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Implanting nitrogen ions improves hardening of silicon oxides 30 percent to 60 percent against ionizing radiation effects. Process reduces sensitivity, but retains stability normally shown by interfaces between silicon and thermally grown oxides.
Technique using boron effectively protects metal-oxide semiconductor devices from ionizing radiation without using shielding materials. Boron is introduced into insulating gate oxide layer at semiconductor-insulator interface.
A general model for time-dependent breakdown in metal-oxide-silicon (MOS) structures is developed and related to experimental measurements on samples deliberately contaminated with Na. A statistical method is used for measuring the breakdown probability as a function of log time and applied field. It is shown that three time regions of breakdown can be explained respectively in terms of silicon surface defects, ion emission from the metal interface, and lateral ion diffusion at the silicon interface.
A heterojunction or Schottky barrier photovoltaic device is described, comprising a conductive base metal layer. A back surface field region was formed at the interface between the device and the base metal layer, a transparent, conductive mixed metal oxide layer in integral contact with the n-type layer of the heterojunction or Schottky barrier device. A metal alloy grid network was included. An insulating layer prevented electrical contact between the conductive metal base layer and the transparent, conductive metal oxide layer.
A heterojunction or Schottky barrier photovoltaic device comprising a conductive base metal layer compatible with and coating predominately the exposed surface of the p-type substrate of the device such that a back surface field region is formed at the interface between the device and the base metal layer, a transparent, conductive mixed metal oxide layer in integral contact with the n-type layer of the heterojunction or Schottky barrier device having a metal alloy grid network of the same metal elements of the oxide constituents of the mixed metal oxide layer embedded in the mixed metal oxide layer, an insulating layer which prevents electrical contact between the conductive metal base layer and the transparent, conductive metal oxide layer, and a metal contact means covering the insulating layer and in intimate contact with the metal grid network embedded in the transparent, conductive oxide layer for conducting electrons generated by the photovoltaic process from the device.
Thin-oxide (40-50 A) metal oxide semiconductor (MOS) structures are shown to exhibit, before large levels of electron tunnel injection, the near-ideal behavior predicted for a uniform trapezoidal barrier with thick-oxide properties. The oscillatory field dependence caused by electron-wave interference at the Si/SiO2 interface suggests an abrupt, one-monolayer barrier transition (approximately 2.5 A) consistent with earlier work. After tunnel injection of 10 to the 17th - 5 x 10 to the 18th electrons/sq cm, the barrier undergoes appreciable degradation, leading to enhanced tunneling conductance. Reproducible behavior is observed among different samples. This effect is found to be consistent with the generation of positive states in the region of the oxide near the Si/SiO2 interface (less than 20 A), where the tunneling electrons emerge into the oxide conduction band.
X-ray photoelectron spectroscopy analysis and sliding friction experiments were conducted with hot-pressed, polycrystalline Ni-Zn and Mn-Zn ferrites in sliding contact with various transition metals at room temperature in a vacuum of 30 nPa. The results indicate that the coefficients of friction for Ni-Zn and Mn-Zn ferrites in contact with metals are related to the relative chemical activity in these metals: the more active the metal, the higher is the coefficient of friction. The coefficients of friction for the ferrites correlate with the free energy of formation of the lowest metal oxide. The interfacial bond can be regarded as a chemical bond between the metal atoms and the oxygen anions in the ferrite surfaces. The adsorption of oxygen on clean metal and ferrite surfaces increases the coefficients of friction for the Ni-Zn and Mn-Zn ferrite-metal interfaces.
Environmental, chemical and crystallographical effects on the fundamental nature on friction and wear of the ferrites in contact with metals, magnetic tapes and themselves are reviewed. The removal of adsorbed films from the surfaces of ferrites results in very strong interfacial adhesion and high friction in ferrite to metal and ferrite to magnetic tape contacts. The metal ferrite bond at the interface is primarily a chemical bond between the metal atoms and the large oxygen anions in the ferrite surface, and the strength of these bonds is related to the oxygen to metal bond strength in the metal oxide. The more active the metal, the higher is the coefficient of friction. Not only under adhesive conditions, but also under abrasive conditions the friction and wear properties of ferrites are related to the crystallographic orientation. With ferrite to ferrite contact the mating of highest atomic density (most closely packed) direction on matched crystallographic planes, that is, 110 directions on /110/planes, results in the lowest coefficient of friction.
