Achieving superlubricity with 2D transition metal carbides (MXenes) and MXene/graphene coatings
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2D materials↗
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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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Intrinsic thermal interfacial resistance measurement in bonded metal–polymer foils
Heat conduction through bonded metal–polymer interfaces often limits the overall heat transfer in electronic packaging, batteries, and heat recovery systems. To design the thermal circuit in such systems, it is essential to measure the thermal interfacial resistance (TIR) across ~1 µm to 100 µm junctions. Previously reported TIR of metal–polymer junctions utilize ASTM E1530-based two-block systems that measure the TIR by applying pressure across the interface through external heating and cooling blocks. Here, we report a novel modification of the ASTM-E1530 technique that employs integrated heaters and sensors to provide an intrinsic TIR measurement of an adhesively bonded metal–polymer junction. We design the measurement technique using finite element simulations to either passively suppress or actively compensate the lateral heat diffusion through the polymer, which can minimize the systematic error to ≲5%. Through proof-of-concept experiments, we report the TIR of metal–polymer interfaces made from DuPont’s Pyralux double-side copper-clad laminates, commonly used in flexible printed circuit boards. Our TIR measurement errors are <10%. We highlight additional sources of errors due to non-idealities in the experiment and discuss possible ways to overcome them. Our measurement technique is also applicable to interfaces that are electrically insulating such as adhesively joined metal–metal junctions and sputter-coated or welded metal–polymer junctions. Altogether, the technique is capable of measuring TIR ≳10 –5 m 2 KW –1 in bonded metal–polymer foils and can be tailored for in situ measurements in flexible electronics, circuit packaging, and other hybrid metal–polymer systems.
47 OTHER INSTRUMENTATION↗
Chromium-Free Coating for Al Alloy Corrosion Protection Based on a Novel Ti/Mg Oxyfluoride
Chromium-free corrosion protection of aluminum alloys comparable to that of chromates (Cr(VI)) is demonstrated using a TiF 6 2– fluoro-anion-based coating recipe containing boric acid and a Mg salt. Boric acid drove TiF 6 2– hydrolysis enabling up to micrometer-scale thick coatings. The Mg salt led to deposition of a novel crystalline phase Ti/Mg oxyfluoride coating with an approximate composition of Ti 5 MgO 7 F 8 . Corrosion protection performance was characterized by polarization resistance measurements during immersion in 5% aqueous NaCl solution and neutral salt fog exposure following ASTM B.117. The performance is discussed in terms of the presence of fluoride in the coating enabling active behavior during its gradual depletion (in corrosion environments) toward a final composition approaching TiO 2 . This active corrosion protection mechanism may be more generally applicable for transition metal-based coatings that do not have high oxidation state oxo-anions, but do have stable fluoro-anions.
36 MATERIALS SCIENCE↗
Progress and Perspectives: Zirconium Electrodeposition from Different Electrolytes
Zirconium (Zr) possesses outstanding properties, including exceptional chemical resistance and a high melting point, and is therefore desirable for use in a wide variety of challenging environments, such as in nuclear reactors and the chemical processing industry. To minimize the amount of Zr required for any given application, developing methods for generating metallic Zr coatings is highly advantageous. Owing to Zr’s highly negative reduction potential, electrodeposition in traditional solvents at near ambient temperatures remains challenging and thus not well understood. Due to the extreme conditions required to deposit this metal, extensive work has been conducted in molten salt electrolytes, however the broad applicability of this methodology is limited due to its corrosivity. The primary focus of this article is to present an overview of Zr’s electrochemical behavior and to consolidate the efforts of researchers in exploring electrodeposition techniques for Zr involving aqueous, organic, ionic liquid, deep eutectic, and molten salt solvents. With this information, we highlight trends across solvent systems and opportunities for future research.
