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At least 937 records · Page 52

A kinetic model for the thermal nitridation of SiO2/Si

To explain the observed nitrogen distributions in thermally nitridated SiO2 films, a kinetic model is proposed in which the nitridation process is simulated, using the first-order chemical kinetics and Arrhenius dependence of the diffusion and reaction rates on temperature. The calculations show that initially, as the substrate reacts with diffusing nitrogen, a nitrogen-rich oxynitride forms at the SiO2-Si interface, while at nitridation temperatures above 1000 C, an oxygen-rich oxynitride subsequently forms at the interface, due to reaction of the substrate with an increasingly concentrated oxygen displaced by the slower nitridation of the SiO2. This sequence of events results in a nitrogen distribution in which the peak of the interfacial nitrogen concentration occurs away from the interface. The results are compared with the observed nitrogen distribution. The calculated results have correctly predicted the positions of the interfacial nitrogen peaks at the temperatures of 800, 1000, and 1150 C. To account for the observed width of the interfacial nitrogen distribution, it was found necessary to include in the simulations the effect of interfacial strain.

Vasquez, R. P.↗

Large Eddy Simulation of Cryogenic Injection Processes at Supercritical Pressure

This paper highlights results from the first of a series of hierarchical simulations aimed at assessing the modeling requirements for application of the large eddy simulation technique to cryogenic injection and combustion processes in liquid rocket engines. The focus is on liquid-oxygen-hydrogen coaxial injectors at a condition where the liquid-oxygen is injected at a subcritical temperature into a supercritical environment. For this situation a diffusion dominated mode of combustion occurs in the presence of exceedingly large thermophysical property gradients. Though continuous, these gradients approach the behavior of a contact discontinuity. Significant real gas effects and transport anomalies coexist locally in colder regions of the flow, with ideal gas and transport characteristics occurring within the flame zone. The current focal point is on the interfacial region between the liquid-oxygen core and the coaxial hydrogen jet where the flame anchors itself.

Oefelein, Joseph C.↗

Large Eddy Simulation of Cryogenic Injection Processes at Supercritical Pressure

This paper highlights results from the first of a series of hierarchical simulations aimed at assessing the modeling requirements for application of the large eddy simulation technique to cryogenic injection and combustion processes in liquid rocket engines. The focus is on liquid-oxygen-hydrogen coaxial injectors at a condition where the liquid-oxygen is injected at a subcritical temperature into a supercritical environment. For this situation a diffusion dominated mode of combustion occurs in the presence of exceedingly large thermophysical property gradients. Though continuous, these gradients approach the behavior of a contact discontinuity. Significant real gas effects and transport anomalies coexist locally in colder regions of the flow, with ideal gas and transport characteristics occurring within the flame zone. The current focal point is on the interfacial region between the liquid-oxygen core and the coaxial hydrogen jet where the flame anchors itself.

Oefelein, Joseph C.↗

Shock-induced bubble jets: a dual perspective of bubble collapse and interfacial instability theory

Interactions between shock waves and gas bubbles in a liquid can lead to bubble collapse and high-speed liquid jet formation, relevant to biomedical applications such as shock wave lithotripsy and targeted drug delivery. This study reveals a complex interplay between acceleration-induced instabilities that drive jet formation and radial accelerations causing overall bubble collapse under shock wave pressure. Using high-speed synchrotron X-ray phase contrast imaging, the dynamics of micrometre-sized air bubbles interacting with laser-induced underwater shock waves are visualised. These images offer full optical access to phase discontinuities along the X-ray path, including jet formation, its propagation inside the bubble, and penetration through the distal side. Jet formation from laser-induced shock waves is suggested to be an acceleration-driven process. A model predicting jet speed based on the perturbation growth rate of a single-mode Richtmyer–Meshkov instability shows good agreement with experimental data, despite uncertainties in the jet-driving mechanisms. The jet initially follows a linear growth phase, transitioning into a nonlinear regime as it evolves. To capture this transition, a heuristic model bridging the linear and nonlinear growth phases is introduced, also approximating jet shape as a single-mode instability, again matching experimental observations. Upon piercing the distal bubble surface, jets can entrain gas and form a toroidal secondary bubble. Linear scaling laws are identified for the pinch-off time and volume of the ejected bubble relative to the jet’s Weber number, characterising the balance of inertia and surface tension. At low speeds, jets destabilise due to capillary effects, resulting in ligament pinch-off.

