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At least 847 records · Page 47

Computational and Experimental Investigation of Interfacial Area in Near-Field Diesel Spray Simulation

The dense spray region in the near-field of diesel fuel injection remains an enigma. This region is difficult to interrogate with light in the visible range and difficult to model due to the rapid interaction between liquid and gas. In particular, modeling strategies that rely on Lagrangian particle tracking of droplets have struggled in this area. To better represent the strong interaction between phases, Eulerian modeling has proven particularly useful. Models built on the concept of surface area density are advantageous where primary and secondary atomization have not yet produced droplets, but rather form more complicated liquid structures. Surface area density, a more general concept than Lagrangian droplets, naturally represents liquid structures, no matter how complex. These surface area density models, however, have not been directly experimentally validated in the past due to the inability of optical methods to elucidate such a quantity. Optical diagnostics traditionally measure near-spherical droplet size far downstream, where the spray is optically thin. Using ultra-small-angle x-ray scattering (USAXS) measurements to measure the surface area and x-ray radiography to measure the density, we have been able to test one of the more speculative parts of Eulerian spray modeling. In conclusion, the modeling and experimental results have been combined to provide insight into near-field spray dynamics.

42 ENGINEERING↗

Probing Solid–Solid Interfacial Reactions in All-Solid-State Sodium-Ion Batteries with First-Principles Calculations

We present an exposition of first-principles approaches to elucidating interfacial reactions in all-solid-state sodium-ion batteries. We will demonstrate how thermodynamic approximations based on assumptions of fast alkali diffusion and multispecies equilibrium can be used to effectively screen combinations of Na-ion electrodes, solid electrolytes, and buffer oxides for electrochemical and chemical compatibility. We find that exchange reactions, especially between simple oxides and thiophosphate groups to form PO 4 3– , are the main cause of large driving forces for cathode/solid electrolyte interfacial reactions. A high reactivity with large volume changes is also predicted at the Na anode/solid electrolyte interface, while the Na 2 Ti 3 O 7 anode is predicted to be much more stable against a broad range of solid electrolytes. We identify several promising binary oxides, Sc 2 O 3 , SiO 2 , TiO 2 , ZrO 2 , and HfO 2 , that are similarly or more chemically compatible with most electrodes and solid electrolytes than the commonly used Al 2 O 3 is. Finally, we show that ab initio molecular dynamics simulations of the NaCoO 2 /Na 3 PS 4 interface model predict that the formation of SO 4 2– -containing compounds and Na 3 P is kinetically favored over the formation of PO 4 3– -containing compounds, in contrast to the predictions of the thermodynamic models. As a result, this work provides useful insights into materials selection strategies for enabling stable electrode/solid electrolyte interfaces, a critical bottleneck in designing all-solid-state sodium-ion batteries, and outlines several testable predictions for future experimental validation.

25 ENERGY STORAGE↗

Biologically inspired reinforcement using polydopamine of polymer bound composites

Interfacial strength plays a critical role in the mechanical properties of a composite system. In this work, a proven mock high explosive (HE), 5-iodo-2’-deoxyuridine (IDOX) was coated by the adhesive promoting polymer polydopamine (PDA), then formulated with an Estane binder system to form an improved HE mock composite. An extensive comparison study of mechanical properties was performed to determine the effects, if any, of PDA on the composite system. To aid in interpretation of the mechanical test data, neutron reflectometry experiments were performed to determine the thickness and structure of the as deposited PDA films. The mechanical performance of PDA-treated IDOX was then compared to untreated specimens by compression testing in the Brazilian disk geometry. The results strongly suggested that the structure of PDA consists of two layers: one low in density caused by polymer agglomerates attaching to the substrate during polymerization, and the second high in density caused by controlled linear deposition of polydopamine. Finally, the mechanical testing showed that PDA greatly increased the stiffness and yield strength of IDOX based mocks without causing any disruption to the underlying crystal system.

