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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Architecting a Stable High-Energy Aqueous Al-Ion Battery

Aqueous Al-ion batteries (AAIBs) are the subject of great interest due to the inherent safety and high theoretical capacity of aluminum. The high abundancy and easy accessibility of aluminum raw materials further make AAIBs appealing for grid-scale energy storage. However, the passivating oxide film formation and hydrogen side reactions at the aluminum anode as well as limited availability of the cathode lead to low discharge voltage and poor cycling stability. Here, we proposed a new AAIB system consisting of an Al x MnO 2 cathode, a zinc substrate-supported Zn-Al alloy anode, and an Al(OTF) 3 aqueous electrolyte. Through the in situ electrochemical activation of MnO, the cathode was synthesized to incorporate a two-electron reaction, thus enabling its high theoretical capacity. The anode was realized by a simple deposition process of Al 3+ onto Zn foil substrate. The featured alloy interface layer can effectively alleviate the passivation and suppress the dendrite growth, ensuring ultralong-term stable aluminum stripping/plating. The architected cell delivers a record-high discharge voltage plateau near 1.6 V and specific capacity of 460 mAh g -1 for over 80 cycles. Finally, this work provides new opportunities for the development of high-performance and low-cost AAIBs for practical applications.

25 ENERGY STORAGE↗
DOE OSTI2026

Progress Towards Synthesis of Uranium Chloride Fuel Salts Using Zinc Chloride

Reliable, scalable methods for producing high-purity actinide chloride salts are needed to support molten salt reactor fuel development and deployment. This report describes the continued development and demonstration of a bench-scale chlorination and purification apparatus using a zinc chloride-based method for synthesizing uranium chloride fuel salts. In this approach, uranium metal is chlorinated by ZnCl2 to produce LiCl-KCl-UCl3. Reaction with three aliquots of added uranium metal was used to generate a target uranium concentration of 30 wt %. While this concentration was chosen for initial testing of the apparatus and method, the final uranium concentration is not limited to 30 wt %. The zinc metal generated in the reaction forms an immiscible layer that was removed by volatilization at moderately high temperatures. Electrochemical measurements confirmed the removal of zinc and applied sensing methods indicated the uranium concentration to be approximately 25 wt %. These initial results demonstrate that the bench-scale chlorination apparatus is an effective platform for the synthesis and purification of uranium chloride salts using ZnCl2. This method shows promise for application to industry-relevant salt systems such as NaCl-UCl3. Further development is recommended to optimize reagent loading, zinc removal, and avoid possible U-Zn alloy formation.

Dulovic, Stephanie↗
DOE OSTI2019

Influencing mechanism of pre-existing nanoscale Al 5 Fe 2 phase on Mg–Fe interface in friction stir spot welded Al-free ZK60–Q235 joint

Al-free ZK60 magnesium (Mg) alloy sheet was selected as substrate material of Mg–steel pinless friction stir spot welding (FSSW), avoiding the effect of the Al element in the substrate on the alloying reaction of Mg-iron (Fe) interface. The sound FSSW joint of ZK60 Mg alloy and Q235 steel with a hot-dipped aluminum (Al)-containing zinc (Zn) coating was successfully realized. The detailed microstructural examinations proved that Al 5 Fe 2 phase at the Mg-Fe interface came from the pre-existing Al 5 Fe 2 phase in the coating and acted as the transition layer for promoting the metallurgical bonding of Mg and Fe. The interfaces with well-matched lattice sites among Fe, Al 5 Fe 2 and Mg were formed during FSSW. A low energy interface with good match of lattice sites ((002) Al5Fe2 //(110) Fe , [110] Al5Fe2 //[13] Fe ) between Al 5 Fe 2 and Fe was identified. For the interface between Al5Fe2 and Mg, an orientation relationship of ( 6 2 ¯ 2 ) A l 5 F e 2 / / ( 3 1 ¯ 1 ¯ 2 ¯ ) M g and [ 1 5 ¯ 8 ¯ ] A l 5 F e 2 / / [ 2 4 ¯ 23 ] M g was observed. The tensile–shear load of the ZK60–steel joint could reach 4.6 kN. Moreover, the joint fracture occurred at the interface between the Al5Fe2 layer and the Mg alloy substrate, suggesting the brittle fracture characteristic.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Evaluating the bond strength and fracture mechanisms of cold-sprayed zinc coating on AZ91 magnesium substrate via a combined experimental and computational approach

