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The reaction between barium sulfide and water, a reaction found in several sulfur based thermochemical cycles, was investigated kinetically at 653-866 C. Gaseous products were hydrogen and hydrogen sulfide. The rate determining step for hydrogen formation was a surface reaction between barium sulfide and water. An expression was derived for the rate of hydrogen formation.
Routes to area-and especially site-selective atomic layer deposition (ALD) remain an enticing challenge in precision surface science, despite the potentially game-changing capability for many energy applications. An unparalleled level of surface reaction control is required to direct ALD to select sites on the same nominal material, for example, targeted growth on distinct phases, facets, step-edges, and/or defects. However, as a sequential surface synthesis method, ALD is uniquely suited to these challenges, including the possibility of selective deposition at defective surface atom arrangements. Here, we computationally identify conditions for site-selective ALD through hydration of surface defects, including oxygen vacancies and titanium interstitials on low-index rutile TiO 2 facets. First-principles computation is used to predict, as a function of temperature, the hydroxylation of defects that are targeted by proton-exchange-mediated ALD processes. In situ ellipsometric measurements of ALD Al 2 O 3 nucleation on TiO 2 (110) single crystals prepared with and without abundant oxygen vacancies demonstrate striking contrast, corroborating computational predictions and revealing a mechanistically clear path to site-selective ALD.
To improve upon the performance of chemical rockets, the nuclear reactor has been applied to a rocket propulsion system using hydrogen gas as working fluid and a graphite-composite forming a part of the structure. Under the boundary layer approximation, theoretical predictions of skin friction coefficient, surface heat transfer rate and surface regression rate have been made for laminar/turbulent dissociated hydrogen gas flowing over a flat graphite surface. The external stream is assumed to be frozen. The analysis is restricted to Mach numbers low enough to deal with the situation of only surface-reaction between hydrogen and graphite. Empirical correlations of displacement thickness, local skin friction coefficient, local Nusselt number and local non-dimensional heat transfer rate have been obtained. The magnitude of the surface regression rate is found low enough to ensure the use of graphite as a linear or a component of the system over an extended period without loss of performance.
Sulfide superionic conductors (e.g., argyrodite Li 6 PS 5 Cl, LPSCl) are extremely promising for all solid-state batteries, but poor atmospheric stability and high interfacial reactivity limit widespread adoption. Coating LPSCl powders with ultrathin coatings using atomic layer deposition (ALD) mitigates these problems, protecting against atmospheric degradation and reducing reactivity with Li metal, yielding more stable cycling. Despite significant promise, the ALD mechanism is unknown, hampering the development of new coating chemistries. In this study, we elucidate the mechanism for Al 2 O 3 ALD on LPSCl using trimethyl aluminum (TMA) and H 2 O by combining in situ Fourier transform infrared spectroscopy, ex situ solid-state magic angle spinning nuclear magnetic resonance, UV Raman spectroscopy, X-ray photoelectron spectroscopy, and density functional theory calculations. We determine that ALD Al 2 O 3 nucleates promptly via TMA reaction with native —OH, —SH, and PS 3 -OH groups to form transient C–Al–O(S) species that are rapidly hydrolyzed during the subsequent H 2 O exposure. This reversible transformation maintains surface nucleophilicity and prevents sulfide decomposition. The resulting layer-by-layer growth leads to highly conformal Al 2 O 3 coatings on LPSCl that are readily scalable to ≥ 50 g quantities using a rotating drum fixture. This detailed understanding of ALD surface reactions provides critical insights guiding the selection of future ALD chemistries with improved performance.