Drops and Bubbles: Bubble dynamics↗

A two-phase three-field modeling framework for heat pipe application in nuclear reactors

Heat pipes and two-phase thermosyphons are highly efficient heat transfer devices utilizing continuous evaporation and condensation of working fluid for two-phase heat transport in closed systems. Because of the nearly isothermal and fully passive phase-change heat transfer mechanism, heat pipes and thermosyphons have found many applications in nuclear engineering, space technologies, and other energy systems. High-temperature heat pipes are used in nuclear microreactors to remove fission power from the primary system and are coupled with power conversion systems or process heat applications. Modeling of the two-phase flow phenomena inside a heat pipe is essential to its design and safety analysis. In this study, a comprehensive one-dimensional two-phase three-field flow model has been developed for the analysis of heat pipes in normal operation conditions and transients. The conservation or field equations of mass, momentum, and energy were developed for the liquid film, vapor, and droplet. In addition, constitutive models or correlations were reviewed thoroughly and provided for the closure of the three-field equations. Specific constitutive equations regarding interfacial mass and heat transfer at two interfaces, namely film-gas interface and gas-droplet interface, were reviewed for droplet entrainment and deposition rates as well as film and droplet evaporation rates. Furthermore, mechanistic correlations of annular flow film thickness were recommended for the modeling of the thermosyphons without a wick as a critical constitutive correlation. Furthermore, experimental data needs from new experiments using a prototype working fluid or surrogate fluids for the model validation of high-temperature heat pipes in microreactors were recommended for future research.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Characterization of Polyimide Foams for Ultra-Lightweight Space Structures

Ultra-lightweight materials have played a significant role in nearly every area of human activity ranging from magnetic tapes and artificial organs to atmospheric balloons and space inflatables. The application range of ultra-lightweight materials in past decades has expanded dramatically due to their unsurpassed efficiency in terms of low weight and high compliance properties. A new generation of ultra-lightweight materials involving advanced polymeric materials, such as TEEK (TM) polyimide foams, is beginning to emerge to produce novel performance from ultra-lightweight systems for space applications. As a result, they require that special conditions be fulfilled to ensure adequate structural performance, shape retention, and thermal stability. It is therefore important and essential to develop methodologies for predicting the complex properties of ultra-lightweight foams. To support NASA programs such as the Reusable Launch Vehicle (RLV), Clark Atlanta University, along with SORDAL, Inc., has initiated projects for commercial process development of polyimide foams for the proposed cryogenic tank integrated structure (see figure 1). Fabrication and characterization of high temperature, advanced aerospace-grade polyimide foams and filled foam sandwich composites for specified lifetimes in NASA space applications, as well as quantifying the lifetime of components, are immensely attractive goals. In order to improve the development, durability, safety, and life cycle performance of ultra-lightweight polymeric foams, test methods for the properties are constant concerns in terms of timeliness, reliability, and cost. A major challenge is to identify the mechanisms of failures (i.e., core failure, interfacial debonding, and crack development) that are reflected in the measured properties. The long-term goal of the this research is to develop the tools and capabilities necessary to successfully engineer ultra-lightweight polymeric foams. The desire is to reduce density at the material and structural levels, while at the same time maintaining or increasing mechanical and other properties.

