surface left behind by the cutting tool, plastically deforming the surface material and thereby reducing the roughness of the surface, closing microcracks and otherwise generally reducing or eliminating microscopic surface and subsurface defects, and increasing the microhardness of the surface layer. It has been estimated that if smoothing tools of this type were used in conjunction with cutting tools on sufficiently precise lathes, it would be possible to reduce the roughness of machined surfaces to as little as 3 nm. A tool according to the proposal would consist of a smoothing insert in a metal holder. The smoothing insert would be made from a diamond/metal functionally graded composite rod preform, which, in turn, would be made by sintering together a bulk single-crystal or polycrystalline diamond, a diamond powder, and a metallic alloy at high pressure. To form the spherical smoothing tip, the diamond end of the preform would be subjected to flat grinding, conical grinding, spherical grinding using diamond wheels, and finally spherical polishing and/or buffing using diamond powders. If the diamond were a single crystal, then it would be crystallographically oriented, relative to the machining motion, to minimize its wear and maximize its hardness. Spherically polished diamonds could also be useful for purposes other than smoothing in finish machining: They would likely also be suitable for use as heat-resistant, wear-resistant, unlubricated sliding-fit bearing inserts.
Voronov, Oleg↗
High temperature deformation of hot-pressed polycrystalline orthoenstatite
Artificial hot pressed polycrystalline samples were prepared from purified powder of Bamble, Norway, orthoenstatite, (Mg0.86Fe0.14)SiO3. The uniaxial creep behavior of the polycrystalline orthoenstatite was studied over stress ranges of 10-180 MPa and temperatures of 1500-1700 K (0.82-0.93 T sub m) under two different oxygen fugacities, namely equilibrium (Mo-MoO2 buffer) and a reducing (graphite heating element) atmosphere, respectively. An intergranular glassy phase of different compositions with a cavitational creep deformation were observed. In the Mo-MoO2 buffer atmosphere with PO2 approx. 10 to the minus 11 power - 10 to the minus 13 power atmospheres, the results of an analytical electron microscopy analysis indicate that the glassy phases are richer in Ca and Al due to the residual impurities after hot pressing. In the reducing atmosphere with an oxygen fugacity of PO2 approx. 10 to the minus 3 power - 10 to the minus 25 power atmospheres, the results of analytical electron microscopy analysis indicate that the glassy phase is almost pure silica with the presence of free iron precipitate on grain facets and at triple junctions due to the reduction of bulk materials.
Dehghan-Banadaki, A.↗
Texture Formation in Polycrystalline Thin Films of All‐Inorganic Lead Halide Perovskite
Abstract Controlling grain orientations within polycrystalline all‐inorganic halide perovskite solar cells can help increase conversion efficiencies toward their thermodynamic limits; however, the forces governing texture formation are ambiguous. Using synchrotron X‐ray diffraction, mesostructure formation within polycrystalline CsPbI 2.85 Br 0.15 powders as they cool from a high‐temperature cubic perovskite (α‐phase) is reported. Tetragonal distortions (β‐phase) trigger preferential crystallographic alignment within polycrystalline ensembles, a feature that is suggested here to be coordinated across multiple neighboring grains via interfacial forces that select for certain lattice distortions over others. External anisotropy is then imposed on polycrystalline thin films of orthorhombic (γ‐phase) CsPbI 3‐ x Br x perovskite via substrate clamping, revealing two fundamental uniaxial texture formations; i) I‐rich films possess orthorhombic‐like texture (<100> out‐of‐plane; <010> and <001> in‐plane), while ii) Br‐rich films form tetragonal‐like texture (<110> out‐of‐plane; <110> and <001> in‐plane). In contrast to relatively uninfluential factors like the choice of substrate, film thickness, and annealing temperature, Br incorporation modifies the γ‐CsPbI 3− x Br x crystal structure by reducing the orthorhombic lattice distortion (making it more tetragonal‐like) and governs the formation of the different, energetically favored textures within polycrystalline thin films.
