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At least 217 records · Page 12
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Phase-Selective Synthesis of Rhombohedral WS 2 Multilayers by Confined-Space Hybrid Metal–Organic Chemical Vapor Deposition

Rhombohedral polytype transition metal dichalcogenide (TMDC) multilayers exhibit non-centrosymmetric interlayer stacking, which yields intriguing properties such as ferroelectricity, a large second-order susceptibility coefficient χ (2) , giant valley coherence, and a bulk photovoltaic effect. These properties have spurred significant interest in developing phase-selective growth methods for multilayer rhombohedral TMDC films. Here, in this study, we report a confined-space, hybrid metal–organic chemical vapor deposition method that preferentially grows 3R-WS 2 multilayer films with thickness up to 130 nm. We confirm the 3R stacking structure via polarization-resolved second-harmonic generation characterization and the 3-fold symmetry revealed by anisotropic H 2 O 2 etching. The multilayer 3R WS 2 shows a dendritic morphology, which is indicative of diffusion-limited growth. Multilayer regions with large, stepped terraces enable layer-resolved evaluation of the optical properties of 3R-WS 2 via Raman, photoluminescence, and differential reflectance spectroscopy. These measurements confirm the interfacial quality and suggest ferroelectric modification of the exciton energies.

3R-WS2↗
DOE OSTI2023

PtCo/MWCNTs Prepared by a Microwave‐assisted Polyol Method for Selective Cinnamaldehyde Hydrogenation

Abstract Using microwave irradiation, PtCo alloy nanoparticles were deposited within a few minutes on COOH‐functionalized MWCNT supports. The obtained catalysts were used for selective hydrogenation of cinnamaldehyde, a reaction whose products are widely used in various fields. In the selective cinnamaldehyde hydrogenation to cinnamyl alcohol, microwave‐prepared catalysts (generically, Pt x Co y ‐MW) outperformed a catalyst prepared by the conventional method (Pt 1 Co 2 ‐con). The highest selective hydrogenation to cinnamyl alcohol, 89%, was obtained using Pt 1 Co 2 ‐MW, while Pt 1 Co 2 ‐con showed a selectivity of 76%. Characterization results confirmed that the microwave prepared samples had a stronger interaction between Pt and Co than that in the Pt 1 Co 2 ‐con sample. The alloyed Co altered the electronic structure of Pt, leading to favorable adsorption of the C=O bond by the lone‐pair electrons of its oxygen atom. Moreover, the Pt 1 Co 2 ‐MW sample showed neglectable change in catalytic performance (e. g., cinnamaldehyde conversion and selective hydrogenation to cinnamyl alcohol) during recycling experiments.

Wang, Kaiying↗
NASA NTRS2002

Solar Selective Coatings Developed for Space Power Applications

A solar collector having the combined properties of high solar absorptance, low infrared emittance, and high thermal conductivity is envisioned for space power applications on minisatellites. A high solar absorptance is needed to collect as much of the incident solar radiation as possible and a low infrared emittance is needed to minimize radiant energy losses. A lightweight material having a high thermal conductivity is needed to transport the absorbed energy to where it is needed. Such a solar collector may be used with a low temperature-differential heat engine to provide electric power to the minisatellite components or as a source of thermal energy for a thermal bus that would heat remote regions of the spacecraft. The key to such a collector is the use of cermet coatings. Cermet coatings are composed of molecular islands of metal embedded in a three-dimensional matrix of dielectric. Recent research on molecular mixtures of aluminum and aluminum oxide at the NASA Glenn Research Center has yielded cermet coatings with a solar absorptance a of 0.797 and an infrared emittance epsilon of 0.131, yielding an alpha/epsilon ratio of 6. Although additional work is needed to further increase the alpha/epsilon ratio, these coatings are attractive owing to their potential durability in the space environment. The aluminum oxide surface should provide substantial protection from the atomic oxygen found in low Earth orbit. To help minimize emittance, these coatings are deposited on a smooth surface. The selected surface is aluminum that has been diamond turned to a mirror finish. Cermet coatings are manufactured by sputter deposition. To achieve the desired variable composition, Glenn's researchers implemented a novel approach using a cylindrical target composed of aluminum and aluminum oxide. Rotating the cylinder during the deposition process yields a coating of variable composition. A photograph of the custom-made aluminum and aluminum oxide cylindrical target installed in the sputter deposition chamber is shown.