This paper presents the results of a NIAC Phase I study into the use of a propulsively hopping robot for the exploration of Europa’s rugged, icy surface. Named the“Steam Propelled Retrieval Robot for Ocean Worlds,” SPARROW is a multi-thruster robot passively gimballed within a protective, spherical shell, which enables it to freely rotate, self-right, and tumble over chaotic terrains. SPARROW is envisioned as a soccerball-sized payload to a primary lander mission. Europa’s abundant surface ice would be harvested as an in situ propellant source. The principal objective of SPARROW would be to increase the science return of a Europa landed asset by enabling access to distal, spatially distributed geologic units. The design of mobility systems for Europa is challenging, due in part to its almost entirely unconstrained surface topography and strength. Images returned by Voyager and Galileo yielded resolutions on the order of hundreds of meters per pixel, with localized regions reaching 6 meters per pixel—still far larger than a typical rover. A key benefit of SPARROW’s hopping, impact-tolerant design, is that it eliminates the need for a piori information on the terrain topography and surface strength; no surface reaction forces are required for motion. In this context, SPARROW is entirely terrain agnostic. In this paper we detail the results of three study objectives: i) to quantify the energy required to collect surface ice, change its phase, and maintain propellant temperature, ii) to identify control and estimation strategies that enable SPARROW to successfully reach, and return from, regions of scientific interest, and iii) to characterize the impact of SPARROW’s range on likely science return. Five water-based propellant architectures are presented alongside their mass, power, and volume requirements. Monte Carlo simulations of SPARROW hopping and tumbling over 1 km of glacial ice are summarized, characterizing SPARROW’s sensitivity to uncertainty in: initial conditions, thrust control, and cage-terrain interaction. Finally, a science traceability matrix is presented, which details the effect of sortie range on three science goals: constraining Europa’s evolutionary morphology, assessing sub-surface ocean habitability, and searching for life and/or biosignatures.
Harnessing aluminum oxidation energy requires navigating the particle's passivation shell composed of alumina. The shell is a barrier to aluminum oxidation but can also exothermically react with halogenated species and therefore contribute to the overall energy generated during aluminum particle combustion. Fluorination reactions with alumina have been studied because fluorine is abundant in binder formulations that commonly surround aluminum particles in an energetic mixture. However, iodine has emerged as an alternative halogenated-based binder or oxidizer because iodine gas provides ancillary benefits such as chemical neutralization of biological agents or sterilization of contaminated environments. Furthermore, this study used density functional theory (DFT) calculations to evaluate potential reaction pathways for aluminum–iodine combustion. Relative to fluorinated fragments such as HF and F – , the adsorption energies associated with HI and I– are nearly triple the exchange reaction energy available from fluorination reactions with alumina (–189 and –278 kJ mol –1 for HI and I – , respectively). However, exchange reactions between iodinated species and the alumina surface are energetically unfavorable. These results explain that through adsorption, alumina surface exothermic reactions with iodine are more energetic than with fluorine fragments. Experiments performed with differential scanning calorimetry (DSC) confirm the higher magnitude of energy generated for iodination compared with fluorination reactions with alumina. Additionally, strong adsorption energies can promote synthesis of new shell chemistries. Adsorption in solution will promote alumina dissolution and iodine precipitation reactions to produce hydroxyl complexes and iodinated species synthesized on the surface of the particle, thereby replacing alumina with alternative passivation shell chemistry.
The Steam Propelled Autonomous Retrieval Robot (SPARROW) for Ocean Worlds was a Phase I mission concept study funded under the NASA NIAC program. This report represents the findings of that study and recommendations for future work. SPARROW, envisioned as a soccer ball-sized payload to a primary lander mission, is a propulsively hopping robot for the exploration of Europa's rugged, icy surface. A multi-thruster, passively gimballed robot within a protective, spherical shell, SPARROW is able to freely rotate, self-right, and tumble over chaotic terrains. Europa's abundant surface ice would be harvested as an in situ propellant source. The principal objective of SPARROW is to increase the science return of a Europa landed asset by enabling access to distal, spatially distributed geologic units. The design of mobility systems for Europa is challenging, due in part to its almost entirely unconstrained surface topography and strength. Images returned by Voyager and Galileo yielded resolutions on the order of hundreds of meters per pixel, with localized regions reaching 6 meters per pixel—still far larger than a typical rover. A key benefit of SPARROW's hopping, impact-tolerant design, is that it eliminates the need for a priori information regarding terrain topography and surface strength; no surface reaction forces are required for motion. In this context, SPARROW is believed to be entirely terrain agnostic. In this report we detail the results of three study objectives: i) to quantify the energy required to collect surface ice, change its phase, and maintain propellant temperature, ii) to identify control and estimation strategies that enable SPARROW to successfully reach, and return from, regions of scientific interest, and iii) to characterize the impact of SPARROW's range on likely science return. Five water-based propellant architectures are presented alongside their mass, power, and volume requirements. Monte Carlo simulations of SPARROW hopping and tumbling over 1 km of glacial ice are summarized, characterizing SPARROW's sensitivity to uncertainty in: initial pose, thrust profile, and vehicle-terrain interaction. A science traceability matrix is presented, which details the effect of sortie range on three science goals: constraining Europa's evolutionary morphology, assessing sub-surface ocean habitability, and searching for life and/or biosignatures.