A study on the field-induced surface-charge region in 3C silicon carbide (SiC) using 1 MHz capacitance-voltage (C-V) measurements at room temperature is here reported. A double column mercury probe was used on oxidized SiC substrates to form metal-oxide-semiconductor (MOS) structures. These structures were characterized in terms of the substrate doping profile, effective fixed oxide charge, and interface trap density. A distinctive feature of the MOS C-V curves from accumulation to inversion is that after going into deep depletion the capacitance rises to its equilibrium inversion level during the voltage sweep. Capacitance transient measurements indicate that the minority-carrier generation occurs at the SiO2/SiC interface.
Porcelain-enamel ground coats were prepared and applied under conditions that gave various degrees of adherence between enamel and a low-carbon steel (enameling iron). The variations in adherence were produced by (a) varying the amount of cobalt-oxide addition in the frit, (b) varying the type of metallic-oxide addition in the frit, keeping the amount constant at 0.8 weight percent, (c) varying the surface treatment of the metal before application of the enamel, by pickling, sandblasting, and polishing, and (d) varying the time of firing of the enamel containing 0.8 percent of cobalt oxide. Specimens of each enamel were given the standard adherence test of the Porcelain Enamel Institute. Metallographic sections were made on which the roughness of interface was evaluated by counting the number of anchor points (undercuts) per centimeter of specimen length and also by measuring the length of the interface and expressing results as the ratio of this length to the length of a straight line parallel to the over-all direction of the interface.
Analytical models useful for predicting ceramic thermal barrier coating (TBC) spalling life in aircraft gas turbine engines are presented. Electron beam-physical vapor deposited (EB-PVD) and plasma sprayed TBC systems are discussed. TBC spalling was attributed to a combination of mechanisms such as metal oxidation at the ceramic-metal interface, ceramic-metal interface stress concentrations at free surfaces due to dissimilar materials, ceramic-metal interface stresses caused by local radius of curvature and interface roughness, material properties and mechanical behavior, transient temperature gradients across the ceramic layer and component design features. TBC spalling life analytical models were developed based on observations of TBC failure modes and plausible failure theories. TBC failure was assumed to occur when the imposed stresses exceeded the material strength (at or near the ceramic-metal interface). TBC failure knowledge gaps caused by lack of experimental evidence and analytical understanding are noted. The analytical models are considered initial engineering approaches that capture observed TBC failure trends.
Analytical models for predicting ceramic thermal barrier coating (TBC) spalling life in aircraft gas turbine engines are presented. Electron beam-physical vapor deposited (EB-PVD) and plasma sprayed TBC systems are discussed. An overview of the following TBC spalling mechanisms is presented: metal oxidation at the ceramic-metal interface, ceramic-metal interface stress singularities at edges and corners, ceramic-metal interface stresses caused by radius of curvature and interface roughness, material properties and mechanical behavior, temperature gradients, component design features and object impact damage. TBC spalling life analytical models are proposed based on observations of TBC spalling and plausible failure theories. TBC spalling was assumed to occur when the imposed stresses exceed the material strength (at or near the ceramic-metal interface). TBC failure knowledge gaps caused by lack of experimental evidence and analytical understanding are noted. The analytical models are considered initial engineering approaches that capture observed TBC failure trends.
Li-O2 batteries have traditionally used carbon based electrodes (graphite, buckypaper) as the cathode of choice due to its good electrical conductivity, stability against non-aqueous electrolytes like Dimethyl ether (DME) and ease of handling. But, the carbon cathode also leads to formation of carbonate by-products that increase overpotentials during charging leading to degradation of cathode and reduction of cyclability. In this work, we investigate some of the well-known oxides as cathodes with focus on the interface between the oxide surfaces and the discharge product: Li2O2, in the Li-O2 battery using first principles computations. Our results show that attention must be paid on choosing the appropriate surface of the oxides. We extend the analysis to suggest other possible oxide chemistries that should be investigated as cathodes in Li-O2 batteries.
Li-O2 batteries have traditionally used carbon based electrodes (graphite, buckypaper) as the cathode of choice due toits good electrical conductivity, stability against non-aqueous electrolytes like dimethoxyethane (DME) and ease ofhandling. But, the carbon cathode also leads to formation of carbonate by-products that increase overpotentials duringcharging leading to degradation of the cathode and reduction of cyclability. Recent investigations have focused on using metal-oxides like SnO2, TiO2 as viable cathodes-alternatives in Li-O2 systems. In this paper, we investigate transparent conducting oxides (TCOs) as cathodes with focus on the interface between the TCO surfaces and the discharge product, Li2O2, in the Li-O2 battery using first principles computations.
