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At least 325 records · Page 18

Ground-Based Testing of TiB2 and Al2O3/TiB2 Response to Space Environment

Two materials, titanium diboride and an alumina/titanium diboride composite, exhibit characteristics favorable for use in multiple space applications. These characteristics include low mass (4.52 gm/cc), high strain rate impact resistance, high temperature use (3000oC M.P.), thermal and electrical conductivity, thermal shock resistance, and high visible-range reflectivity. Additionally, the presence of boron in these materials gives them the potential to shield against neutron radiation as well as charged radiation. These materials are flying on MISSE 6 to assess material changes resulting from exposure to the space environment. This study provides a preliminary, ground-based examination of these materials' interactions with individual components of the space environment, in particular atomic oxygen (AO) and neutron radiation, in order to better predict and understand post-flight results. Individual specimens are exposed to ground state AO and surface oxidation is measured. Equivalent exposures of up to 13 months show no rapid oxidation, however evidence indicates some surface oxidation occurring. Other samples are placed near a polyethylene moderated, one Ci Am/Be neutron source to determine their shielding capability. Comparisons between exposed and shielded indium foil, which is activated by transmitted neutrons, measure each material's ability to shield neutrons. Preliminary results indicate a significant shielding benefit provided by both materials.

Jefferies, Sharon A.↗

Different interfacial reactivity of lithium metal chloride electrolytes with high voltage cathodes determines solid-state battery performance

A deep understanding of the interaction of the surface of cathode materials with solid electrolytes is crucial to design advanced solid-state batteries (SSBs). This is especially true for the new class of lithium metal chloride (Li-M-Cl) solid electrolytes which are receiving rapidly growing attention due to their very high oxidative stability (>4 V) in combination with good ionic conductivity that can enable long cell cycle life. While Li-M-Cl electrolytes typically contain resource-limited metals (M) such as indium or rare earths, work has focused on substituting M with more abundant elements such as zirconium. Via operando resistance measurements using intermittent current interruption we explore the dynamic evolution of the interphase at the surface of Ni-rich NCM85 or NCM111 cathode particles inside a working SSB with three different Li-(M 1 ,M 2 )-Cl catholytes (Li 3 InCl 6 , Li 2 Sc 1/3 In 1/3 Cl 4 and Li 5/2 Y 1/2 Zr 1/2 Cl 6 ) to reveal the impact of the cationic metal substitution on the interfacial chemistry. We show that the metal plays a critical role in determining high voltage stability, contrary to prior assumptions. Using a combination of cyclic voltammetry and ultraviolet photoelectron spectroscopy measurements of the electronic band structure to assess oxidative stability; coupled with DFT calculations and ToF-SIMS to evaluate products formed at the interface at different upper cutoff potentials and degrees of delithiation, we are able to differentiate between electrochemical and chemical degradation. We find that Li 2 Sc 1/3 In 1/3 Cl 4 yields the highest (and Li 3 InCl 6 the lowest) stability against electrochemical oxidation, while Li 5/2 Y 1/2 Zr 1/2 Cl 6 undergoes a detrimental chemical reaction with oxygen released from Ni-rich NCM85 at high potentials, resulting in fast capacity fading. Altogether, our work establishes a platform for the metrics and an approach that can be utilized to efficiently evaluate the stability of new halide SEs in SSB cells.