42 ENGINEERING↗

A Comprehensive Investigation into the Effect of a Low Surface Energy Treatment on Gas Hydrate, Asphaltene, and Wax Formation, Deposition, and Adhesion

The formation/precipitation and deposition of pipeline solids, such as gas hydrates, asphaltenes, and waxes have long plagued production fields. Given the vast differences in chemistries of these solids, any current prevention or mitigation strategy, particularly for cases in which multiple issues are a concern, is likely to involve an extensive assortment of chemical additives that are both costly and add complexity to the system. Surface treatments (coatings), on the other hand, present a relatively viable option for management strategies. A chemically and physically robust surface treatment with the ability to address deposition issues for multiple pipeline solids could not only decrease the operating expenditures for a field through material cost savings and obviation of downstream separation, but could also simplify produced fluids by eliminating additional chemicals from the mixture. The purpose of this study was to explore the feasibility of a particular surface treatment as part of a solids management strategy. This work used an omniphobic surface treatment to probe its effects on gas hydrate, asphaltene, and wax deposition. Specifically, an interfacial tensiometer (IFT) collected contact angle measurements for wettability studies. High-pressure rocking cells studied gas hydrate nucleation and deposition. A bench-scale flow loop quantified the deposition of oil and asphaltenes after a set time period. Finally, a mechanical shear device measured the adhesion force of wax deposits on untreated/treated surfaces. Static contact angle results showed that the omniphobic surface treatment had reduced surface interaction with water droplets in air, altering from the complete wetting on corroded surfaces to slightly hydrophobic conditions of greater than 100°. In addition, rocking-cell tests indicated that these omniphobic surface treatments may prevent gas hydrate deposition for up to 72 hours. The gas hydrate rocking-cell tests also demonstrated possible increases in induction time and occasional elimination of hydrate nucleation with the surface treatment. Finally, the surface treatment application, which also decreased surface roughness, showed that crude oil and asphaltene particles deposition, as well as the shear required to remove solidified wax deposits, could be reduced by a large factor. Overall, promising results were recorded for all major flow-assurance solids in the presence of the surface treatment.

Engineering↗

Role of the metal-support interface in the hydrodeoxygenation reaction of phenol

In this paper, the effect of interfacial sites between Pd particles and Nb 2 O 5 species is investigated by testing a series of Pd-Nb 2 O 5 /SiO 2 catalysts with different niobium loadings for the HDO reaction of phenol in the gas phase. Important differences in the selectivity to deoxygenated product were observed depending on the presence of niobium oxide close to Pd particles, which reveals the key role of the type of active phase in the control of reaction steps. It was found that Pd/SiO 2 catalyst promotes hydrogenation pathways, producing cyclohexanone as the major product. For Pd-Nb 2 O 5 /SiO 2 catalyst containing a Nb/Pd molar ratio of 0.5, a sharp increase in the selectivity to benzene is observed (7.5-fold). Increasing the Nb/Pd molar ratio, the formation of benzene is enhanced. The results showed that the Pd-Nb 2 O 5 interface, composed by an oxophilic oxide in the perimeter of the metal particle, is responsible for the activation of the Csingle bondO bond, promoting the deoxygenation reaction.

09 BIOMASS FUELS↗

Interfacial and Confinement-Mediated Organization of Gas Hydrates, Water, Organic Fluids, and Nanoparticles for the Utilization of Subsurface Energy and Geological Resources

Harnessing the subsurface geologic environments in an efficient and environmentally sustainable manner is challenged by uncertainties associated with predicting the fate of fluids and sustaining porosity and permeability in subsurface geologic environments. Some of these uncertainties arise from confined and interfacially induced structures of fluids in subsurface geologic environments. The formation of gas hydrates, phase transitions of confined fluids, assembly and deposition of heavy hydrocarbons, and the agglomeration and fate of nanoparticles in confined environments are summarized in this review. Nanoscale confinement contributes to anisotropic structures and dynamics of fluids, which is the basis for anomalous phase transition thermodynamics, reactivity, transport, and geomechanical behavior. In this review, we discuss the structures of confined fluids and deviation in observed properties from bulk fluids. The factors influencing the structures of confined fluids can be generally divided into two groups: (a) pore characteristics including pore size, pore surface chemistry, and pore geometry and (b) confined fluid/solid characteristics such as molecular structure, concentrations, charges, pore filling, and presence of additives. Scientific advancements and knowledge gaps in our understanding of the structures of confined fluids and the associated differences in observed properties compared to bulk fluids are discussed. Here, the phenomena discussed in this review are of particular relevance to our efforts in harnessing the subsurface environments for a low carbon future by increasing the utilization of geothermal energy, using CO 2 as a working fluid, and storing CO 2 in subsurface geologic environments.