Magnesium (Mg) alloys are ideal candidates for automotive applications due to their high strength to weight ratio, castability, recyclability etc., however, they lack corrosion and oxidation resistance. Solid-state deposition techniques, such as cold spray, have been demonstrated to enhance their corrosion resistance as it relies on the severe plastic deformation of powder particles upon impact with the substrate to form a metallurgical bond with the substrate and within the coating. At cold sprayed interfaces, a heterogeneous microstructure is formed that includes some porosity, oxides and intermetallics which can significantly affect coating performance. Thus, establishing a direct correlation between the interface microstructure and its properties can aid in designing optimal cold spray parameters. In this study, we investigated the microstructure and mechanical properties of a zinc (Zn) coating deposited on a high pressure die cast (HPDC) AZ91 Mg substrate via high resolution scanning transmission electron microscopy, in situ micro-tensile testing, and finite element method (FEM) modeling. Micro-tensile pillars fabricated using the plasma focused ion beam (PFIB) successfully isolates the coating-substrate interface within the gauge length. The average bond strength of Zn-Mg interface was determined to be ∼140 MPa with failure occurring partially at the interface and mostly into the coatings. A detailed microstructural characterization revealed evidence of a strong metallurgical bonding at the Zn-Mg interface and formation of the C14 MgZn 2 laves phase interlayer resulting in a mixed mode of fracture during the micro-tensile experiments. FEM modeling reveals the stress distribution along the interfaces and suggests that a MgZn 2 layer thickness between 200–400 nm is optimum to increase the bond strength and minimize the triaxiality. Such a site-specific interfacial analysis with correlative computational modeling provides crucial insight into the overall performance of cold spray interfaces.

Bond strength↗
DOE OSTI2020

Biaxial Strains Mediated Oxygen Reduction Electrocatalysis on Fenton Reaction Resistant L1 0 ‐PtZn Fuel Cell Cathode

Abstract PtM alloy catalysts (e.g., PtFe, PtCo), especially in an intermetallic L1 0 structure, have attracted considerable interest due to their respectable activity and stability for the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs). However, metal‐catalyzed formation of ·OH from H 2 O 2 (i.e., Fenton reaction) by Fe‐ or Co‐containing catalysts causes severe degradation of PEM/catalyst layers, hindering the prospects of commercial applications. Zinc is known as an antioxidant in Fenton reaction, but is rarely alloyed with Pt owing to its relatively negative redox potential. Here, sub‐4 nm intermetallic L1 0 ‐PtZn nanoparticles (NPs) are synthesized as high‐performance PEMFC cathode catalysts. In PEMFC tests, the L1 0 ‐PtZn cathode achieves outstanding activity (0.52 A mg Pt −1 at 0.9 V iR ‐free , and peak power density of 2.00 W cm −2 ) and stability (only 16.6% loss in mass activity after 30 000 voltage cycles), exceeding the U.S. DOE 2020 targets and most of the reported ORR catalysts. Density function theory calculations reveal that biaxial strains developed upon the disorder‐order (A1L1 0 ) transition of PtZn NPs would modulate the surface PtPt distances and optimize PtO binding for ORR activity enhancement, while the increased vacancy formation energy of Zn atoms in an ordered structure accounts for the improved stability.

Liang, Jiashun↗
DOE OSTI2020

Advanced cast aluminum alloys for automotive engine application with superior high-temperature properties

A high fatigue strength aluminum alloy comprises in weight percent copper 3.0-3.5%, iron 0-1.3%, magnesium 0.24-0.35%, manganese 0-0.8%, silicon 6.5-12.0%, strontium 0-0.025%, titanium 0.05-0.2%, vanadium 0.20-0.35%, zinc 0-3.0%, zirconium 0.2-0.4%, a maximum of 0.5% other elements and balance aluminum plus impurities. The alloy defines a microstructure having an aluminum matrix with the Zr and the V in solid solution after solidification. The matrix has solid solution Zr of at least 0.16% after heat treatment and solid solution V of at least 0.20% after heat treatment, and both Cu and Mg are dissolved into the aluminum matrix during the heat treatment and subsequently precipitated during the heat treatment. A process for heat treating an Al—Si—Cu—Mg—Fe—Zn—Mn—Sr-TMs alloy comprises heat treating the alloy to produce a microstructure having a matrix with Zr and V in solid solution after solidification.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Material-Dependent Antagonistic Effects between Soot and ZDDP