25 ENERGY STORAGE↗

Liquid metal drop ejection

The aim of this project was to demonstrate the possibility of ejecting liquid metals using drop on demand printing technology. The plan was to make transducers for operation in the 100 MHz frequency range and to use these transducers to demonstrate the ability to eject drops of liquid metals such as gallium. Two transducers were made by indium bonding piezoelectric lithium niobate to quartz buffer rods. The lithium niobate plates were thinned by mechanical polishing to a thickness of 37 microns for operation at 100 MHz. Hemispherical lenses were polished in the opposite ends of the buffer rods. The lenses, which focus the sound waves in the liquid metal, had an F-number equals 1. A mechanical housing was made to hold the transducers and to allow precise control over the liquid level above the lens. We started by demonstrating the ability to eject drops of water on demand. The drops of water had a diameter of 15 microns which corresponds to the wavelength of the sound wave in the water. A videotape of this ejection was made. We then used a mixture of Gallium and Indium (used to lower the melting temperature of the Gallium) to demonstrate the ejection of liquid metal drops. This proved to be difficult because of the oxide skin which forms on the surface of the liquid. In some instances, we were able to eject metal drops, however, this was not consistent and reproducible. An experiment was set up at NASA-Lewis to stabilize the process of drop on demand liquid metal ejection. The object was to place the transducer and liquid metal in a vacuum station so that no oxide would form on the surface. We were successful in demonstrating that liquid metals could be ejected on demand and that this technology could be used for making sheet metal in space.

Khuri-Yakub, B. T.↗

Experiments with the low melting indium-bismuth alloy system

The following is a laboratory experiment designed to create an interest in and to further understanding of materials science. The primary audience for this material is the junior high school or middle school science student having no previous familiarity with the material, other than some knowledge of temperature and the concepts of atoms, elements, compounds, and chemical reactions. The objective of the experiment is to investigate the indium-bismuth alloy system. Near the eutectic composition, the liquidus is well below the boiling point of water, allowing simple, minimal hazard casting experiments. Such phenomena as metal oxidation, formation of intermetallic compound crystals, and an unusual volume increase during solidification could all be directly observed. A key concept for students to absorb is that properties of an alloy (melting point, mechanical behavior) may not correlate with simple interpolation of properties of the pure components. Discussion of other low melting metals and alloys leads to consideration of environmental and toxicity issues, as well as providing some historical context. Wetting behavior can also be explored.

Krepski, Richard P.↗

Stable Cadmium-Free Quantum Dot Optical Down-Converters for Solid State Lighting

Quantum dots (QDs) have been used in commercial solid-state lighting (SSL) applications to improve the energy efficiency of light generation at warm color temperatures. By increasing the amount of QDs used in each product, further energy savings are possible; however, traditional QDs contain cadmium, which has regulatory limits on its concentration in consumer products. As described within this final technical report, we have established that heavy-metal free QDs made from indium phosphide (InP) exhibit highly efficient emission at the temperatures and fluxes relevant to SSL. However, the maintenance of this emission is compromised during long term operation due to QD oxidation. We have identified multiple methods to slow the oxidation rate, which has improved the operational stability of these materials more than 200 times longer than at the project start. Beyond these improvements, heavy-metal free QDs require a further hundred-fold increase in stability to enable use in mid-power SSL and a ten-fold increase in stability to enable use in diffuse SSL applications. The outcomes of this project demonstrate feasibility for the use of heavy-metal free QDs in commercial SSL applications with potential use in diffuse SSL applications in the near term (1-2 years) pending market need.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Sequential Infiltration Synthesis of Multinary Metal Oxides: The Role of Precursor Diffusion and Reactivity

Understanding volatile metal–organic precursor transport in polymer matrices during sequential infiltration synthesis (SIS) is critical to the design of hybrid materials of tailored composition and uniform structure. Here, we investigate the diffusion and reaction behavior of diethylzinc (DEZ) in poly(methyl methacrylate) (PMMA) matrices with variable indium and zinc incorporation. Unlike conventional SIS where precursors adduct or react directly with the polymer backbone, DEZ shows minimal interaction with PMMA. However, DEZ may interact strongly with In–OH or Zn–OH moieties that are previously incorporated into a PMMA thick film. Using spectroscopic ellipsometry, X-ray photoelectron spectroscopy depth profiling, and EDX line scans, we quantify Zn incorporation as a function of exposure time, polymer thickness, and previous infiltration steps. The Zn distribution evolves from surface-localized to deep within the ∼1 μm thick film with increasing DEZ exposures up to 30 min. A reaction-diffusion model incorporating a hindering factor to capture diffusivity decay due to product accumulation reproduces the Zn depth profile and yields physically meaningful parameters to guide future growth. Furthermore, this study provides a framework for interpreting metal–organic precursor infiltration behavior and highlights the utility of model-guided SIS process design.