42 ENGINEERING↗
CFD/FEA Co-Simulation Framework for Analysis of the Thermal Barrier Coating Design and Its Impact on the HD Diesel Engine Performance
Thermal barrier coatings (TBCs) have been investigated both experimentally and through simulation for mixing controlled combustion (MCC) concepts as a method for reducing heat transfer losses and increasing cycle efficiency, but it is still a very active research area. Early studies were inconclusive, with different groups discovering obstacles to realizing the theoretical potential. Nuanced papers have shown that coating material properties, thickness, microstructure, and surface morphology/roughness all can impact the efficacy of the thermal barrier coating and must be accounted for. Adding to the complexities, a strong spatial and temporal heat flux inhomogeneity exists for mixing controlled combustion (diesel) imposed onto the surfaces from the impinging flame jets. In support of the United States Department of Energy SuperTruck II program goal to achieve 55% brake thermal efficiency on a heavy-duty diesel engines, this study sought to develop a deeper insight into the inhomogeneous heat flux from mixing controlled combustion on thermal barrier coatings and to infer concrete guidance for designing coatings. To that end, a co-simulation approach was developed that couples high-fidelity computational fluid dynamics (CFD) modeling of in-cylinder processes and combustion, and finite element analysis (FEA) modeling of the thermal barrier-coated and metal engine components to resolve spatial and temporal thermal boundary conditions. The models interface at the surface of the combustion chamber; FEA modeling predicts the spatially resolved surface temperature profile, while CFD develops insights into the effect of the thermal barrier coating on the combustion process and the boundary conditions on the gas side. The paper demonstrates the capability of the framework to estimate cycle impacts of the temperature swing at the surface, as well as identify critical locations on the piston/thermal barrier coating that exhibit the highest charge temperature and highest heat fluxes. In addition, the FEA results include predictions of thermal stresses, thus enabling insight into factors affecting coating durability. An example of the capability of the framework is provided to illustrate its use for investigating novel coatings and provide deeper insights to guide future coating design.
42 ENGINEERING↗
Nanowire-based hydrodesulfurization catalysts for hydrocarbon fuels
The present development is a metal particle coated nanowire catalyst for use in the hydrodesulfurization of fuels and a process for the production of the catalyst. The catalyst comprises titanium(IV) oxide nanowires wherein the nanowires are produced by exposure of a TiO2—KOH paste to microwave radiation. Metal particles selected from the group consisting of molybdenum, nickel, cobalt, tungsten, or a combination thereof, are impregnated on the metal oxide nanowire surface. The metal impregnated nanowires are sulfided to produce catalytically-active metal particles on the surface of the nanowires The catalysts of the present invention are intended for use in the removal of thiophenic sulfur from liquid fuels through a hydrodesulfurization (HDS) process in a fixed bed reactor. The presence of nanowires improves the HDS activity and reduces the sintering effect, therefore, the sulfur removal efficiency increases.
Sunkara, Mahendra Kumar↗
Nanowire-based hydrodesulfurization catalysts for hydrocarbon fuels
The present development is a metal particle coated nanowire catalyst for use in the hydrodesulfurization of fuels and a process for the production of the catalyst. The catalyst comprises titanium(IV) oxide nanowires wherein the nanowires are produced by exposure of a TiO2—KOH paste to microwave radiation. Metal particles selected from the group consisting of molybdenum, nickel, cobalt, tungsten, or a combination thereof, are impregnated on the metal oxide nanowire surface. The metal impregnated nanowires are sulfided to produce catalytically-active metal particles on the surface of the nanowires The catalysts of the present invention are intended for use in the removal of thiophenic sulfur from liquid fuels through a hydrodesulfurization (HDS) process in a fixed bed reactor. The presence of nanowires improves the HDS activity and reduces the sintering effect, therefore, the sulfur removal efficiency increases.