Steele, Julian A.↗
In situ temperature profile measurements with high-energy X-rays as a probe of optical floating zone crystal growth environment
The ability of optical floating zone (OFZ) furnaces to rapidly produce large single crystals of complex emerging materials has had a transformative effect on many scientific fields that require samples of this type. However, the crystal growth process within the OFZ furnace is not well understood owing to the challenges involved in monitoring the high-temperature crystal growth process. Novel beamline-compatible optical furnaces that approximate the inhomogeneous growth environment within an OFZ furnace have been fabricated and tested in high-energy synchrotron beamlines. In this paper, it is demonstrated that temperature profiles can be effectively extracted from powder diffraction data collected on polycrystalline ceramic rods heated at their tip. Furthermore, these measured temperature profiles can be accurately reproduced using a heat-transfer model that accounts for solid-state thermal conduction, partial sample lamp power absorption, convective air cooling and radiative cooling, allowing key thermal parameters such as thermal conductivity to be extracted from experimental data.
36 MATERIALS SCIENCE↗
Major Effects of Nonmetallic Inclusions on the Fatigue Life of Disk Superalloy Demonstrated
The fatigue properties of modern powder metallurgy disk alloys can vary because of the different steps of materials and component processing and machining. Among these variables, the effects of nonmetallic inclusions introduced during the powder atomization and handling processes have been shown to significantly degrade low-cycle fatigue life. The levels of inclusion contamination have, therefore, been reduced to less than 1 part per million in state-of-the-art nickel disk powder-processing facilities. Yet the large quantities of compressor and turbine disks weighing from 100 to over 1000 lb have enough total volume and surface area for these rare inclusions to still be present and limit fatigue life. The objective of this study was to investigate the effects on fatigue life of these inclusions, as part of the Crack Resistant Disk Materials task within the Ultra Safe Propulsion Project. Inclusions were carefully introduced at elevated levels in a nickel-base disk superalloy, U720, produced using powder metallurgy processing. Multiple strain-controlled fatigue tests were then performed on extracted test specimens at 650 C. Analyses were performed to compare the low-cycle fatigue lives and failure initiation sites as functions of inclusion content and fatigue conditions. Powder of the nickel-base superalloy U720 was atomized in argon at Special Metals Corporation, Inc., using production-scale high-cleanliness powder-processing facilities and handling practices. The powder was then passed through a 270-mesh screen. One portion of this powder was set aside for subsequent consolidation without introduced inclusions. Two other portions of this powder were seeded with alumina inclusions. Small, polycrystalline soft (Type 2) inclusions of about 50 mm diameter were carefully prepared and blended into one powder lot, and larger hard (Type 1) inclusions of about 150 mm mean diameter were introduced into the other seeded portion of powder. All three portions of powder were then sealed in separate containers, hot isostatically pressurized, extruded, forged into subscale disks, and heat treated. Low-cycle-fatigue specimens were then extracted, machined, and tested. Fatigue tests were performed at 650 C in closed-loop servohydraulic testing machines using induction heating and axial extensometers. All tests were continued to failure, and fractographic evaluations were performed on all specimens to determine the crack initiation sites. A large majority of the failures in specimens with introduced inclusions occurred at cracks initiating from inclusions at the specimen surface, as shown for each type of inclusion in the following bar chart. The inclusions significantly reduced fatigue life from unseeded material levels, as shown in the bar chart. These effects were found to depend on the strain range, strain ratio, and inclusion size. Tests at lower strain ranges and higher strain ratios resulted in larger effects of inclusions on life. Inclusion effects on life were thereby maximized in tests at the lowest strain range of 0.6 percent and the most positive strain ratio of 0.5. Under these conditions, small Type 2 inclusions reduced life substantially-- about 20 times, whereas large Type 1 inclusions dramatically reduced life 100 times. These results clearly demonstrate that it is essential to include the effects of inclusions for realistic predictions of disk fatigue life. Important issues, including temperature dependence, crack initiation versus propagation, surface treatments, realistic disk features and machining, and realistic disk spin testing will be addressed to accurately model inclusion effects on disk fatigue life. Fatigue life varied from well over 105 cycles for no inclusions to a little over 103 cycles for 100-micrometer inclusions. A single crack initiating at a surface-connected seeded inclusion caused failure in each case.