diethylzinc↗

Effects of strain, disorder, and Coulomb screening on free-carrier mobility in doped cadmium oxide

Here, the interplay of stress, disorder, and Coulomb screening dictating the mobility of doped cadmium oxide (CdO) is examined using Raman spectroscopy to identify the mechanisms driving dopant incorporation and scattering within this emerging infrared optical material. Specifically, multi-wavelength Raman and UV-vis spectroscopies are combined with electrical Hall measurements on a series of yttrium (X = Y) and indium (X = In) doped X:CdO thin-films. Hall measurements confirm n-type doping and establish carrier concentrations and mobilities. Spectral fitting along the low-frequency Raman combination bands, especially the TA+TO(X) mode, reveals that the evolution of strain and disorder within the lattice as a function of dopant concentration is strongly correlated with mobility. Coupling between the electronic and lattice environments was examined through analysis of first- and second-order longitudinal–optical phonon–plasmon coupled modes that monotonically decrease in energy and asymmetrically broaden with increasing dopant concentration. By fitting these trends to an impurity-induced Fröhlich model for the Raman scattering intensity, exciton–phonon and exciton–impurity coupling factors are quantified. These coupling factors indicate a continual decrease in the amount of ionized impurity scattering with increasing dopant concentration and are not as well correlated with mobility. This shows that lattice strain and disorder are the primary determining factors for mobility in donor-doped CdO. In aggregate, the study confirms previously postulated defect equilibrium arguments for dopant incorporation in CdO while at the same time identifying paths for its further refinement.

42 ENGINEERING↗

Oxidation and protection of fiberglass-epoxy composite masts for photovoltaic arrays in the low Earth orbital environment

Fiberglass-epoxy composites are considered for use as structural members for the mast of the space station solar array panel. The low Earth orbital environment in which space station is to operate is composed mainly of atomic oxygen, which has been shown to cause erosion of many organic materials and some metals. Ground based testing in a plasma asher was performed to determine the extent of degradation of fiberglass-epoxy composites when exposed to a simulated atomic oxygen environment. During exposure, the epoxy at the surface of the composite was oxidized, exposing individual glass fibers which could easily be removed. Several methods of protecting the composite were evaluated in an atomic oxygen environment and with thermal cycling and flexing. The protection techniques evaluated to date include an aluminum braid covering, an indium-tin eutectic and a silicone based paint. The open aluminum braid offered little protection while the CV-1144 coating offered some initial protection against atomic oxygen, but appears to develop cracks which accelerate degradation when flexed. Coatings such as the In-Sn eutectic may provide adequate protection by containing the glass fibers even though mass loss still occurs.

Rutledge, Sharon K.↗

A Molten Salt Electrochemical Process for the Preparation of Cost-Effective p-Block (Coating) Materials

Solar energy applications rely heavily on p-block elements and transition metals. Silicon is, by far, the most commonly used material in photovoltaic cells and accounts for about 85% of modules sold presently. Of late, thin film photovoltaic cells have gained momentum because of their higher efficiencies. Most of these thin film devices are made out of just five elements, namely, cadmium, tellurium, selenium, indium, gallium and copper. The present manuscript describes an elegant and inexpensive molten salt-based electrolytic process for fabricating a tellurium-coated metallic substrate. A three-electrode set up was employed to coat iridium with tellurium from a molten bath containing lithium chloride, lithium oxide and tellurium tetrachloride (LiCl-Li 2 O-TeCl 4 ) at 650 °C for a duration ranging from 30 to 120 min under a galvanostatic mode. The tellurium coating was observed to be thick, uniform, smooth and homogeneous. Additionally, the deposited tellurium did not chemically react with the iridium substrate to form intermetallic compounds, which is a good feature from the standpoint of the device’s performance characteristics. The present process, being generic in nature, shows the potential for the manufacture of both the coated substates and high-purity elements not just for tellurium but also for other p-block elements.