Meador, Michael↗

Formation Mechanisms, Crystal Structure, and Interfacial Reactivity of (Mixed) Metal Sulfide Nanoparticles Produced via Biological versus Abiotic Systems

The primary goals of this project were to understand the formation mechanisms and reactivity of mix-metal sulfide nanophases (Cu-Fe, Ni-Fe, Co-Fe sulfides) produced via biological and abiotic pathways that are relevant to low-temperature aqueous environments. These mix-metal sulfide nanophases have been identified in a range of natural and anthropogenic systems and are considered to play key roles in the biogeochemical cycling of elements, biomineralization, environmental remediation, resource recovery, eco-toxicity, and the origin and evolution of life. Using a comparative approach, we aimed to elucidate: (i) if these mix-metal sulfides tend to form nanoscale phases regardless of their formation pathways; (ii) what mechanisms are involved in the biological and abiotic crystallization processes; (iii) what phases form that have been otherwise expected; and (iv) if we can combine the experimental results with what we see and surmise from field studies to facilitate a more comprehensive understanding regarding the origin and biogeochemical roles of these mix-metal sulfides. Along a related pathway of electron transfer in nano-systems, in this case dealing with Fe-oxides instead of Fe-sulfides, we have continued to explore the reactions and solid products of heterogeneous catalytic oxidation of aqueous Mn(II) by dissolved oxygen in the presence of iron oxides (hematite) nanoparticles. The nano-Mn-oxides produced are known to be efficient sorbents of transition metal elements, including Cu, Ni, and Co studied in our sulfide work.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

CFA-17-12798: Nanostructured Ceramic Membranes for Enhanced Tritium Management

This project focuses on the novel use of interfacial hydrated layers in ionic conducting ceramic materials for tritiated water (HTO) adsorption and recovery. Low-temperature water adsorption properties of nanoscale structured ceramics combined with hydrogen isotope exchange in their hydrated layers could provide a low-cost and transformative avenue to address tritium management challenges.

08 HYDROGEN↗

The onset of alloying in Cu-Ni powders under high-shear consolidation

Friction consolidation (FC) is a solid phase processing methodology that densifies a material through high-shear deformation and pressure at elevated temperature. The method has garnered interest in the scientific community because of its ability to produce extremely refined and homogeneous microstructures, off-axis texture development, and improved material properties. This manuscript presents an investigation of Cu and Ni material mixing via evaluation of morphological evolution, grain boundary characterization, and compositional analysis to provide insights on the operational alloying mechanisms occurring under high shear and elevated temperature. Using correlative microscopy techniques, we show alloying progresses via a combination of grain boundary diffusion and interfacial roughening at heterophane boundaries. Evidence supporting Cu infiltration along Ni-Ni grain boundaries along with asymmetric diffusion of Cu into Ni grains is highlighted. The resultant, consolidated microstructure was produced directly from a powder compact in ~30 s and exhibited a submicron, equiaxed grain size.

36 MATERIALS SCIENCE↗

Design of enhanced porous organic cage solubility in Type 2 porous liquids

Decreasing cost of technologies for direct air capture of carbon can be achieved through the design of new materials with high CO 2 selectivity that can be incorporated into existing industrial processes. An emerging class of materials for these applications are porous liquids (PLs). PLs are mixtures of porous hosts and solvents with intrinsic porosity due to steric exclusion of solvent from inside the porous host. It is currently unknown how solvent -porous host interactions affect porous host solubility in the bulk solvent. Here, in this study, density functional theory simulations were used to investigate interactions between nine solvents and a CC13 porous organic cage (POC). Calculations identified that solvent molecules were the most stable when placed either inside the CC13 POC or in the pore window compared to interfacial binding sites. Structural changes to the CC13 POC correlated with reported experimental solubilities, including expansion of the CC13 POC with solvent molecule infiltration and expansion or contraction of the pore window. Based on these results, new PL design guidelines should include compositions with (1) high concentrations of POCs with flexible cage structures that can expand when solvated and (2) solvent molecule-POC combinations that contract the pore window during solvent molecule-host binding.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Bond Selective Photochemistry at Metal Nanoparticle Surfaces: CO Desorption from Pt and Pd