Gabb, Timothy P.↗
Enhancing Properties with Distortion: A Comparative Study of Two Iron Phosphide Fe 2 P Polymorphs
Iron phosphide (Fe 2 P) crystallizes in its own hexagonal crystal structure type (h-Fe 2 P). As found in meteorites, orthorhombic polymorph (o-Fe 2 P) was originally reported as a high-temperature and high-pressure phase. Recently, o-Fe 2 P was described as being stable at ambient pressure, yet no synthetic methods were developed for single-crystal growth or single-phase bulk powder synthesis. Here, we report a successful method for growing o-Fe 2 P single crystals and synthesizing phase-pure polycrystalline samples using tin-flux. In situ powder X-ray diffraction studies showed that the phase transition from o-Fe 2 P to h-Fe 2 P occurs at about 873 K, and below that temperature, the formation of the o-Fe 2 P phase is favored thermodynamically rather than kinetically. Systematic comparison of transport, magnetic, and electrocatalytic properties of both h-Fe 2 P and o-Fe 2 P phases showed a substantial impact of the crystal structure on properties. The orthorhombic structural distortion resulted in considerable changes in magnetic properties, with the o-Fe 2 P phase exhibiting a 60% lower Fe magnetic moment and a substantially higher ferromagnetic Curie temperature than h-Fe 2 P. Further, electrochemical measurements toward the hydrogen evolution reaction in acidic media showed that the o-Fe 2 P phase requires an 80 mV lower overpotential than the h-Fe 2 P phase to generate a current density of -10 mA/cm 2 , and their electronic structures suggest that the higher density of states at the Fermi energy is the origin of superior catalytic activity in o-Fe 2 P.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Cleavable quaternary oxychlorides with high magnetic ordering temperatures
Quaternary oxychlorides derived from Ruddlesden–Popper 3d transition metal oxides offer a route to cleavable crystals with bulk antiferromagnetic ordering temperatures reaching at least 550 K. Here, we study the magnetic, optical, and mechanical behavior of Sr 2 FeO 3 Cl, Ca 2 FeO 3 Cl, Ca 3 Fe 2 O 5 Cl 2 , and Sr 3 Fe 2 O 5 Cl 2 . Through optical absorption measurements, we show that these antiferromagnetic semiconductors have optical band gaps of ≈2.1(1) eV. The magnetic ordering symmetries and temperatures were probed by neutron powder diffraction and Mössbauer spectroscopy on polycrystalline samples, demonstrating Néel temperatures (T N ) near room temperature in the single layer Sr 2 FeO 3 Cl (T N ≈ 311 K) and Ca 2 FeO 3 Cl (T N ≈ 360 K), and the double-layer compound Sr 3 Fe 2 O 5 Cl 2 has T N ≈ 545 K. The high-spin moments of Fe 3+ lie within the basal plane and the magnetic structures are compensated within each magnetic layer and characterized by magnetic propagation vectors k = ($\frac{1}{2}$ $\frac{1}{2}$ 0). Magnetization results demonstrate the quasi-2D nature of the magnetism, with a broad maximum in the susceptibility near 2T N for Sr 2 FeO 3 Cl. Scotch tape tests and mechanical exfoliation onto SiO 2 confirm the micaceous nature of these crystals with cleavage down to a single unit cell (two magnetic layers) achieved for Sr 3 Fe 2 O 5 Cl 2 . In conclusion, this paper highlights strong antiferromagnetic interactions, semiconducting band gaps, and cleavability of quaternary Fe-based oxychlorides and motivates future work on crystals and exfoliated flakes of these and related oxyhalide systems.
36 MATERIALS SCIENCE↗
RuO2 - ARCS - powder 300 K
Inelastic neutron scattering data on RuO2 polycrystalline 300 K, ARCS.
inelastic neutron scattering↗