36 MATERIALS SCIENCE↗

An x ray photoelectron spectroscopy study of Au(x)In(y) alloys

Four gold-indium alloys were studied by x ray photoelectron spectroscopy. The binding energies and intensity ratios of the Au 4f7/2 and In 3d5/2 core levels were determined for the bulk alloy compositions of Au(10 percent In), Au3In, AuIn, and AuIn2. These values were determined for the native oxides on the materials, for the surfaces prepared by ion bombardment to remove the oxide and for surfaces scraped in-situ with a ceramic tool to expose the bulk composition. These results furnish calibration values that allow determination of the composition of thin films of this alloy system. In addition the binding energies add to the data base for understanding the effect of alloying on core level binding energies. As an illustration, these results are used to determine the composition of a series of alloy films formed by incongruent evaporation of an alloy charge.

Jayne, Douglas T.↗

Indium and thallium extraction into betainium bis(trifluoromethylsulfonyl)imide ionic liquid from aqueous hydrochloric acid media

The partitioning behavior of indium and thallium ions between aqueous hydrochloric acid solutions and hydrophobic betainium bis(trifluoromethylsulfonyl)imide ionic liquid was studied using a standard liquid–liquid extraction technique. The experiments were mainly carried out by means of a radiochemical method, using 111 In and 201 Tl medical radionuclides at an ultra-trace concentration. Both mono- and trivalent thallium were utilized and the highest oxidation state (3+) was produced by adding either chlorine or bromine water to the aqueous phase prior to extraction. The metal ion transfer was optimized by varying the aqueous concentration of hydrochloric acid and by introducing zwitterionic betaine as an extracting agent into the aqueous phase. It was found that the highest D values of In(III), Tl(III) and Tl(I) in the investigated chemical systems were up to 200, 70, and 1, respectively. The influence of the addition of lithium salt, having common with the ionic liquid counterion, and the variation of mixing time on the distribution ratio of the metal ions were also studied. Finally, to understand the underlying extraction mechanism of the metal ions and to propose the predominant extracted species, mathematical models based on ion pair formation and ion exchange were developed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Silicon dioxide with a silicon interfacial layer as an insulating gate for highly stable indium phosphide metal-insulator-semiconductor field effect transistors

A novel gate insulator consisting of silicon dioxide (SiO2) with a thin silicon (Si) interfacial layer has been investigated for high-power microwave indium phosphide (InP) metal-insulator-semiconductor field effect transistors (MISFETs). The role of the silicon interfacial layer on the chemical nature of the SiO2/Si/InP interface was studied by high-resolution X-ray photoelectron spectroscopy. The results indicated that the silicon interfacial layer reacted with the native oxide at the InP surface, thus producing silicon dioxide, while reducing the native oxide which has been shown to be responsible for the instabilities in InP MISFETs. While a 1.2-V hysteresis was present in the capacitance-voltage (C-V) curve of the MIS capacitors with silicon dioxide, less than 0.1 V hysteresis was observed in the C-V curve of the capacitors with the silicon interfacial layer incorporated in the insulator. InP MISFETs fabricated with the silicon dioxide in combination with the silicon interfacial layer exhibited excellent stability with drain current drift of less than 3 percent in 10,000 sec, as compared to 15-18 percent drift in 10,000 sec for devices without the silicon interfacial layer. High-power microwave InP MISFETs with Si/SiO2 gate insulators resulted in an output power density of 1.75 W/mm gate width at 9.7 GHz, with an associated power gain of 2.5 dB and 24 percent power added efficiency.