In contrast to the traditional perspective that thermal fluctuations are insignificant in surface dynamics, here we report their influence on surface reaction dynamics. Using real-time low-energy electron microscopy imaging of NiAl(100) under both vacuum and O 2 atmospheres, we demonstrate that transient temperature variations substantially alter the direction of atom diffusion between the surface and bulk, leading to markedly different oxidation outcomes. During heating, substantial outward diffusion of atoms from the bulk to the surface results in step growth. Conversely, cooling induces considerable inward diffusion of adatoms, producing a distinct oxide morphology. In both scenarios, initially formed oxide islands impede local atomic step mobility, thereby increasing step length due to mass transfer between the surface and bulk, with atomic steps acting as adatom sinks during heating and sources during cooling. Furthermore, we show that this pinning effect on atomic step mobility can be mitigated by applying persistent temperature fluctuations. As a result, understanding these nuances is vital for accurately predicting and dynamically manipulating the performance of active materials in various chemical processes under transient thermal conditions.
Triple oxygen isotope measurements have been used as tracers for classifying meteorites, as indicators of atmospheric chemistry and as a proxy for primary productivity among other uses. These utilities rely on the mass dependency of most chemical reactions: δ17O is proportional to δ18O by roughly a factor of 0.5. However,in detail it is known that mass-dependency factorsvary. Constraints on mass dependency are well established for equilibrium isotope effects, but similar constraints for kinetic isotope effects are lacking.Here, we provide constraints for isotope effects generated by unidirectional chemical reactions (i.e. kinetic isotope effects, KIEs). A simplified Monte Carlo model is used to estimatethe range of kinetic isotope effects. It is found that the range of KIEs exceeds the range of equilibrium isotope effects such that some mass dependent kinetic isotope effects could be mistaken for being mass-independent. For the16O-17O-18O system,Δ′17Ovariations as large 0.8‰ can be generated from a single reaction step. Two case studies from published literature, on the thermal decomposition of calcite (CaCO3) and brucite (Mg(OH)2), are used to test the extreme limits of the modeled results. Isotope fractionationsgenerated fromdensity functional theory models of the surface reaction steps are shownto match the published data. The fractionation models are strictly mass dependent thus this result suggests thermal decomposition of calcite is also mass dependent. Although oxygen is the focus here, our approach applies to any system with more than two isotopes.
Heteroepitaxy on colloidal semiconductor nanocrystals is an essential strategy for manipulating their optoelectronic functionalities. However, their practical synthesis typically leads to scattered and unexpected outcomes due to the intervention of multiple reaction pathways associated with complicated side products of reactants. Here, the heteroepitaxy mechanism of zinc chalcogenide initiated on indium phosphide (InP) colloidal nanocrystals is elucidated using the precursors, zinc carboxylate and trialkylphosphine selenide. The high magnetic receptivity of 77 Se and the characteristic longitudinal optical phonon mode of ZnSe allowed for monitoring the sequence of epilayer formation at the molecular level. The investigation revealed the sterically hindered acyloxytrialkylphosphonium and diacyloxytrialkylphosphorane to be main intermediates in the surface reaction, which retards the metal ion adsorption by a large steric hindrance. The transformation of adsorbates to the crystalline epilayer was disturbed by surface oxides. Raman scattering disclosed the pathway of secondary surface oxidation triggered by carboxylate ligands migrated from zinc carboxylate. The surface-initiated heteroepitaxy protocol is proposed to fabricate core/shell heterostructured nanocrystals with atomic-scale uniformity of epilayers. Despite the large lattice mismatch of ZnS to InP, we realised a uniform and interface defect-free ZnS epilayer (~0.3 nm thickness) on InP nanocrystals, as evidenced by a high photoluminescence quantum yield of 97.3%.