While soot in engine oil is known to accelerate the wear of diesel and gasoline direct-injection compression-ignition engines, there is a lack of consensus on the wear mechanism though various hypotheses have been proposed in the literature. Particularly, some recently observed antagonistic effects between soot and a common lubricant antiwear additive, zinc dialkyldithiophosphate (ZDDP), while others did not. The discrepancy is, in part, explained by the strong alloy dependence of such antagonism discovered in this study. Specifically, four alloys, 52100 steel and M2, M50, and A2 tool steels, are tested in lubricants containing carbon black (CB, a soot surrogate) with and without ZDDP present. Adding the CB alone to the oil increases the wear rate for all steel alloys as expected. However, distinct wear performance is observed for the four steel alloys when ZDDP is introduced to the CB-containing oil: while the 52100 steel has notable wear reduction, the three tool steels suffer significant wear increase. Comprehensive tribofilm characterization suggests that the Mo content in the steel alloy and the sulfur from ZDDP strongly influence wear behavior. The combination of CB/Mo-catalyzed sulfidation and CB-accelerated abrasion is hypothesized to be responsible for the high wear of the Mo-alloyed tool steels.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Electrical and structural properties of binary Ga–Sb phase change memory alloys

Material properties of Ga–Sb binary alloy thin films deposited under ultra-high vacuum conditions were studied for analog phase change memory (PCM) applications. Crystallization of this alloy was shown to occur in the temperature range of 180–264 °C, with activation energy >2.5 eV depending on the composition. X-ray diffraction (XRD) studies showed phase separation upon crystallization into two phases, Ga-doped A7 antimony and cubic zinc-blende GaSb. Synchrotron in situ XRD analysis revealed that crystallization into the A7 phase is accompanied by Ga out-diffusion from the grains. X-ray absorption fine structure studies of the local structure of these alloys demonstrated a bond length decrease with a stable coordination number of 4 upon amorphous-to-crystalline phase transformation. Mushroom cell structures built with Ga–Sb alloys on ø110 nm TiN heater show a phase change material resistance switching behavior with resistance ratio >100 under electrical pulse measurements. TEM and Energy Dispersive Spectroscopy (EDS) studies of the Ga–Sb cells after ∼100 switching cycles revealed that partial SET or intermediate resistance states are attained by the variation of the grain size of the material as well as the Ga content in the A7 phase. A mechanism for a reversible composition control is proposed for analog cell performance. These results indicate that Te-free Ga–Sb binary alloys are potential candidates for analog PCM applications.

Ume, Rubab (ORCID:0000000324766900)↗
DOE OSTI2023

Microstructural evolution and intermetallic formation in Zn-3Mg (wt%) powder mixture processed by high-pressure torsion

Severe plastic deformation (SPD) techniques have been used extensively over the past 40 years for producing strong metals and alloys. High-pressure torsion (HPT) is one of the most promising SPD techniques for achieving high strength through nanoscale grain refinement and phase transformation. In this research, a mixture of pure zinc (Zn) and magnesium (Mg) powders, Zn-3Mg (wt%), was HPT-processed under a pressure of 6 GPa for 1, 5, 10, 20, and 30 turns at room temperature to achieve a high strength biodegradable material. In order to understand the effects of pre-consolidation on the resulting microstructure and hardness, HPT processing was performed on loose powders placed in the die and also on a pre-compacted powder mixture and the resulting HPT disks were characterized by X-ray diffraction, scanning electron microscopy, atom probe tomography, and Vickers microhardness. In both cases, the HPT disk microstructures contained nanoscale grains, and stable and metastable strain-induced intermetallics, but an unusual softening appeared at large shear strains. Grain size, grain morphology, and the formation of different intermetallics were analyzed to explain the unusual hardness distribution, and it was found that an inverse Hall-Petch relationship between hardness and grain size exists. It is suggested that thermally-activated phenomena such as grain boundary sliding contributed to the strain-induced softening of this nano-structured biomaterial due to its low melting point. Finally, the current results are compared with those for HPT-processed cast alloys and hybrids of the same composition.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Zinc treatment to enhance nickel electrode performance for liquid alkaline water electrolyzers

Raney Ni treatment is introduced to the surface of Ni mesh anode electrodes, enhancing liquid alkaline water electrolyzer performance. The surface of the Ni mesh is alloyed with Zn, deposited by either an aqueous infiltration of Zn salt or direct reaction with Zn foil. The extent of alloying is controlled by a heat treatment step. For both processes, fine porosity and enhanced surface area are obtained after leaching the Zn out of the surface alloy layer. The observed electrode surface structure and performance is quite sensitive to the thermal treatment temperature. The enhanced surface area improves full cell performance by 90 mV for infiltrated Zn treated at 600 °C and by 185 mV for Zn foil reacted at 425 °C (at 2 A cm −2 and 80 °C). In conclusion, the Zn treatment methods produce stable operating performance, exhibiting no decay after 150 h for the infiltrated Zn treated at 600 °C, and a decay rate of 4.6 μV h −1 over 100 h for the Zn foil reacted at 425 °C (at 1 A cm −2 and 80 °C).