Jaworske, Donald A.↗
DOE OSTI2025

Selectivity of tris complexation for Ni(II), Co(II), and Fe(II) and its effect on carbonate precipitation under alkaline conditions

Simultaneous critical element recovery and ex-situ carbon mineralization of low-grade ultramafic deposits have garnered increasing interest. Understanding the selectivity of metal complexing organic ligands for various divalent metals present in ultramafic rocks during carbonate mineralization is required to optimize this process. Here we evaluate 2-amino-2-(hydroxymethyl)-1,3-propanediol (i.e., Tris) as a model for bidentate ligands that bind divalent metals with both amine and alcohol groups in alkaline conditions (pH 8–10.5) at 25 °C and 80 °C in carbonate-buffered solutions. Protonated Tris forms a stronger complex with metal ions and is selective for trace metals with Ni(II) > Co(II) > Fe(II) during carbonate precipitation, with the rates decreasing but selectivity increasing at lower temperature and lower pH. At 25 °C, metastable amorphous hydrated carbonates form, regardless of the amount of Tris present or pH values. At 80 °C and pH 8, the Co and Fe carbonates that form are a mixture of rosasite-group minerals (Co 2 CO 3 (OH) 2 (H 2 O) and Fe 2 CO 3 (OH) 2 ) and pure carbonates (sphaerocobaltite: CoCO 3 and siderite: FeCO 3 ), with the latter more stabilized with increasing Tris concentration. In mixed metal solutions without Tris at 25 °C where Fe:Ni or Fe:Co is 2:1, Fe increases the rates of Ni or Co carbonate precipitation. However, with increasing Tris concentration the presence of Ni or Co inhibits Fe carbonate precipitation. At 80 °C without Tris, Ni or Co substitute into the iron chukanovite (Fe 2 CO 3 (OH) 2 ) lattice, increasing Ni or Co carbonate precipitation rates. Increasing Tris concentration only slightly inhibits Fe and Co precipitation, but slows Ni precipitation up to 10 times, with Fe progressively partitioning into more pure carbonate phases with distinct crystalline morphologies. These findings suggest bidentate amine-bearing ligands may be effective at Ni and Co recovery during carbon mineralization of Fe-bearing ultramafic deposits at relatively low temperatures and slightly alkaline pH.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Wafer-scale growth of two-dimensional, phase-pure InSe

Two-dimensional (2D) indium monoselenide (InSe) has attracted significant attention as an ultrathin III–VI semiconductor with a combination of favorable attributes that are comparable to those of III–V semiconductors and van der Waals 2D transition-metal dichalcogenides. Nevertheless, there has been no demonstration of large-area synthesis of 2D InSe due to the complexity of the binary In-Se system and the difficulties in promoting lateral growth. Here, we report the polymorph-selective synthesis of epitaxial 2D InSe by metal-organic chemical vapor deposition (MOCVD) over 2-in wafers. We achieve polymorph-selective epitaxial growth of InSe on c-plane sapphire via flow modulation to control the Se/In ratio. The layer-by-layer growth allows thickness control with tunable optical properties comparable to those of bulk crystals. We also demonstrate gate-tunable electrical transport with a field-effect mobility comparable to that of single-crystalline flakes. Importantly, these results indicate that InSe grown by MOCVD could be an effective channel material for back-end-of-line integration in logic transistors.