Simulation experiments to determine lunar surface reaction to lunar probe impact, noting impact flash, flash duration and emitted light spectrum
A small and light weight microconical interface fitting may be attached to the surface of a space vehicle or equipment to provide an attachment device for an astronaut or robot to capture the space vehicle or equipment. The microconical interface fitting of the present invention has an axisymmetrical conical body having a base portion with a torque reaction surface for preventing rotation of the interface grasping tool; a cavitated, sunken or hollowed out intermediate locking portion which has a cavity shaped for receiving the latches of the grasping tool and an upper guiding portion for guiding the grasping tool into axial alignment with the microconical interface fitting. The capture is accomplished with an interface grasping tool. The grasping tool comprises an outer sleeve with a handle attached, an inner sleeve which may be raised and lowered within the outer sleeve with a plurality of latches supported at the lower end and a cam to raise and lower the inner sleeve. When the inner sleeve is at its lowest position, the latches form the largest diameter opening for surrounding the microconical fitting and the latches form the smallest diameter or a locking, grasping position when raised to the highest position within the outer sleeve. The inner sleeve may be at an intermediate, capture position which permits the latches to be biased outwardly when contacting the microconical fitting under very low forces to grasp the fitting and permits capture (soft docking) without exact alignment of the fitting and the tool.
This chapter covers the epitaxy of complex oxides on common inorganic semiconductors. The chapter opens with an introduction, motivating the subject and highlighting key general challenges (Section 6.1). We then proceed to describe the general steps of the growth procedure in Section 6.2, which concludes with an overall discussion about trade-offs and expectation management, with an emphasis on the oxide–semiconductor interface. From there, the text describes oxide growth on the common semiconductors, starting with silicon (Section 6.3), where surface reactions and oxidation are the most challenging aspects. Oxide epitaxy on germanium is described in Section 6.4, which is a less challenging oxide growth scheme on semiconductors. Section 6.5 describes oxide epitaxy on gallium arsenide, one of the more challenging schemes, where interface stability and surface preparation pose key challenges. Finally, in Section 6.6, oxide epitaxy on gallium nitride is described, where the lattice mismatch takes the stage as the key challenge. Altogether, this chapter aims to provide the reader with the practical knowledge, tactics and strategies for oxide epitaxy on semiconductors.
Teflon has been identified as suitable material for use in oxygen-enriched atmospheres because of its low specific enthalpy of combustion that is, less than 1500 cal/gram. However, once ignited, Teflon burns in a heterogeneous reaction until total consumption or depletion of oxygen occurs. A model is developed for the burning of Teflon in pure, high-pressure oxygen, 3.4 to 68.9 MPa. The Teflon polymer chain dissociates via monomer units due to pyrolysis. These monomer units diffuse to the surface due to free convection. The model consists of coupled mass and energy balances for the polymer and an energy balance for the free convection of product gases. The model is used to obtain appropriate kinetic parameters for the dissociation and surface reactions. The model is validated against experimental measurements of Teflon discs supported on aluminum rods (2216) at oxygen pressures of 3.4, 6.8, 34.4, and 68.9 MPa. The model simulates the temperature distribution in the product gases above burning Teflon.