LAWE↗
DOE OSTI2023

From Inside Out: How the Buried Interface, Shell Defects, and Surface Chemistry Conspire to Determine Optical Performance in Nonblinking Giant Quantum Dots

“Giant” or core/thick‐shell quantum dots (gQDs) are an important class of solid‐state quantum emitter characterized by strongly suppressed blinking and photobleaching under ambient conditions, and reduced nonradiative Auger processes. Together, these qualities provide distinguishing and useful functionality as single‐ and ensemble‐photon sources. For many applications, operation at elevated temperatures and under intense photon flux is desired, but performance is strongly dependent on the synthetic method employed for thick‐shell growth. Here, a comprehensive analysis of gQD structural properties “from the inside out” as a function of shell‐growth method is reported: successive ionic layer adsorption and reaction (SILAR) and high‐temperature continuous injection (HT‐CI), or sequential combinations of the two. Key correlations across synthesis methods, structural features (interfacial alloying, stacking‐fault density and surface‐ligand identity), and performance metrics (quantum yield, single‐gQD photoluminescence under thermal/photo stress, charging behavior and quantum‐optical properties) are identified. Surprisingly, it is found that interfacial alloying is the strongest indicator of gQD stability under stress, but this parameter is not the determining factor for Auger suppression. Furthermore, quantum yield is strongly influenced by surface chemistry and can approach unity even in the case of high shell‐defect density, while introduction of zinc‐blende stacking faults increases the likelihood that a gQD exhibits charged‐state emission.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2022

The state of zinc in methanol synthesis over a Zn/ZnO/Cu(211) model catalyst

The active chemical state of zinc (Zn) in a zinc-copper (Zn-Cu) catalyst during carbon dioxide/carbon monoxide (CO 2 /CO) hydrogenation has been debated to be Zn oxide (ZnO) nanoparticles, metallic Zn, or a Zn-Cu surface alloy. We used x-ray photoelectron spectroscopy at 180 to 500 millibar to probe the nature of Zn and reaction intermediates during CO 2 /CO hydrogenation over Zn/ZnO/Cu(211), where the temperature is sufficiently high for the reaction to rapidly turn over, thus creating an almost adsorbate-free surface. Tuning of the grazing incidence angle makes it possible to achieve either surface or bulk sensitivity. Hydrogenation of CO 2 gives preference to ZnO in the form of clusters or nanoparticles, whereas in pure CO a surface Zn-Cu alloy becomes more prominent. Here, the results reveal a specific role of CO in the formation of the Zn-Cu surface alloy as an active phase that facilitates efficient CO 2 methanol synthesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Robust passivation of CdSeTe based solar cells using reactively sputtered magnesium zinc oxide

Magnesium zinc oxide (MZO, Mg x Zn 1-x O) is a leading emitter for CdTe-based solar cells due to its transparency and the ability to tune its conduction band offset with the absorber. Devices employing alloyed cadmium selenide telluride (CST, CdSe y Te 1-y ) absorbers achieved high efficiency (>19%) using MZO deposited by reactive sputtering over a broad composition range (3.68–3.92 eV, x: 0.20–0.35). Minimal differences in implied and measured open circuit voltage indicate that the contacts are well passivated and highly selective across the spectrum of MZO employed. Device performance insensitivity to MZO composition, which is not observed in CdTe devices, is attributed to the formation of an oxygenated interface layer. Se volatility creates a group VI deficiency at the interface that drives O migration from the MZO into the absorber. This introduces conductivity in the emitter not present in its as-deposited state, contributing to the exceptional performance observed. It is shown that the quality of device passivation depends on the oxidation state of the as-deposited MZO such that intelligent control and management of the reactive sputtering process is required.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Electrodeposited Aluminum Oxide as Alternative to Conventional Pretreatments