2D materials↗
NASA NTRS2001

Apparatus and process for freeform fabrication of composite reinforcement preforms

A solid freeform fabrication process and apparatus for making a three-dimensional reinforcement shape. The process comprises the steps of (1) operating a multiple-channel material deposition device for dispensing a liquid adhesive composition and selected reinforcement materials at predetermined proportions onto a work surface; (2) during the material deposition process, moving the deposition device and the work surface relative to each other in an X-Y plane defined by first and second directions and in a Z direction orthogonal to the X-Y plane so that the materials are deposited to form a first layer of the shape; (3) repeating these steps to deposit multiple layers for forming a three-dimensional preform shape; and (4) periodically hardening the adhesive to rigidize individual layers of the preform. These steps are preferably executed under the control of a computer system by taking additional steps of (5) creating a geometry of the shape on the computer with the geometry including a plurality of segments defining the preform shape and each segment being preferably coded with a reinforcement composition defining a specific proportion of different reinforcement materials; (6) generating programmed signals corresponding to each of the segments in a predetermined sequence; and (7) moving the deposition device and the work surface relative to each other in response to these programmed signals. Preferably, the system is also operated to generate a support structure for any un-supported feature of the 3-D preform shape.

Yang, Junsheng↗
NASA NTRS2000

Friction and Wear Properties of Selected Solid Lubricating Films: Magnetron-Sputtered and Plasma-Assisted, Chemical-Vapor-Deposited Diamondlike Carbon Films - Part 3

To evaluate commercially developed dry solid film lubricants for aerospace bearing applications, an investigation was conducted to examine the friction and wear behavior of magnetron-sputtered diamondlike carbon (MS DLC) and plasma-assisted, chemical-vapor-deposited diamondlike carbon (PACVD DLC) films in sliding contact with 6-mm-diameter American Iron and Steel Institute (AISI) 440C stainless steel balls. Unidirectional sliding friction experiments were conducted with a load of 5.9 N (600 g), a mean Hertzian contact pressure of 0.79 GPa (maximum Hertzian contact pressure of L-2 GPa), and a sliding velocity of 0.2 m/s. The experiments were conducted at room temperature in three environments: ultrahigh vacuum (vacuum pressure, 7x10(exp -7) Pa), humid air (relative humidity, approx.20 percent), and dry nitrogen (relative humidity, <1 percent). The resultant films were characterized by scanning electron microscopy, energy-dispersive x-ray spectroscopy, and surface profilometry. Marked differences in the friction and wear of the DLC films investigated herein resulted from the environmental conditions. The main criteria for judging the performance of the DLC films were coefficient of friction and wear rate, which had to be less than 0.3 and on the order of 10(exp -6) cu mm/N-m or less, respectively. MS DLC films and PACVD DLC films met the criteria in humid air and dry nitrogen but failed in ultrahigh vacuum, where the coefficients of friction were greater than the criterion, 0.3. In sliding contact with 440C stainless steel balls in all three environments the PACVD DLC films exhibited better tribological performance (i.e., lower friction and wear) than the MS DLC films. All sliding involved adhesive transfer of wear materials: transfer of DLC wear debris to the counterpart 440C stainless steel and transfer of 440C stainless steel wear debris to the counterpart DLC film.

Miyoshi, Kazuhisa↗
NASA NTRS2012

Method and system for near-field spectroscopy using targeted deposition of nanoparticles

There is provided in one embodiment of the invention a method for analyzing a sample material using surface enhanced spectroscopy. The method comprises the steps of imaging the sample material with an atomic force microscope (AFM) to select an area of interest for analysis, depositing nanoparticles onto the area of interest with an AFM tip, illuminating the deposited nanoparticles with a spectrometer excitation beam, and disengaging the AFM tip and acquiring a localized surface enhanced spectrum. The method may further comprise the step of using the AFM tip to modulate the spectrometer excitation beam above the deposited nanoparticles to obtain improved sensitivity data and higher spatial resolution data from the sample material. The invention further comprises in one embodiment a system for analyzing a sample material using surface enhanced spectroscopy.