Ongoing exploration and future mission2001110444 s to Mars have given impetus to research on the use of natural resources of the planet. Since carbon dioxide (CO2) constitutes approximately 95% of the Mars atmosphere and since it reacts directly and vigorously with several metals, this investigation focuses on metal-CO2 reactions as a possible combination for rocket-propellant production and energy generation. Magnesium (Mg) has been initially selected as the metal fuel owing to its low ignition temperature and high specific impulse and burning rate in CO2. Our studies in this field started with low gravity (g) combustion tests of Mg in O2, CO2, and CO. Reduced gravity provided a clear picture of the burning phenomena by eliminating the intrusive buoyant flows in high-temperature metal reactions and by removing the destructive effect of gravity on the shape of molten metal samples. Suspended cylindrical metal samples of 2, 3, and 4-mm in diameter and length were radiatively ignited in low-g to generate free-floating samples exhibiting a spherically symmetric flame with increasing metal-oxide accumulation in an outer shell. For the Mg-CO2 combination, burning times twice as long as in normal-g and five times longer than in Mg-O2 flames were observed, revealing a diffusion-controlled reaction. The burning time is proportional to the square of the sample diameter. In tests conducted with pure CO, combustion was not possible without constant heating of the sample due to the formation of a thick carbon-containing coating around the Mg sample generated by surface reactions. The following work presents two new studies that attempt to explain some of the low-g experimental observations. First, a simplified one-dimensional, quasi-steady numerical model is developed to obtain temperature, species concentrations, and burning rates of the spherically symmetric diffusion flame around the Mg sample burning in O2 and CO2. Second, a Planar Laser Induced Fluorescence (PLIF) technique is implemented to provide spatially resolved measurements of magnesium oxide (MgO) in the reaction zone of Mg samples burning in O2 and CO2. These experiments reveal fundamental differences between the two combustion systems.
A model system of Mars soil analog materials (MSAMs) was prepared, and the properties of these clays, such as chemical composition, surface-ion composition, water adsorption isotherms, and reflectance spectra, were examined. The results of these studies, performed along with simulations of the Viking Labeled Release Experiement using MSAMs, indicate that surface iron and adsorbed water are important determinants of clay behavior, as evidenced by changes in reflectance, water absorption, and clay surface reactions. The paper discusses the relevance of these results to the two major questions raised by prior explorations of Mars: has there ever been abundant water on Mars, and why is the iron found in the Martian soil not readily seen in the reflectance spectra of the surface?
The heat transfer to the stagnation point of an ablating carbonaceous heat shield, where both the gas-phase boundary layer and the heterogeneous surface reactions are not in chemical equilibrium, is examined. Specifically, the nonequilibrium changes in the mass fraction profiles of carbon species calculated for frozen flow are studied. A set of equations describing the steady-state, nonequilibrium laminar boundary layer in the axisymmetric stagnation region, over an ablating graphite surface, is solved, with allowance for the effects of finite rate of carbon vaporization.
A novel dual laser flash photolysis-long path absorption-resonance fluorescence technique has been employed to study the kinetics of the important stratospheric reaction 0((sup 3)P(sub j)) + Br yields(k1) BrO((sup 2)P(sub J)) + O2 as a function of temperature (231-328 K) and pressure (25-150 Torr) in N2 buffer gas. The experimental approach preserves the principal advantages of the flash photolysis method, i.e., complete absence of surface reactions and a wide range of accessible pressures, but also employs techniques which are characteristic of the discharge flow method, namely chemical titration as a means for deducing the absolute concentration of a radical reactant and use of multiple detection axes. We find that k1 is independent of pressure, and that the temperature dependence of k1 is adequately described by the Arrhenius expression k1(T) = 1.91 x 10(exp -11)(230/J) cu cm/ molecule.s; the absolute accuracy of measured values for k1 is estimated to vary from +/- 20 percent at at T approximately 230 K to +/- 30 percent at T approximately 330 K. Our results demonstrate that the O((sup 3)P(sub j)) + BrO rate coefficient is significantly faster than previously 'guesstimated,' and suggest that the catalytic cycle with the O((sup 3)P(sub j)) + BrO reaction as its rate-limiting step is the dominant stratospheric BrO(x), odd-oxygen destruction cycle at altitudes above 24 km.