Sunkara, Mahendra K.↗
Infrared fluorescent coatings
The present invention provides for a composition comprising a pigment, wherein the composition is suitable for coating a surface that is, or is expected to be, exposed to the sun. The pigment comprises particles that fluoresce in sunlight, thereby remaining cooler in the sun than coatings pigmented with non-fluorescent particles. The particles comprise solids that fluoresce or glow in the visible or near infrared (NIR) spectra, or that fluoresce when doped. Suitable dopants include, but are not limited to, ions of rare earths and transition metals. A coating composition includes: (i) a film-forming resin; (ii) an infrared reflective pigment; and (iii) an infrared fluorescent pigment different from the infrared reflective pigment. When the coating composition is cured to form a coating and exposed to radiation comprising fluorescence-exciting radiation, the coating has a greater effective solar reflectance (ESR) compared to the same coating exposed to the radiation comprising fluorescence-exciting radiation except without the infrared fluorescent pigment. A multi-layer coating including the coating composition, and a substrate at least partially coated with the coating composition is also disclosed. A method of reducing temperature of an article includes applying the coating composition to at least a portion of the article.
Zalich, Michael Andrew↗
Infrared fluorescent coatings
The present invention provides for a composition comprising a pigment, wherein the composition is suitable for coating a surface that is, or is expected to be, exposed to the sun. The pigment comprises particles that fluoresce in sunlight, thereby remaining cooler in the sun than coatings pigmented with non-fluorescent particles. The particles comprise solids that fluoresce or glow in the visible or near infrared (NIR) spectra, or that fluoresce when doped. Suitable dopants include, but are not limited to, ions of rare earths and transition metals. A coating composition includes: (i) a film-forming resin; (ii) an infrared reflective pigment; and (iii) an infrared fluorescent pigment different from the infrared reflective pigment. When the coating composition is cured to form a coating and exposed to radiation comprising fluorescence-exciting radiation, the coating has a greater effective solar reflectance (ESR) compared to the same coating exposed to the radiation comprising fluorescence-exciting radiation except without the infrared fluorescent pigment. A multi-layer coating including the coating composition, and a substrate at least partially coated with the coating composition is also disclosed. A method of reducing temperature of an article includes applying the coating composition to at least a portion of the article.
Zalich, Michael Andrew↗
Environmental degradation of electroplated nickel and copper coated SS316H in molten FLiNaK salt
Corrosion of nickel and copper electroplated coatings on SS316H in molten FLiNaK salt was studied. 500- and 1000-hour static corrosion tests were performed in molten FLiNaK at 700 degrees Celsius. Characterization of the coatings following corrosion indicated that they did not degrade in the molten salt during the corrosion experiment and fully protected the underlying SS316H from chromium dissolution. Interdiffusion between the copper coating and SS316H was extremely limited, interdiffusion between the nickel coating and SS316H. Diffusion modelling revealed that the nickel coatings still significantly reduced chromium dissolution over 60 years despite the interdiffusion.
36 MATERIALS SCIENCE↗
MeV x-ray production from a petawatt laser in the regime of a relativistically transparent preplasma, with applications to radiography
Bright sources of mega-electron volt (MeV) x-rays have many unique applications, including nuclear physics, radiation oncology, and imaging high areal density systems. High intensity lasers (>1018 W cm−2) incident on mm-thick metal targets can deliver MeV x-rays via the bremsstrahlung process, providing sources with ultrashort duration (∼ps) and small source size (∼100 μm). Here, we report on a reproducible regime of laser-driven MeV x-ray sources, where the x-ray dose can be further increased by 60% by coating the metal target with micrometers of plastic. High fidelity numerical simulations indicate that the interaction is a result of relativistic transparency in the preplasma. Though relativistic transparency is present in both cases, the greater sound speed and smaller ion inertia of the plastic target allow the laser to more deeply penetrate and couple more efficiently to electrons. Radiography with this system demonstrates a resolving power < 300 μm, important for imaging applications.