Tears of wine is a phenomenon frequently observed as a ring of wine formed near the top of the glass generates droplets that fall back into the wine. This phenomenon can be explained by the Marangoni effect driven by the surface tension created via gradient on concentration and temperature along with the interface between two phases. Besides being observed while drinking wine, the Marangoni effect is crucial for welding metals, manufacturing integrated circuits, and growing crystals; the Marangoni effect might be also crucial in supporting lunar habitats and other extraterrestrial endeavors as vacuum and reduced gravity are expected to augment the Marangoni effect on extraterrestrial molten soil leading to sustainable extraterrestrial in-situ resources utilization (ISRU). Preliminary Marangoni effect assessment on molten lunar regolith was conducted via JSC-1A lunar regolith simulant under vacuum yielding a spontaneous upwards migration of a uniform molten thin-film front that climbed the crucible wall covering the entire wall’s surface and reaching the crucible’s top end. A temperature gradient within the melt’s bulk and along the crucible’s wall generates a surface tension large enough not only to form a meniscus within the three-phase junction (crucible’s wall, bulk melt, and vacuum) but also to supersede the gravitational force to create the upwards migration of a thin film front originated on the meniscus. The observed extensive wettability of the melt with the crucible surface, an additional key factor besides surface tension necessary to sustain upwards migration, is atypical to what it has been witnessed on molten JSC-1A lunar regolith simulant under non-vacuum conditions and smaller sample sizes. The unique formation and self-migration of a thin-film front could enable key ISRU processes such as thin-film coating, crystal growth, and feedstock generation for additive 3D printing. Further assessment on the higher-temperature vacuum-driven decomposition of the uniform thin-film front as it climbed the crucible’s wall revealed a significant decomposition of various simulant’s metal-oxide components into their respective oxygen and metal elements strengthening the feasibility of extraterrestrial generation and fractional separation of oxygen and metals/alloys with none or minimal need for terrestrial precursors. The Marangoni effect assessment on molten JSC-1A lunar regolith simulant clearly opens novel pathways in future extraterrestrial ISRU endeavors including manufacturing and mining. Extraterrestrial mining will require an operational approach completely different from the terrestrial one that heavily relies on not only mechanical excavation and transportation but also post-processing; an in-situ all-in-one process might be feasible via these two coupled phenomena, self-migration and decomposition.
For practical, economical, and sustainable human missions to the Moon, processing of lunar regolith and metal oxides is necessary for localized production of oxygen (O2) and metals that can be repurposed as rocket propellant, life support O2, and in-space manufactured parts. The primary candidates for in-situ resource utilization (ISRU) regolith processing are carbothermic reductions and molten regolith electrolysis (MRE) which both produce oxygen and a reduced, deoxygenated metallic slag. A metal separation technique is still required to capture and purify metals from the deoxygenated slag for reuse in areas such as metallic part fabrication, structural or design frameworks, and metal catalyst production. The Marangoni Effect is best explained as mass transfer along an interface driven by surface tension gradients induced by temperature and concentration differences. Due to the temperature gradients, molten metal can be transported in this fashion to create thin films. This method can transport molten metal in the absence of gravity or mechanical motion and greatly increases the available surface area for a vacuum fractional separation process. In this study, a novel vacuum furnace induces the Marangoni Effect to fractionally decompose and separate valuable metals (e.g., aluminum) from thin films of molten metal via vacuum distillation. The proposed work will examine lunar regolith, metal-based recycling feedstocks, and metallic slags produced from the carbothermal reduction of regolith. Data and observations from this study could produce a simple yet effective method of refining lunar derived metals by taking advantage of the high vacuum environment present on the lunar surface.