Kapoor, V. J.↗

Tuning the Product Distribution of Acetylene Dimerization through Bimetallic Metal–Organic Framework-Supported Nanoporous Systems

Metal-organic frameworks (MOFs) are receiving increased attention due to their well-defined structures that allow the determination of structure-property relationships. MOFs have been used as heterogeneous catalyst supports in a variety of fashions including for confinement of metal nanoparticles, which have demonstrated enhanced resistance to aggregation, a common issue in amorphous metal oxide supports. Cu and In catalysts were installed in the Zr-based MOF NU-907, being confined within the nanoporous structure. The Cu catalyst is known to, under various conditions, either selectively hydrogenate acetylene to ethylene or generate C4 products such as butenes and 1,3-butadiene, an important feedstock for rubber and adhesives. The addition of indium to the Cu catalyst is intended to serve as a promoter to produce C4 products by decreasing the surface coverage of copper while still allowing for C-C coupling. When employed for acetylene dimerization, InCu-NU-907 shows slightly decreased C4 production overall but enhanced 1,3-butadiene production compared to all other catalysts studied herein. These catalysts were thoroughly characterized by a range of techniques to confirm structural integrity and porosity and probe the nature of the interactions of indium with the Cu nanoparticle active site.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Emissive Colloidal GaAs Quantum Dots

Colloidal quantum dots offer tunable optical properties for optoelectronic applications, but the synthesis of high-quality III–V quantum dots (QDs) other than indium pnictides, and particularly GaAs, has remained elusive due to synthetic challenges. Colloidal GaAs QDs have been reported very recently and have shown only weak band-edge photoluminescence. Here, we demonstrate a large-scale synthesis of colloidal GaAs QDs in molten salts, followed by a high-temperature surface treatment with K 2 S, which removes native oxide and enables uniform zinc chalcogenide shell growth on GaAs. These QDs demonstrate bright band-edge photoluminescence and electroluminescence in QD LED devices. Low-temperature spectroscopy reveals a well-resolved exciton fine structure with distinct bright-state splitting and temperature-independent decay dynamics from 4 to 100 K. These results establish a practical pathway for the preparation of high-quality colloidal GaAs QDs from molten salts with potential applications in quantum technologies and optoelectronics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Rapid thermal annealing of indium phosphide compound semiconductors

The rapid thermal annealing (RTA) of indium phosphide (InP) substrates using a proximity contact method and silicon nitride encapsulation is investigated. The surface conditions of the InP substrates following cleaning with procedures A and B are analyzed. Procedure A involves using an iodic acid solution to remove work-damage InP surface layers and B is a degasssing process and hydrofluoric acid solution for native oxide removal. AES, XPS, and SIMS data of the proximity contact and silicon nitride encapsulated annealed samples are examined. The data reveal that RTA using proximity contact with silicon wafers does not provide adequate protection; however, the InP sample is successfully annealed when protected by a silicon nitride encapsulant.

Biedenbender, Michael D.↗

Task 12 PV Sustainability - Environmental Life Cycle Assessment of Residential PV and Battery Storage Systems