Anderson, Mark S.↗
DOE OSTI2023

Ion soft landing: A unique tool for understanding electrochemical processes

Ion soft landing (SL) is a preparative mass spectrometry approach that enables deposition of mass- and charge-selected gaseous ions onto surfaces with controlled kinetic energy. The unique capabilities of SL provide an opportunity to populate electrode–electrolyte interfaces (EEIs) with well-defined intact electroactive ions of known composition, thereby facilitating the characterization of their intrinsic electrochemical properties. Here, in this perspective, we describe the SL technique and discuss how it may be used to study the effect of the charge state, stoichiometry, and composition of large redox active molecules and clusters on their electron transfer kinetics. SL has enabled the characterization of redox-active species that cannot be purified and examined using conventional bulk-phase separation and deposition approaches. Furthermore, precise control over the deposition process provides an opportunity to prepare and characterize well-defined EEIs relevant to energy storage and conversion, catalysis, and sensing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Long-Term Stability in Perovskite Solar Cells Through Atomic Layer Deposition of Tin Oxide

Robust contact schemes that boost stability and simplify the production process are needed for perovskite solar cells (PSCs). We codeposited perovskite and hole-selective contact while protecting the perovskite to enable deposition of SnOx/Ag without the use of a fullerene. The SnOx, prepared through atomic layer deposition, serves as a durable inorganic electron transport layer. Tailoring the oxygen vacancy defects in the SnOx layer led to power conversion efficiencies (PCEs) of >25%. Our devices exhibit superior stability over conventional p-i-n PSCs, successfully meeting several benchmark stability tests. They retained >95% PCE after 2000 hours of continuous operation at their maximum power point under simulated AM1.5 illumination at 65degrees C. Additionally, they boast a certified T97 lifetime exceeding 1000 hours.

c60↗
NASA NTRS2021

Thermal Radiator for CO2 Deposition in Deep Space Transit (FY21 XHab Final Report - University of North Texas)

This UNT Senior design team was tasked by NASA to develop a variable conductance thermal radiator prototype for CO2 deposition for deep space transit. NASA selects university teams every year to partake in the X-HAB Academic Innovation Challenge, with this year’s number of teams being six. Air Revitalization is a crucial system for any space travel, be it for Low Earth Orbit, such as the International Space Station, or for deep space transit. Current systems, such as the Carbon Dioxide Removal Apparatus aboard the ISS, require upkeep and maintenance, which cannot be done on long distance space missions. For the past several years, NASA has done research on Cryogenic systems for Carbon Dioxide removal. These systems operate on the fact that Carbon Dioxide freezes at a higher temperature than Oxygen and Nitrogen, so Carbon Dioxide can be frozen out of the cabin atmosphere without the use of filters, which degrade over time. To cool the cabin air down to a temperature where Carbon Dioxide freezes, Stirling cryocoolers have been used, which have shown promise in the hope of Carbon Dioxide deposition for Cabin Air Revitalization. Cryogenic systems are much more reliable but require significant energy input to operate. Physical systems, such as radiators, have generally not been used for this task, as there is a need to be able to “turn off” the rejection of heat to allow the frozen carbon dioxide to be collected. However, with working fluids pumped through a physical radiator, that aspect of operation can be achieved. The goal of this challenge is to determine the effectiveness of a variable conductance thermal radiator that can reject heat to deep space, without the use of a dedicated cryocooler to remove energy from the cabin air. The proposed design uses piping, hot and cold working fluids, and non-condensable gas to absorbl heat from the cabin air on one side of the radiator and reject the heat to deep space by means of thermal radiation. As well, the system will allow for the recovery of deposited Carbon Dioxide. The UNT X-HAB 2021 team will create a model radiator and test its performance with simulated heat sources and sinks and extrapolate those data points to analyze for real world conditions.

Travis Seaver↗
DOE OSTI2021

Grafted nickel-promoter catalysts for dry reforming of methane identified through high-throughput experimentation