Introduction: In-Situ Resource Utilization (ISRU) is the process of extracting local resources to produce commodities for propulsion, life support systems, and off-planet construction rather than transporting consumables from Earth. Molten Regolith Electrolysis (MRE) is a novel ISRU method of extracting oxygen gas and metal alloy from lunar regolith. The MRE process involves placing lunar regolith between two electrodes, through which current is passed, to melt the regolith and reduce the metal oxide constituents by direct electrolysis (e.g. FeO, SiO2, MgO, Al2O3) into oxygen gas and metal alloys. The oxygen is liquefied and used as propellant for landers, while the metals (e.g. Ferro-alloys) are further processed and used in structural building materials and parts manufacturing. A system model was developed that accounted for the major processes of an MRE plant (from excavation of raw materials to storage of products) to assess the feasibility of a lunar MRE plant. The System Engineering and Integration (SE&I) ISRU Modeling and Analysis (SIMA) team utilized its previously documented system sizing model, the Mission Analysis and Integration Tool (MAIT) [1] as framework of the system model. MAIT uses MATLAB/Simulink to integrate subsystem models into a complete system model of the MRE plant. Total mass, volume, and power requirements were computed for numerous iterations of a MRE plant. System Model: Figure 1: MRE Plant Block Diagram The regolith excavation model determines the mass and power needed to excavate sufficient regolith. The preheating auger initiates the regolith heating process before regolith enters the MRE re-actor to reduce the energy required to turn the solid into a molten liquid. The MRE reactor is modeled in COMSOL Multiphysics and based on the research by Dominguez, Sibille, and Schreiner [2, 3, 4]. This preliminary reactor model provides an accurate calculation of thermal equilibrium during electrochemical operation of the reactor system to assess the optimal mass and power required to process the inlet flow of regolith. The model also computes the outlet flowrates of oxygen and molten products. For this analysis, the primary components of the metal alloy considered were iron and silicon. The oxygen is then purified using an Yttrium Stabilized Zirconia (YSZ) electrode, followed by liquefaction using a 90K cryocooler to be stored as liquid oxygen in insulated cylindrical tanks. In future iterations of the system model, the molten metal tapped from the MRE reactor will undergo additional processing or refinement. However, downstream handling of metals is currently a technology gap that is missing a high TRL subsystem model. Therefore, for this analysis, the accumulated metal alloy stream terminates after leaving the MRE reactor. Study Goals: This analysis investigates multiple input variables to the system to determine the sensitivity of a (near) complete plant at full-scale. This preliminary investigation ran parametric sweeps on the MRE reactor geometry, electrical current supply, layers of multi-layer insulation (MLI) on the reactor, size of the electrodes in the oxygen purification model, and regolith composition (based on landing site location). Three production targets of oxygen (1,000, 10,000, and 50,000 kg/yr) were investigated for this analysis. The parametric sweeps conducted in this analysis provide valuable insight into the expected impact of the various model inputs on plant size. This information can be used to identify the most critical components of the plant and guide future decisions on allocating funding for research and development, providing subsystem developers with appropriate interfaces with downstream and upstream processes, and assessing the overall feasibility of MRE when compared to other ISRU plants. References: [1] Carlson, A. et al. (2024) ICES, ICES-2024-53. [2] Dominguez, D.A., and Sibille, L. (2011) AIAA, AIAA-2011-700. [3] Schreiner, S.S. (2015) MIT, Dissertation. [4] Schreiner, S.S. et al. (2016) ASR, 57(7), pp.1585-1603.
To produce drop-in quality biofuels following the thermochemical conversion of biomass via catalytic fast pyrolysis (CFP), hydrodeoxygenation (HDO) reactions can be performed to remove excess oxygen and create a more stable bio-oil product. HDO reactions involve co-feeding the CFP vapor-phase product and H2 gas over bi-functional catalysts, such as noble-metal catalysts supported on reducible metal oxides (e.g., Pt/TiO2). Recent model-compound studies, focusing on important classes of species in the CFP vapor mixture, have sought to determine the role of the various Pt/TiO2 actives sites (i.e., Pt-metal, TiO2-support, Pt-TiO2-interfacial sites) in producing the observed desired deoxygenation and undesired decarboxylation/decarbonylation products. One important class of compounds in the CFP vapor-phase product is carboxylic acids (e.g., acetic acid). Prior experimental work on acetic acid HDO (AA-HDO) found that Pt/C and Pt/TiO2 catalysts favored the formation of undesired C-C and desired C-O bond-dissociation products; however, the fundamental surface chemistry driving this shift in selectivity has not been established. This presentation employs atomic-scale modeling to determine, through comparisons of adsorption and reaction energetics, how Pt-metal, Pt-TiO2-interface, and interfacial-vacancy sites catalyze the competing reaction pathways for AA-HDO. Our analysis indicates that hydroxyl vacancies at the Pt-TiO2 interface are critical for lowering barriers for C-O bond-cleavage steps, such that they become favorable/competitive with respect to C-C bond-dissociation steps.