42 ENGINEERING↗

Facet-dependent electron transfer induces distinct arsenic reallocations on hematite

The interfacial electron transfer (ET) between electron shuttling compounds and iron (Fe) oxyhydroxides plays a crucial role in the reductive dissolution of Fe minerals and the fate of surface-bound arsenic (As). However, the impact of exposed facets of highly crystalline hematite on reductive dissolution and As immobilization is poorly understood. In this study, we systematically investigated the interfacial processes of the electron shuttling compound cysteine (Cys) on various facets of hematite and the reallocations of surface-bound As(III) or As(V) on the respective surfaces. Our results demonstrate that the ET process between Cys and hematite generates Fe(II) and leads to reductive dissolution, with more Fe(II) generated on {001} facets of exposed hematite nanoplates (HNPs). Reductive dissolution of hematite leads to significantly enhanced As(V) reallocations on hematite. Nevertheless, upon the addition of Cys, a raipd release of As(III) can be halted by its prompt re-adsorption, leaving the extent of As(III) immobilization on hematite unchanged throughout the course of reductive dissolution. This is due to that Fe(II) can form new precipitates with As(V), a process that is facet-dependent and influenced by water chemistry. Electrochemical analysis reveals that HNPs exhibit higher conductivity and ET ability, which is beneficial for reductive dissolution and As reallocations on hematite. In conclusion, these findings highlight the facet-dependent reallocations of As(III) and As(V) facilitated by electron shuttling compounds and have implications for the biogeochemical processes of As in soil and subsurface environments.

54 ENVIRONMENTAL SCIENCES↗

Fluid – Fluid Interfacial Area and Its Impact on Relative Permeability - A Pore Network Modeling Study

Abstract Relative permeability (kr) is commonly modeled as an empirical function of phase saturation. Although current empirical models can provide a good match of one or two measured relative permeabilities using saturation alone, they are unable to predict relative permeabilities well when there is hysteresis or when physical properties such as wettability change. Further, current models often result in relative permeability discontinuities that can cause convergence and accuracy problems in simulation. To overcome these problems, recent research has modeled relative permeability as a state function of both saturation (S) and phase connectivity (X). Pore network modeling (PNM) data, however, shows small differences in relative permeability for the same S-X value when approached from a different flow direction. This paper examines the impact of one additional Minkowski parameter (Mecke and Arns, 2005), the fluid-fluid interfacial area, on relative permeability to identify if that satisfactorily explains this discrepancy. We calculate the total fluid-fluid interfacial areas (IA) during two-phase (oil/water) flow in porous media using pore network modeling. The area is calculated from PNM simulations using the areas associated with corners and throats in pore elements of different shapes. The pore network is modeled after a Bentheimer sandstone, using square, triangular, and circular pore shapes. Simulations were conducted for numerous primary drainage and imbibition cycles at a constant contact angle of 0° for the wetting phase. Simultaneous measurements of capillary pressure, relative permeability, saturation, and phase connectivity are made for each displacement. Fluid-fluid interfacial area is calculated from the PNM capillary pressure, the fluid location in the pore elements, and the pore element dimensional data. The results show that differences in the relative permeability at the same (S,X) point is explained well by differences in the fluid-fluid interfacial area (IA). That is, for a larger change in IA at these intersection points, the permeability difference is greater. That difference in relative permeability approaches zero as the difference in IA approaches zero. This confirms that relative permeability can be modeled better as a unique function of S, X, and IA. The results also show that an increase in IA restricts flow decreasing the nonwetting (oil) phase permeability. This decrease is caused by an increase in the throat area fraction compared to the corner area as the total area IA increases. The wetting phase relative permeability, however, shows the inverse trend, in that its relative permeability is greater when IA becomes larger owing to a greater fraction of the total area associated with the corners. The area IA, however, impacts the nonwetting phase relative permeability more than the wetting phase relative permeability. Corner flow improves the wetting phase relative permeability because the wetting phase is continuous there. Finally, a sensitivity analysis shows that relative permeability a is more sensitive to change in S than they are for IA for the case studied implying that if only two parameters are used to model relative permeability it is better to choose S and X.