High-throughput synthesis of a series of monometallic and bimetallic catalysts (45 bimetallic and 50 monometallic samples) consisting of nickel and one of nine different metal promoters (B, Co, Cu, Fe, Mg, Mn, Sn, V and Zn) supported on one of six different metal oxides alumina, ceria, magnesia, silica and titania) is carried out via organometallic grafting using a robotic platform. The catalysts are evaluated for their activity and selectivity for the dry reforming of methane at a feed ratio of CH 4 :CO 2 of 1 at 650–800 °C in a parallel flow reactor system. The type of oxide support prevails over the type of additive for both catalyst activity and stability. On Al 2 O 3 and MgO, Fe was found to be the best promoter; on SiO 2 , Cu is the best promoter at 700 °C and higher, while on TiO 2 , Mn is found to enhance the conversion at 800 °C. On CeO 2 , all additives except Fe have beneficial effects. Twenty-five catalysts show > 90% methane conversion with ten catalysts showing > 95% conversion at 800 °C with the H 2 :CO ratios ranging from 0.8 to 1.2. Amongst the ten highest performers, NiFe/Al 2 O 3 and NiFe/MgO are more active than Ni/Al 2 O 3 and Ni/MgO, respectively and were stable over a period of 25 h at 800 °C. Characterization on the as-prepared samples reveals highly dispersed phase, while after reduction in H 2 , highly dispersed and reduced nickel particles up to 10 nm are formed. The particles do not increase in size under dry reforming reaction conditions at 800 °C. An increased hydrogen consumption observed during H 2 -TPR of the nickel particles is positively correlated with methane conversion for Al 2 O 3 -based catalysts. The resistance to deactivation by coking and variation in coke structure are investigated by spectroscopic and microscopic methods to identify the relationship between metal promoters, alloy formation, and type of surface carbon deposits. Carbon whiskers were observed on the ten selected spent samples and are preferentially deposited on Ni rather than on the promoters. Carbon nanotube formation and metal particle removal from support were not observed to cause deactivation while amorphous carbon formation was clearly linked to catalyst deactivation, as amorphous carbon could encapsulate nickel, either on the support or at the end of the carbon nanotube. Furthermore, the organometallic grafting technique is an efficient and suitable technique for synthesizing highly dispersed and homogeneous phases which lead to high conversion and high durability for dry reforming of methane.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Synthesis of platinum nanoparticles on strontium titanate nanocuboids via surface organometallic grafting for the catalytic hydrogenolysis of plastic waste

Pt/SrTiO 3 (Pt/STO), prepared on small scale by atomic layer deposition (ALD), is a capable heterogeneous catalyst for the selective hydrogenolysis of polyolefins to hydrocarbon oils, providing a promising approach for upcycling plastic waste. However, because deposition by ALD is costly and resource-intensive, a new synthesis of Pt/STO is needed to effectively scale catalyst production and pursue the commercialization of upcycling processes. To that effect, this work details a scalable deposition method for Pt/STO made by surface organometallic chemistry (SOMC) techniques using Pt(II) acetylacetonate or and trimethyl(methylcyclopentadienyl)platinum. The STO support was calcined (550 °C), treated with ozone (200 °C), and finally steamed (200 °C) to afford a clean STO surface populated with only hydroxyl groups. Pt precursors were dissolved in toluene and deposited onto STO. After reduction at 300 °C, the STO support was decorated with 1.0–1.5 nm Pt nanoparticles. The size and loading of these nanoparticles were varied by employing a multi-cycle deposition and oxidation and/or reduction process designed to ALD techniques. In conclusion, these Pt/STO catalysts hydrogenolyzed isotactic polypropylene into liquid products (>95% yield) with average molecular weights of 200–300 Da (~25 carbon atoms) and narrow size distributions at 300 °C and 180 psi H 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Origin of dislocation structures in an additively manufactured austenitic stainless steel 316L

In this experiment, the origin of dislocation structures in AM stainless steels was systematically investigated by controlling the effect of thermal stress through geometric constraints for the first time. Stainless steel 316L parts were produced in the form of “1D” rods, “2D” walls, and "3D" rectangular prisms to evaluate the effect of constraints to thermal expansion/shrinkage on the development of defect microstructures and to elucidate the origin of additively manufactured (AM) dislocation microstructures. Dislocation density, organization, chemical micro-segregation, precipitate structures, and misorientations were analyzed as a function of increasing constraints around solidifying material in 1D, 2D, and 3D components built using both directed energy deposition (DED) and powder-bed selective laser melting (SLM). In DED parts, the dislocation density was not dependent on local misorientations or micro-segregation patterns, but evolved from approximately ρ ⊥ = 10 12 m -2 in 1D parts to ρ ⊥ = 10 14 m -2 in 3D parts, indicating that it is primarily thermal distortions that produce AM dislocation structures. In DED 3D parts and SLM parts, dislocation densities were highest (ρ ⊥ ≈ 10 14 m -2 ) and corresponded to the formation of dislocation cells approximately 300-450 nm in diameter. Dislocation cells overlapped with dendrite micro-segregation in some but not all cases. The results illustrate that dendritic micro-segregation, precipitates, or local misorientations influence how the dislocations organize during processing, but are not responsible for producing the organized cell structures. Furthermore, this work shows that AM dislocation structures originate due to thermal distortions during printing, which are primarily dictated by constraints surrounding the melt pool and thermal cycling.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Nanoscale Measurements of Charge Transfer at Cocatalyst/Semiconductor Interfaces in BiVO 4 Particle Photocatalysts