The use of visible photon fluxes to influence catalytic reactions on metal nanoparticle surfaces has attracted attention based on observations of reaction mechanisms and selectivity not observed under equilibrium heating. These observations suggest that photon fluxes can selectively impact the rates of certain elementary steps, creating nonequilibrium energy distributions among various reaction pathways. However, quantitative studies validating these hypotheses on metal nanoparticle surfaces are lacking. Here, we examine the influence of continuous wave visible photon fluxes on the CO desorption rates from 1 to 2 nm diameter Pt and Pd nanoparticle surfaces supported on γ-Al 2 O 3 . Temperature-programmed desorption measurements quantified via diffuse reflectance infrared Fourier transform spectroscopy demonstrate that visible photon fluxes significantly enhanced the rate of CO desorption from Pt nanoparticles in a wavelength-dependent manner. 440 nm photons most efficiently promoted CO desorption from Pt nanoparticle surfaces, aligning with the excitation energy for the interfacial electronic transition within the Pt–CO bond. Conversely, visible photon fluxes had no measurable influence on CO desorption rates from Pd nanoparticle surfaces after accounting for photon-induced heating. Density functional theory calculations demonstrate that the Pt–CO bond exhibits a narrower LUMO resonance, stronger coupling between the photoexcitation and forces induced on the metal–C bond, and vibrational energy dissipation that more effectively couples to desorption as compared to Pd–CO. These results demonstrate the specificity photons provide in facilitating chemical reactions on metal nanoparticle surfaces and substantiate the idea that photon fluxes can steer processes and outcomes of catalytic reactions in ways not achievable by equilibrium heating.

desorption↗

Efficient BiVO 4 /CoFeO x H y photoanodes using controlled annealing and conformal linear-sweep electrocatalyst photodeposition

Although monoclinic bismuth vanadate (BiVO 4 ) is a promising photoanode for solar water splitting, its practical use is hindered by imperfect photocurrent generation/collection, low photovoltage compared to the bandgap, and corrosion side reactions that limit durability. Here, we introduce a controlled-annealing sol–gel process for BiVO 4 thin-film photoanodes along with an optimized linear-sweep-voltammetry photodeposition of CoFeO x H y cocatalysts. The resulting BiVO 4 films annealed at 550 °C exhibited a photocurrent density of 4.1 mA/cm 2 at 1.23 V RHE under 1 sun AM 1.5G solar simulation and a low onset potential of 0.26 V RHE due to high majority carrier conductivity, a crystalline bulk with reduced defects as evidenced by x-ray photoelectron spectroscopy and photoluminescence lifetime analysis, and thus enhanced photocarrier collection. However, significant degradation in performance was found due to interfacial photocorrosion. To protect the surface and speed the oxygen-evolution reaction CoFeO x H y cocatalyst layers were deposited. By varying the number of consecutive sweeps and adjusting the applied bias range, an ultra-thin (~15 nm) CoFeO x H y cocatalyst layer was uniformly grown deposited over 30 cycles on the BiVO 4 surface. The resulting BiVO 4 /CoFeO x H y yielded 4.03 mA/cm 2 at 1.23 V RHE and onset potential of 0.24 V RHE , with stable operation (~15 % loss in photocurrent at 1.23 V RHE relative to ~60 % loss in the uncatalyzed control sample). These conformal CoFeO x H y catalytic layers function simultaneously to selectively collect photoexcited holes from the BiVO 4 , catalyze the water-oxidation reaction, and protect the BiVO 4 from photodegradation.