70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
Transferring Liquid Metal to form a Hybrid Solid Electrolyte via a Wettability-Tuning Technology for Lithium-Metal Anodes
Integrating solid-state electrolyte (SSE) into Li-metal anodes has demonstrated great promise to unleash the high energy density of rechargeable Li-metal batteries. However, fabricating a highly cyclable SSE/Li-metal anode remains a major challenge because the densification of the SSE is usually incompatible with the reactive Li metal. Here, a liquid-metal-derived hybrid solid electrolyte (HSE) is proposed, and a facile transfer technology to construct an artificial HSE on the Li metal is reported. By tuning the wettability of the transfer substrates, electron- and ion-conductive liquid metal is sandwiched between electron-insulating and ion-conductive LiF and oxides to form the HSE. The transfer technology renders the HSE continuous, dense, and uniform. The HSE, having high ion transport, electron shut-off, and mechanical strength, makes the composite anode deliver excellent cyclability for over 4000 h at 0.5 mA cm(-2) and 1 mAh cm(-2) in a symmetrical cell. When pairing with LiFePO4 and sulfur cathodes, the HSE-coated Li metal dramatically enhances the performance of full cells. Therefore, this work demonstrates that tuning the interfacial wetting properties provides an alternate approach to build a robust solid electrolyte, which enables highly efficient Li-metal anodes.
li-metal anodes↗
Thermoluminescence and optically stimulated luminescence response of Al 2 O 3 coatings deposited by mist-chemical vapor deposition
Aluminum oxide (Al 2 O 3 ) is a widely used ceramic material which can be applied as a protective coating on metallic structures to improve corrosion resistance and mechanical properties. Al 2 O 3 also has great potential as a functional thin film device in optoelectronics. When it is doped with carbon (Al 2 O 3 :C), this material system can serve as a reliable radiation dosimeter. The combination of optoelectronic, dosimetric, and protective properties demonstrated by Al 2 O 3 uniquely positions it for dual use applications in nuclear forensics, nonproliferation and safeguards, emergency response, retrospective dosimetry, and nondestructive inspection. Here, in this study, an innovative ultrasonic mist-chemical vapor deposition (Mist-CVD) system was used to deposit thin (nm level) Al 2 O 3 coatings on 304 stainless steel substrates. The single aliquot regeneration (SAR) and additive dose reconstruction techniques were then used to investigate the thermoluminescence (TL) and optically stimulated luminescence (OSL) response of the coated substrates to increasing doses of β irradiation. This study demonstrates that nm-thick Al 2 O 3 coatings hold promise as novel nano-dosimeters which could be leveraged for a series of applications such as nonproliferation and safeguards, retrospective dosimetry, and nondestructive inspection.
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
Comparison of Na 2 SO 4 , K 2 SO 4 and Na 2 SO 4 -K 2 SO 4 deposit induced hot corrosion of a β-NiAl coating
Here, hot corrosion behaviour of a β-NiAl coating induced by Na 2 SO 4 , K 2 SO 4 , and Na 2 SO 4 -K 2 SO 4 deposits was investigated at 700 °C in air + 300 ppm SO 2 . To provide an insight into the corrosion mechanisms, phase equilibria of the Na 2 SO 4 -K 2 SO 4 -NiO-SO 3 system were calculated using an in-house developed thermodynamic database. The attack rates and morphologies could be correlated with the deposit compositions and their reactions with oxides. K 2 SO 4 and Na 2 SO 4 -K 2 SO 4 deposits are more corrosive than Na 2 SO 4 . This is attributed to a reduction of the melting temperature of the deposit and the formation of Ni-containing mixed sulphate phases in the presence of K 2 SO 4 .