Iron and zinc phosphate pretreatments are still heavily used in both the oil & gas and automotive industries as adhesion promoters for paints and E-coat systems. These solutions are known to generate hazardous sludges and rinse water which must be periodically disposed of, a problem made worse by the increasing desire for aluminum alloy incorporation in vehicles. This presentation will introduce novel electrodeposited aluminum oxide pretreatments as a sustainable alternative to phosphates. The aluminum oxide coatings improve corrosion resistance and paint adhesion, generate no hazardous waste streams, are cost-effective, and can be applied to any metal surface. This new type of surface pretreatment can conform to TT-C-490 Type IV and VI for Military applications on both ferrous and non-ferrous surfaces as well as automotive specifications for equivalent civilian markets. The thin aluminum oxide treatment also supports the development of lightweight coatings systems for automotive and aerospace applications without sacrificing performance and is a perfect complement to the E-coating process. Since aluminum oxide uses a chemical binding mechanism for paints, the surface can even be modified to offer excellent paint adhesion and corrosion resistance directly to top-coats without the need for primer. This opens a pathway to fewer coating steps for simplified paint application and lightweight, next-generation coatings systems.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Cesium Removal from Surrogate Pyroprocessing Salt by Electrodeposition

Active metals in used nuclear fuel dissolve into the salt during pyroprocessing and are not removed by electrorefining or drawdown operations. The buildup of 137 Cs over time increases the heat load and ionizing radiation level of the salt such that it must be replaced frequently, resulting in a significant amount of salt waste. An effective means of managing cesium in the molten salt electrolyte would increase the efficiency of pyroprocessing and decrease the volume of salt waste requiring disposal. A previous report summarized issues that must be addressed when developing a removal strategy and assessed the suitability of existing methods and remaining technological gaps to their application (Rose and Thomas 2023). Cesium is extremely stable in molten salt as a chloride—even more stable than the LiCl-KCl eutectic base salt used for pyroprocessing fuel—which makes removing cesium a challenge. However, sufficiently strong atomic interactions occur between active metal species and liquid metals that make the electrodeposition of active metal fission products into liquid metal electrodes energetically favorable. The feasibility of recovering cesium from LiCl-KCl pyroprocessing salt through electrodeposition into liquid metals is eing assessed by identifying potentially effective liquid metals and performing tests to determine the effectiveness of electrodepositing cesium from a LiCl/KCl salt into these liquid metals. Previous studies investigating the electrodeposition of Sr 2+ , and Ba 2+ into zinc, cadmium, bismuth, lead, tin and antimony have shown that alkali and alkaline earth metals can be electrodeposited at liquid metal cathodes (Kim et al., 2018). The removal of Ba 2+ and Sr 2+ was measured to be more efficient than the removal of monovalent cations due to the greater thermochemical driving force for alloying those elements with the liquid metal (Jang et al. 2022). Because the equilibrium potentials are dependent on the interactions of the active metal in the liquid metal, it is likely that the other alkali metals Li + , and K + , will deposit from LiCl/KCl salt with the Cs + . Therefore, application of this method to recover active metals from pyroprocessing salt will benefit from the use of a liquid metal and set of operating conditions that sufficiently increase the reduction potential of cesium to remove cesium from the waste salt with an acceptable amount of co-deposited lithium and potassium.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2023

Atmospheric Pressure Plasma Treatment of Magnesium Alloy for Enhanced Coating Adhesion and Corrosion Resistance

Atmospheric pressure plasma (AP) treatment, using an open-air jet of ionized CO 2 , N 2 , or air, was applied to AZ91D Mg alloy surfaces to investigate its effects on primer coating adhesion and corrosion resistance. The CO 2 and air AP treatments formed an O- and C-rich surface layer (Mg-O-C) consisting of agglomerated nanoparticles and pits with a depth of a few microns and increasing the surface roughness by 6–8 times compared with the reference 600 grit-finished surface. Then, three commercial primers, zinc phosphate (ZnP), chromate-containing epoxy, and MIL23377, were applied on the treated surfaces to evaluate the corrosion resistance associated with the coating adhesion. Microscopic analysis demonstrated stronger interlocking between the primer layer and the nano-/microrough Mg-O-C surface compared to the untreated (600 grit-finished) surfaces, indicating improved coating adhesion and corrosion resistance. Crosscut tests of the MIL23377 primer on the CO 2 and air AP-treated surfaces showed the highest level of adhesion, ASTM class 5B. Salt spray corrosion tests showed that after 8 days of exposure, the primer coatings on air AP-treated surfaces had corrosion areas that were more than four times smaller than that of the 600 grit-finished surface. The N 2 AP treatment showed similar adhesion enhancement. The preliminary operation expenses for AP treatment using CO 2 , N 2 , and air were estimated at USD 30.62, USD 35.45, and USD 29.75 (from an air cylinder)/USD 0.66 (from an air compressor) per m 2 , respectively.

36 MATERIALS SCIENCE↗