42 ENGINEERING↗

Dynamic Surface Incorporation of Pb 2+ Ions at the Actively Dissolving Calcite (104) Surface

The reaction of dissolved Pb 2+ with calcite surfaces at near-equilibrium conditions involves adsorption of Pb 2+ and precipitation of secondary heteroepitaxial Pb-carbonate minerals. A more complex behavior is observed under far-from-equilibrium conditions, including strong inhibition of calcite dissolution, development of microtopography, and near-surface incorporation of multiple monolayers (ML) of Pb 2+ without precipitation of secondary phases [where 1 ML ≡ 1 Ca/20.2 Å 2 , the crystallographic site density of the calcite (104) lattice plane]. However, the mechanistic controls governing far-from-equilibrium reactivity are not well understood. Here, in this study, we observe the interfacial incorporation of dissolved Pb 2+ during the dissolution of calcite (104) surfaces at pH ~3.7 in a flow-through reaction cell, revealing the formation of a ~1 nm thick Pb-rich calcite layer with a total Pb coverage of ~1.4 ML. These observations of the sorbed Pb distribution used resonant anomalous X-ray reflectivity, X-ray fluorescence, and nanoinfrared atomic force microscopy. We propose that this altered surface layer represents a novel sorption mode that is stabilized by conditions of sustained disequilibrium. This behavior may significantly impact the transport of dissolved metals during disequilibrium processes occurring in acid mine drainage and subsurface CO 2 injection and, if appropriately accounted for, could improve the predictive capability of geochemical reactive-transport models.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Self-Assembly of Flexible Linear–Semiflexible Bottlebrush–Flexible Linear Triblock Copolymers

Block copolymer (BCP) self-assembly is a fundamental process in which incompatible blocks spontaneously form organized microstructures with broad practical applications. Classical understanding is that the domain spacing is limited by the contour length of the polymer backbone. Here, using a combination of molecular design, chemical synthesis, small-/wide-angle X-ray scattering, transmission electron microscopy, and electron tomography, we discover that this molecular picture does not hold for architecturally semiflexible BCPs. For strongly segregated linear–semiflexible bottlebrush–linear triblock copolymers, the size of the bottlebrush domain can be twice the bottlebrush backbone contour length. The mechanism of such anomalous self-assembly is likely that the interfacial repulsion between the incompatible blocks is large enough to pull a part of the linear end blocks into the bottlebrush domain. This effectively increases the bottlebrush domain size. Moreover, the semiflexible bottlebrush widens the regime for the cylinder morphology that is associated with the volume fraction of the end blocks fC SFB ∈ (0.10, >0.41). This window is much wider than that for flexible linear BCPs, fC F ∈ (0.14, 0.35), and that predicted by the recent self-consistent field theory for linear-bottlebrush BCPs of the same chemistry and molecular architecture. Finally, our experimental findings reveal previously unrecognized mechanisms for the self-assembly of architecturally complex BCPs.

36 MATERIALS SCIENCE↗

Ion-dependent protein–surface interactions from intrinsic solvent response

Significance Hard–soft interfaces between inorganic surfaces and biomolecules promote self-assembly processes with broad implications in biogeochemistry, energy sciences, nanomedicine, and origins of life. Yet, detailed molecular-scale understanding of inorganic–biomolecule interactions and their dependence on solution conditions is missing. We present a theory for the initial stages of inorganic–biomolecule assembly based on the far-field response of water, using experimentally characterized interactions between muscovite surfaces and mica-binding proteins as model systems. Our work connects molecular details of the solution to assembly outcomes and suggests the initial driving forces for assembly are dominated by long-range, ion-specific interactions. The connections made between interfacial structure and long-range surface–biomolecule interactions provide insights toward a predictive understanding of biomolecular self-assembly on mineral surfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Computational Analysis of the Effect of Structured Packing Design on Absorption Column Hydrodynamics for Post-Combustion Carbon Capture Applications