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Synthesis and Surface Attachment of Molecular Re(I) Complexes Supported by Functionalized Bipyridyl Ligands
Eleven 2,2'-bipyridine (bpy) ligands functionalized with attachment groups for covalent immobilization on silicon surfaces were prepared. Five of the ligands feature silatrane functional groups for attachment to metal oxide coatings on the silicon surfaces, while six contain either alkene or alkyne functional groups for attachment to hydrogen-terminated silicon surfaces. The bpy ligands were coordinated to Re(CO) 5 Cl to form complexes of the type Re(bpy)(CO) 3 Cl, which are related to known catalysts for CO 2 reduction. Six of the new complexes were characterized using X-ray crystallography. As proof of principle, four molecular Re complexes were immobilized on either a thin layer of TiO 2 on silicon or hydrogen-terminated silicon. The surface-immobilized complexes were characterized using X-ray photoelectron spectroscopy, IR spectroscopy, and cyclic voltammetry (CV) in the dark and for one representative example in the light. The CO stretching frequencies of the attached complexes were similar to those of the pure molecular complexes, but the CVs were less analogous. For two of the complexes, comparison of the electrocatalytic CO 2 reduction performance showed lower CO Faradaic efficiencies for the immobilized complexes than the same complex in solution under similar conditions. In particular, a complex containing a silatrane linked to bpy with an amide linker showed poor catalytic performance and control experiments suggest that amide linkers in conjugation with a redox-active ligand are not stable under highly reducing conditions and alkyl linkers are more stable. So a conclusion of this work is that understanding the behavior of molecular Re catalysts attached to semiconducting silicon is more complicated than related complexes, which have previously been immobilized on metallic electrodes.
14 SOLAR ENERGY↗
Oxide-Encapsulated Ruthenium Oxide Catalysts for Selective Oxygen Evolution in Unbuffered pH-Neutral Seawater
Direct seawater electrolysis is a promising approach to producing green hydrogen in water-scarce environments using renewable energy. However, the undesirable chlorine evolution reaction and hypochlorite evolution reaction compete with the desired oxygen evolution reaction (OER) at the anode electrocatalyst. This issue is most pronounced in unbuffered pH-neutral solutions due to local acidification resulting from the OER. To overcome this challenge, this study provides a comprehensive evaluation of the use of silicon oxide (SiO x ) and titanium oxide (TiO x ) nanoscale overlayers coated on metallic ruthenium (Ru) and ruthenium oxide (RuO x ) thin film electrodes and their ability to block chloride ions from reaching active sites during operation in an unbuffered 0.6 M NaCl electrolyte. Using a combination of (electro)analytical techniques, encapsulated RuO x anodes are shown to effectively suppress Cl - transport to buried catalyst active sites while allowing for the desired OER to occur, leading to increases in OER faradaic efficiency at moderate overpotentials. Evidence for the ability of SiO x overlayers to block Cl - ions from reaching the active buried interface was obtained by monitoring the ν(O-H) stretching mode of OH adsorbates using in situ Raman spectroscopy. Here, this study also reports trade-offs between the activity, selectivity, and stability of bare and encapsulated Ru and RuO x electrocatalysts, finding that the magnitude of these trade-offs strongly depends on the complex interplay between electrode architecture, material properties, and catalytic performance, especially in unbuffered pH-neutral seawater.
58 GEOSCIENCES↗
Investigating the impact of preparation routes on the properties of copper-decorated silicon particles as anode materials for lithium-ion batteries
In recent years, the calendar life of Si has been recognized as a significant issue that must be addressed prior to technology deployment: The carbon conductive additive is a potential source of parasitic side reactions. However, carbon remains essential due to the low electronic conductivity of Si. In this study, we investigate the use of Cu as a conductive additive and potential alternative to carbon. Some Cu-decorated silicon particles (Si Cu ) were prepared using physical vapor deposition (PVD) via sputtering and high-energy milling. Other Si Cu particles were prepared by using a solution method and examined briefly. The milling method caused Cu to appear as island-like features on the Si surface, whereas the PVD method initially produced similar island-like features that gradually developed into a continuous coating around the Si as sputtering time increased. Electrodes fabricated from Si Cu exhibited lower overall resistivity, demonstrating the beneficial effect of Cu in improving electronic percolation through the electrode. Electrochemical tests showed that the milled SiCu exhibited higher capacity retention, improved rate capability, and lower overpotential. Furthermore, Si Cu coupled with an NMC811 cathode exhibited lower leakage currents compared with the baseline silicon, indicating that incorporating Cu provided an additional advantage of minimizing parasitic currents in the cells.
25 ENERGY STORAGE↗