Engineering↗

Effects of variable deceleration periods on Rayleigh-Taylor instability with acceleration reversals

The dynamics of an interfacial flow that is initially Rayleigh-Taylor unstable but becomes statically stable for some intermediate period due to the reversal of the externally imposed acceleration field is studied. We discuss scenarios that consider both single and double-acceleration reversals. The accel-decel (AD) case consists of a single reversal imposed at an instant after the constant acceleration instability has entered a self-similar regime. The layer of mixed fluid ceases to grow upon acceleration reversal, and the dominant mechanics are due to internal wave oscillations. Variation of mass flux and the Reynolds stress anisotropy is observed due to the action of the internal waves. Here, a second reversal of the AD case that is termed as accel-decel-accel, ADA is then explored; the response of the mixing layer is shown to depend strongly on the duration and the periodicity of the Reynolds stress anisotropy of the mixing layer during the deceleration period. We explore the effect of this variable deceleration period after the second acceleration reversal where the flow once again becomes Rayleigh-Taylor unstable based on metrics that include the integral mixing-layer width, bubble and spike amplitudes, mass flux, Reynolds stress anisotropy tensor, and the molecular mixing parameter.

42 ENGINEERING↗

Grafting nanometer metal/oxide interface towards enhanced low-temperature acetylene semi-hydrogenation

Metal/oxide interface is of fundamental significance to heterogeneous catalysis because the seemingly “inert” oxide support can modulate the morphology, atomic and electronic structures of the metal catalyst through the interface. The interfacial effects are well studied over a bulk oxide support but remain elusive for nanometer-sized systems like clusters, arising from the challenges associated with chemical synthesis and structural elucidation of such hybrid clusters. We hereby demonstrate the essential catalytic roles of a nanometer metal/oxide interface constructed by a hybrid Pd/Bi 2 O 3 cluster ensemble, which is fabricated by a facile stepwise photochemical method. The Pd/Bi 2 O 3 cluster, of which the hybrid structure is elucidated by combined electron microscopy and microanalysis, features a small Pd-Pd coordination number and more importantly a Pd-Bi spatial correlation ascribed to the heterografting between Pd and Bi terminated Bi 2 O 3 clusters. The intra-cluster electron transfer towards Pd across the as-formed nanometer metal/oxide interface significantly weakens the ethylene adsorption without compromising the hydrogen activation. As a result, a 91% selectivity of ethylene and 90% conversion of acetylene can be achieved in a front-end hydrogenation process with a temperature as low as 44 °C.

36 MATERIALS SCIENCE↗

Research three-dimensional hierarchical graphite architectures for anodes for fast charging

With current lithium ion batteries optimized for performance under relatively low charge rate conditions, implementation of XFC has been hindered by drawbacks including Li plating, kinetic polarization, and heat dissipation. This project will utilize model-informed design of 3-D hierarchical electrodes to tune key XFC related variables like 1) bulk porosity/tortuosity 2) vertical pore diameter, spacing, and lattice 3) crystallographic orientation of graphite particles relative to exposed surfaces 4) interfacial chemistry of the graphite surfaces through "artificial sEr formation using ALD 5) current collector surface roughness (aspect ratio, roughness factor, etc.). A key aspect of implementing novel electrodes is characterizing them in relevant settings. For this project, ultimately led out of University of Michigan by Neil Dasgupta, that includes both coin cell and 2+ Ah pouch cell testing, as well as comparison testing against baselines. Sandia National Labs will be conducting detailed cell characterization on iterative versions/improvements of the model-based hierarchical electrodes, as well as COTS cells for baseline comparisons. Key metrics include performance under fast charge conditions, as well as the absence or degree of lithium plating. Sandia will use their unique high precision cycling and rapid EIS capabilities to accurately characterize performance and any lithium plating during 6C charging and beyond, coupling electrochemical observations with cell teardown. Sandia will also design custom fixturing to cool cells during rapid charge, to decouple any kinetic effects brought about by cell heating and allow comparisons between different cells and charge rates. Using these techniques, Sandia will assess HOH electrodes from the University of Michigan, as well as aiding in iterative model and electrode design.