Using a life cycle assessment (LCA), the environmental impacts from generating 1 kWh of electricity for self-consumption via a photovoltaic-battery system are determined. The system includes a 10 kWp multicrystalline-silicon photovoltaic (PV) system (solar irradiation about 1350 kWh/m2/year and annual yield 1000 kWh/kWp), an iron phosphate lithium-ion (LiFePO4) battery, and other components such as the control system, battery housing, and two inverters (one for the PV system and one for the battery system). Three options for the AC-coupled system with changing battery capacities (5, 10, or 20 kWh nominal capacity) are investigated. The environmental impacts are assessed using the indicators greenhouse gas emissions and cumulative energy demand (separated into total and non-renewable cumulative energy demand). In addition, the four most important impact categories for PV electricity - respiratory inorganics (particulate matter), acidification, energy carrier resource use, and minerals and metals resource use - are assessed according to the environmental footprint (EF) method. Data are drawn from the DETEC data DQRv2:2018, recent literature, and product details provided by manufacturers. The results show larger environmental impacts of PV-battery systems with increasing battery capacity; for capacities of 5, 10, and 20 kWh, the cumulative greenhouse gas emissions from 1 kWh of electricity generation for self-consumption via a PV-battery system are 80, 84, and 88 g CO 2- eq/kWh, respectively. The cumulative greenhouse gas emissions of PV electricity consumed directly or fed into the grid are 54 g CO 2 -eq/kWh. The corresponding total cumulative energy demands are 5.27, 5.40, and 5.50 MJ oil-eq/kWh, with non-renewable energy carriers contributing 1.16, 1.22, and 1.29 MJ oil-eq/kWh. In the investigated EF impact categories, we similarly observe a larger environmental burden with increasing battery capacity, except in the use of minerals and metals. Our sensitivity analyses show that using a nickel cobalt manganese oxide (NCM) lithium-ion battery, instead of an LiFePO 4 battery, leads to a comparable environmental impact in terms of greenhouse gas emissions and cumulative energy demand. However, the NCM battery increases the impact in the EF categories of acidification and respiratory inorganics by 7 and 10%, respectively, whereas energy carrier resource use decreases by 4% and minerals and metals resource use decrease by 1%. Using a copper indium selenium (CIS) PV panel instead of a multicrystalline-silicon decreases greenhouse gas emissions by 24%, non-renewable cumulative energy demand by 13%, and particulate matter emissions by 60% (the largest decrease). Furthermore, the calculated environmental impacts are sensitive to the assumed battery lifetime. A decrease from 5000 to 3000 charge cycles increases non-renewable cumulative energy demand by 24% and greenhouse gas emissions by 16%. Increasing from 5000 to 7000 charge cycles decreases the environmental impacts by 6% and 7% in terms of non-renewable cumulative energy demand and greenhouse gas emissions, respectively. A utility-scale battery system case study shows that using batteries to store PV electricity overproduction reduces greenhouse gas emissions compared to using natural gas backup electricity generation.

14 SOLAR ENERGY↗

The Subchalcogenides Ir 2 In 8 Q (Q = S, Se, Te): Dirac Semimetal Candidates with Re-entrant Structural Modulation

Subchalcogenides are uncommon compounds where the metal atoms are in unusually low formal oxidation states. They bridge the gap between intermetallics and semiconductors and can have unexpected structures and properties because of the exotic nature of their chemical bonding as they contain both metal–metal and metal–main group (e.g., halide, chalcogenide) interactions. Finding new members of this class of materials presents synthetic challenges as attempts to make them often result in phase separation into binary compounds. We overcome this difficulty by utilizing indium as a metal flux to synthesize large (millimeter scale) single crystals of novel subchalcogenide materials. Herein, we report two new compounds Ir 2 In 8 Q (Q = Se, Te) and compare their structural and electrical properties to the previously reported Ir 2 In 8 S analogue. Ir 2 In 8 Se and Ir 2 In 8 Te crystallize in the $P_{4_2}$/mnm space group and are isostructural to Ir2In8S, but also have commensurately modulated (with q vectors q = 1/6a* + 1/6b* and q = 1/10a* + 1/10b* for Ir 2 In 8 Se and Ir 2 In 8 Te, respectively) low-temperature phase transitions, where the chalcogenide anions in the channels experience a distortion in the form of In–Q bond alternation along the ab plane. Both compounds display re-entrant structural behavior, where the supercells appear on cooling but revert to the original subcell below 100 K, suggesting competing structural and electronic interactions dictate the overall structure. Notably, these materials are topological semimetal candidates with symmetry-protected Dirac crossings near the Fermi level and exhibit high electron mobilities (~1500 cm 2 V –1 s –1 at 1.8 K) and moderate carrier concentrations (~10 20 cm –3 ) from charge transport measurements. This work highlights metal flux as a synthetic route to high quality single crystals of novel intermetallic subchalcogenides with Dirac semimetal behavior.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