Solvent based post-combustion carbon capture technologies have a potential for reducing carbon emissions from fossil-fuel-fired power plants and industrial sources where CO2 emissions are inherently harder to mitigate, such as steel or cement industries. A prominent technology to achieve this is by retrofitting absorption columns to the existing infrastructure. While these systems have been among the less costly alternatives for carbon capture, they still impose a considerable energy penalty to the operation of power plants or industrial facilities. The optimization of CO2 capture rate in solvent-based absorption process is complex as it depends on several factors including CO2 solubility, solvent reaction kinetics and temperature effects on the solubility, reaction rates, surface tension, and thermophysical properties of the solvent and the flue gas. The overall heat and mass transfer also depends on the hydrodynamics, which in turn, is affected by the packing geometry. In the current work, we systematically quantify the effects the design of the structured packing has on the column hydrodynamics, by performing detailed CFD simulations for different geometrical configurations and operating conditions. We then obtain relationships between the key hydrodynamic metrics, such as liquid holdup, interfacial area, wetted area, and pressure drop to the parameters defining the packing geometries and identify new more effective packing designs for the given operating conditions.

Shah, Yash Girish↗

Modeling Functional Organic Chemistry in Arctic Rivers: An Idealized Siberian System

Rivers of the Arctic will become ever more important for the global climate, since they carry a majority of continental dissolved organic carbon flux into the rapidly changing polar ocean. Aqueous organics comprise a wide array of functional groups, several of which are likely to impact coastal and open water biophysical properties. Light attenuation, interfacial films, aerosol formation, gas release and momentum exchange can all be cited. We performed Lagrangian kinetic modeling for the evolution of riverine organic chemistry as the molecules in question make their way from the highlands to Arctic outlets. Classes as diverse as the proteins, sugars, lipids, re-condensates, humics, bio-tracers and small volatiles are all included. Our reduced framework constitutes an idealized northward flow driving a major hydrological discharge rate and primarily representing the Russian Lena. Mountainous, high solute and tundra sources are all simulated, and they meet up at several points between soil and delta process reactors. Turnover rates are parameterized beginning with extrapolated coastal values imposed along a limited tributary network, with connections between different terrestrial sub-ecologies. Temporal variation of our total dissolved matter most closely resembles the observations when we focus on the restricted removal and low initial carbon loads, suggesting relatively slow transformation along the water course. Thus, channel combinations and mixing must play a dominant role. Nevertheless, microbial and photochemical losses help determine the final concentrations for most species. Chemical evolution is distinct for the various functionalities, with special contributions from pre- and post-reactivity in soil and delta waters. Several functions are combined linearly to represent the collective chromophoric dissolved matter, characterized here by its absorption. Tributaries carry the signature of lignin phenols to segregate tundra versus taiga sources, and special attention is paid to the early then marine behaviors of low molecular weight volatiles. Heteropolycondensates comprise the largest percentage of reactive carbon in our simulations due to recombination/accumulation, and they tend to be preeminent at the mouth. Outlet concentrations of individual structures such as amino acids and absorbers lie above threshold values for biophysical influence, on the monolayer and light attenuation. The extent of coastal spreading is examined through targeted regional box modeling, relying on salinity and color for calibration. In some cases, plumes reach the scale of peripheral arctic seas, and amplification is expected during upcoming decades. Conclusions are mapped from the Lena to other boreal discharges, and future research questions are outlined regarding the bonding type versus mass release as permafrost degrades. Dynamic aqueous organic coupling is recommended for polar system models, from headwaters to coastal diluent.

54 ENVIRONMENTAL SCIENCES↗

Modeling Ullage Dynamics of Tank Pressure Control Experiment during Jet Mixing in Microgravity

A CFD model for simulating the fluid dynamics of the jet induced mixing process is utilized in this paper to model the pressure control portion of the Tank Pressure Control Experiment (TPCE) in microgravity1. The Volume of Fluid (VOF) method is used for modeling the dynamics of the interface during mixing. The simulations were performed at a range of jet Weber numbers from non-penetrating to fully penetrating. Two different initial ullage positions were considered. The computational results for the jet-ullage interaction are compared with still images from the video of the experiment. A qualitative comparison shows that the CFD model was able to capture the main features of the interfacial dynamics, as well as the jet penetration of the ullage.

active control↗