25 ENERGY STORAGE↗

Experimental and statistical study on the effect of process parameters on the quality of continuous fiber composites made via additive manufacturing

Ongoing research in additive manufacturing towards structural and industrial application has led to the use of commingled roving as a manufacturing feedstock for printing high fiber volume fraction composites. The prospects of using this technology for high performance applications necessitates the need for a comprehensive experimental investigation into the effects of processing parameters on the quality of an additively manufactured composite printed from commingled roving feedstock. Here, in this work, transverse flexure and void fraction matrix pyrolysis testing are both performed to evaluate composite quality. The transverse flexure test is a testing approach that evaluates the quality of the interfacial fiber-matrix bond while the void fraction test estimates the void content in the printed composite. A full observational study consisting of 27 different test combinations is done to investigate the effects of three different process parameters namely, temperature, pressure, and print speed across three different levels. Composite samples were made from commingled roving of E-glass and amorphous PET using an in-house built continuous fiber composite digital manufacturing system. Least squares regression analysis is performed to study the main, interaction and quadratic effects of process parameters. A statistical regression model having an R2 adjusted value of 80.1% is generated from the transverse flexure study, which is used to explain main and interaction effects and also predict performance. Response surface plots are also generated and are used to optimize process parameters which can subsequently be of help in scaling up composite manufacturing. Results show that all three process parameters are highly statistically significant at the 0.01 level of significance. Pressure * Temperature and Pressure * Printspeed are significant interaction terms. Pressure plays a weightier role when print speed is increased or temperature is decreased as it closes more voids that would ordinarily have been introduced because of drop in polymer melt viscosity. Micrographic analysis is also performed.

36 MATERIALS SCIENCE↗

Research three-dimensional hierarchical graphite architectures for anodes for fast charging

With current lithium ion batteries optimized for performance under relatively low charge rate conditions, implementation of XFC has been hindered by drawbacks including Li plating, kinetic polarization, and heat dissipation. This project will utilize model-informed design of 3-D hierarchical electrodes to tune key XFCrelated variables like 1) bulk porosity/tortuosity 2) vertical pore diameter, spacing, and lattice 3) crystallographic orientation of graphite particles relative to exposed surfaces 4) interfacial chemistry of the graphite surfaces through "artificial sEr' formation using ALD 5) current collector surface roughness (aspect ratio, roughness factor, etc.). A key aspect of implementing novel electrodes is characterizing them in relevant settings. For this project, ultimately led out of University of Michigan by Neil Dasgupta, that includes both coin cell and 2+ Ah pouch cell testing, as well as comparison testing against baselines. Sandia National Labs will be conducting detailed cell characterization on iterative versions/improvements of the model-based hierarchical electrodes, as well as COTS cells for baseline comparisons. Key metrics include performance under fast charge conditions, as well as the absence or degree of lithium plating. Sandia will use their unique high precision cycling and rapid EIS capabilities to accurately characterize performance and any lithium plating during 6C charging and beyond, coupling electrochemical observations with cell teardown. Sandia will also design custom fixturing to cool cells during rapid charge, to decouple any kinetic effects brought about by cell heating and allow comparisons between different cells and charge rates. Using these techniques, Sandia will assess HOH electrodes from the University of Michigan, as well as aiding in iterative model and electrode design.

25 ENERGY STORAGE↗

Bio-inspired Surface Structures to Mitigate Interfacial Particle Adhesion and Erosion - A Review