Semiconductor photocatalyst particles convert solar energy to fuels like H 2 . The particles are often assumed to provide crystalline-facet-dependent electron-hole separation. A common strategy is to deposit HER electrocatalyst on electron-selective facets and OER electrocatalyst on hole-selective facets. A precise understanding of how charge-carrier-selective contacts emerges and how they rationally designed, however, is missing. Using a combination of ex-situ and in-situ conducting-AFM experiments and new ionomer/catalyst-semiconductor test structures, we show how heterogeneity in charge-carrier selectivity can be measured at the nanoscale. We discover that the presence of interface water/electrolyte is critical to induce hole selectivity between the CoO x water-oxidation catalyst and the BiVO 4 light absorber. pH-dependent measurements suggest that negative surface charge on the semiconductor is central to inducing hole selectivity. Furthermore, the work also demonstrates a new approach to control local pH and introduce water using thin-film ionomers compatible with conductive-AFM measurements.

14 SOLAR ENERGY↗
DOE OSTI2022

On-Surface Single-Molecule Identification of Mass-Selected Cyclodextrin-Supported Polyoxovanadates for Multistate Resistive-Switching Memory Applications

Polyoxovanadate anions immobilized on conducting substrates are promising candidates for molecule-based memory technologies. However, strong electronic interactions with the substrate and the formation of larger agglomerates remain bottlenecks on the way to their technical application. We demonstrate that ion soft-landing of mass selected cyclodextrin- functionalized hexavanadates enables to deposit these host-guest complexes as single memory units on surfaces without their quaternary ammonium countercations from solution. The cyclodextrin provides a stabilizing “shell” for the dianions. Further, multistate switching evidenced by the change in molecular resistance has been detected using scanning tunneling microscopy and spectroscopy and attributed to reduction of individual vanadium (+V) centers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Electrodepositing Textured Sn Film as a Highly Reversible Anode for Aqueous Batteries

Electrodepositing metal materials in large capacity, at low potential, and with high reversibility serves as the foundation for any aqueous rechargeable battery chemistry to realize the promises of high energy, low cost, and high safety. However, such a foundation is not solid because of the natural tendency of metals to form irregular, nonplanar, and often dendritic morphologies during electrochemical crystallization, which is further amplified in an acidic environment due to the faster kinetics of the coupled proton and mass-transport processes between hydrated metal ions and free metal atoms. As a typical representative, tin metal (Sn 0 ) has potential to achieve high energy in acidic batteries, but its nonuniform large-particle morphology, obtained from traditional electrodeposition, leads to dead Sn 0 formation and deteriorating reversibility, accompanied by the sustained hydrogen evolution reaction (HER) and active Sn 0 loss. Here, in this study, we report quaternary onium salts as effective interfacial cocations that, via selective adsorption, steadily texturize Sn 0 deposition along the (211) plane, which is intrinsically inert to the HER, thus regulating the film deposition process by favoring the formation of planar Sn 0 film. Such Sn 0 film brings exceptional reversibility in acidic electrolytes, which translates into sustained cycling stability at applicable areal capacities in both anode-half cells (similar to 1500 deposition/dissolution cycles at 5 mAh cm -2 ) and full cells (350 charge/discharge cycles at 5 mAh cm -2 ). Textured electrodeposition with intrinsic HER-suppression capability provides a universal solution for diverse metal anode materials in rechargeable energy-dense aqueous batteries.

Sn metal↗