Lunar dust known as regolith is a huge challenge for lunar exploration missions. Formed over millennia by a complex process involving impacts of meteoroids and micrometeoroids on the lunar surface, lunar dust is porous, highly abrasive with sharp jagged edges, chemically reactive, electrostatically charged and sometimes magnetic. The chemical composition and thickness of the dust layer also varies in different regions of the lunar surface. From samples obtained by previous lunar missions, the average particle size is below 100 microns. This dust has the tendency to strongly adhere to any exposed surfaces, and often degrades the material functionality to eventually cause failure. Any material on the lunar surface is also subject to harsh temperature cycles ranging from -178 ̊C to + 123 ̊C and extreme ultraviolet radiation. While on the lunar surface, different classes of materials would be required for different applications. Advanced materials have been and will be used throughout the lunar lander, habitat, and mission equipment. Examples include: polymeric materials for astronaut protective clothing; metals and ceramics for the lunar lander legs and habitats, and excavating equipment; and semiconductors for solar panels and on-board electronics. In all these applications, the surfaces of the materials are expected or understood to be exposed to the extreme lunar environment condition that includes the regolith dust. During the Apollo missions, the dust clung to and abraded the astronaut’s suits, degraded seals, optics, clogged sensors and reduced performance of thermal radiators. The lunar dust adheres to the surface by various mechanisms, which include electrostatic and Coulombic interactions, Van-der-Waals forces, magnetic forces, mechanical interlocking, chemical bonding and donor-acceptor interactions. There are three primary strategies for developing technologies to minimize the lunar dust adhesion: active, passive and a combination of active and passive. In the active approach, an external energy is needed to prevent or remove particles from collecting on the surface. Mechanically powered brushes and electrodynamic dust screens are two examples. In the passive approach, no external power is needed, and the material surface properties are able to mitigate dust adhesion. A well-known example of this strategy is the low work function coatings for non-stick surfaces. In most cases a combination of active and passive methods might be needed to optimally manage the lunar regolith. The passive method is significantly more attractive as it does not require any external power or an additional control subsystem. These approaches optimize the mission payload and reduce risk. Surface modification to minimize the dust adhesion is thus very important to lunar missions. Here, naturally evolved surface structures might provide guidance for solutions. There are several factors that have to be considered for minimizing particle adhesion to a surface. These include the substrate material properties, surface topography, chemistry, and the characteristics of the adhering particles. When engineering a surface, the substrate material chosen would be dependent on the needs of the application. Tailoring the surface microstructure or chemistry opens up more possibilities for its optimal utilization

Lunar Dust↗

Enriched immersed boundary method (EIBM) for interface-coupled multi-physics and applications to convective conjugate heat transfer

It is challenging to develop numerical methods that simultaneously maintain accuracy of resolving boundary conditions and mesh flexibility to handle the interface in interface-coupled multi-physics problems involving large property discontinuity. On the one hand, boundary-fitted methods possess high accuracy in capturing the interfacial phenomenon but involve complicated volumetric mesh generation, mesh-motion, and even re-meshing procedures. On the other hand, immersed boundary methods (IBM) provide mesh flexibility but sometimes suffer from inferior interface representations, leading to poor enforcement of boundary conditions. This paper presents an enriched immersed boundary method (EIBM) to overcome this challenge and demonstrates its efficacy in conjugate heat transfer, a representative example in interface-coupled multi-physics systems that have implications for many industrial processes. Further, the core technique of the method is to enhance IBM’s accuracy of the fluid–solid interface by enriching the degrees of freedom of the cut elements to enforce temperature and flux compatibilities and resolve all the physical unknowns on the background mesh to simplify the volumetric mesh generation. We implement the EIBM under the framework of a variational multiscale formulation for coupled Navier–Stokes and thermodynamics equations. The enriched DoFs enable better enforcement of temperature and flux compatibilities with large conductivity ratios across the fluid–solid interface. At the same time, the immersed nature of the proposed method still attains mesh flexibility. The EIBM’s accuracy is thoroughly evaluated through a set of examples, ranging from benchmark problems with analytical solutions to real-world cooling processes of a moving metallic structure with complex geometry.

42 ENGINEERING↗

Residual Stresses Modeled in Thermal Barrier Coatings

Thermal barrier coating (TBC) applications continue to increase as the need for greater engine efficiency in aircraft and land-based gas turbines increases. However, durability and reliability issues limit the benefits that can be derived from TBC's. A thorough understanding of the mechanisms that cause TBC failure is a key to increasing, as well as predicting, TBC durability. Oxidation of the bond coat has been repeatedly identified as one of the major factors affecting the durability of the ceramic top coat during service. However, the mechanisms by which oxidation facilitates TBC failure are poorly understood and require further characterization. In addition, researchers have suspected that other bond coat and top coat factors might influence TBC thermal fatigue life, both separately and through interactions with the mechanism of oxidation. These other factors include the bond coat coefficient of thermal expansion, the bond coat roughness, and the creep behavior of both the ceramic and bond coat layers. Although it is difficult to design an experiment to examine these factors unambiguously, it is possible to design a computer modeling "experiment" to examine the action and interaction of these factors, as well as to determine failure drivers for TBC's. Previous computer models have examined some of these factors separately to determine their effect on coating residual stresses, but none have examined all the factors concurrently. The purpose of this research, which was performed at DCT, Inc., in contract with the NASA Lewis Research Center, was to develop an inclusive finite element model to characterize the effects of oxidation on the residual stresses within the TBC system during thermal cycling as well as to examine the interaction of oxidation with the other factors affecting TBC life. The plasma sprayed, two-layer thermal barrier coating that was modeled incorporated a superalloy substrate, a NiCrAlY bond coat, and a ZrO2-8 wt % Y2O3 ceramic top coat. We examined the effect on stress during burner rig thermal cycling of the following independent variables: creep in the bond coat and top coat, oxidation, bond coat coefficient of thermal expansion, number of thermal cycles, and interfacial roughness. All these factors were suspected of influencing TBC failure. The model showed that all the material properties studied had a significant effect on the coating's residual stresses if the interface of the bond coat was rough. Bond coat expansion, bond coat oxidation, and bond coat creep had the highest effect on coating stresses, and these were highly interactive. The model also showed that the mechanism of stress generation during thermal cycling changed with the number of thermal cycles. Bond coat and top coat creep dominated stress generation during early thermal cycles, greatly increasing delamination stresses at the peaks of the bond coat. Therefore, creep is the prime driver for delamination cracking early in life, but cracking is limited to the bond coat peak region. Oxidation of the bond coat, on the other hand, tended to dominate stress generation during later cycles by greatly increasing delamination stresses over bond coat valleys. These results indicate that oxidation is the driver for the continued cracking necessary to cause ceramic layer spallation.

Freborg, A. M.↗

Polarization-Controlled Structural Modulation in the Single Atomic Layer at the PbZr 0.2 Ti 0.8 O 3 /LaNiO 3 Interface

Conductivity modulation via ferroelectric polarization coupling with LaNiO 3 (LNO) is demonstrated at an epitaxial ferroelectric–LNO interface. Conductivity measurements, varying the thickness of the LNO channel, show that this phenomenon is confined to a few atomic layers at the interface. Combining in situ biasing and off-axis holography, we mapped out electrostatic potentials at the PbZr 0.2 Ti 0.8 O 3 (PZT)/LNO/SrTiO 3 (STO) heterostructure upon polarization switching. Using aberration-corrected STEM, the interfacial atomic structures were investigated for the two different PZT polarization states. Polarization in PZT induces a significant change in the in-plane O–Ni–O bond angles, with a 37° modulation in the topmost 1 or 2 LNO unit cells, driven by strain in the oxygen sublattice for the two opposite polarization directions in PZT. Both oxygen and cation sublattices exhibit strain responses exceeding 10% upon switching. This atomic-layer structural modulation highlights a mechanism for functional oxide heterostructure development, offering pathways for advancements in nonvolatile memory, sensors, and energy-efficient transistors.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Boosting catalytic propane oxidation over PGM-free Co 3 O 4 nanocrystal aggregates through chemical leaching: A comparative study with Pt and Pd based catalysts

Rational modification of interfacial structure and chemistry can help effectively tailor the reactivity and stability of heterogeneous catalysts regardless of their elemental or compound natures. In this work, a diluted acidic treatment was designed and utilized to modify the surface structure and chemistry of spinel Co 3 O 4 nanoparticles. Such a chemical leaching strategy has significantly promoted the propane oxidation activity of the PGM-free Co 3 O 4 nanocrystal aggregates. With a much higher activity than the commercial Al 2 O 3 supported Pt and Pd catalysts, these leached nanoparticle aggregates exhibited much more abundant defects, surface Co 2+ and chemisorbed oxygen species. Such surface-modified Co 3 O 4 nanocatalysts have displayed excellent and stable propane oxidation efficiency independent of both O 2 and C 3 H 8 concentrations, where the activities of both commercial Pt (or Pd)/Al 2 O 3 and self-made Pt (or Pd)/CeO 2 catalysts were greatly affected by different O 2 and C 3 H 8 concentrations. Meanwhile, the Co 3 O 4 nanocrystal aggregates catalyst exhibited good performance in presence of water or sulfur dioxide. This facile chemical leaching based technique provides a potential means to make highly active and stable oxide catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