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At least 1,657 records · Page 92

Heat Transfer Coefficient at Cast-Mold Interface During Centrifugal Casting: Calculation of Air Gap

During centrifugal casting, the thermal resistance at the cast-mold interface represents a main blockage mechanism for heat transfer. In addition to the refractory coating, an air gap begins to form due to the shrinkage of the casting and the mold expansion, under the continuous influence of strong centrifugal forces. Here, the heat transfer coefficient at the cast-mold interface h has been determined from calculations of the air gap thickness d{sub a} based on a plane stress model taking into account thermoelastic stresses, centrifugal forces, plastic deformations, and a temperature-dependent Young’s modulus. The numerical approach proposed here is rather novel and tries to offer an alternative to the empirical formulas usually used in numerical simulations for a description of a time-dependent heat transfer coefficient h. Several numerical tests were performed for different coating thicknesses d{sub C}, rotation rates Ω, and temperatures of solidus T{sub sol}. Results demonstrated that the scenario at the interface is unique for each set of parameters, hindering the possibility of employing empirical formulas without a preceding experiment being performed. Initial values of h are simply equivalent to the ratio of the coating thermal conductivity and its thickness (~ 1000 Wm{sup −2} K{sup −1}). Later, when the air gap is formed, h drops exponentially to values at least one order of magnitude smaller (~ 100 Wm{sup −2} K{sup −1}).

36 MATERIALS SCIENCE↗

Numerical Simulation of the Three-Phase Flow of a Bubble Interacting with the Steel–Slag Interface During the Secondary Refining Process

Gas stirring is an effective method for the secondary refining process of steel. The microphenomena among the phases of an argon bubble floating in steel and motion across the steel–slag interface were simulated and discussed with a sharp interface tracking method. A water-model experiment was set to validate the numerical model, and the experimental results showed agreement with the numerical model. A critical size for bubbles to pass the interface was found using the model.

36 MATERIALS SCIENCE↗

Effect of Interface Structure on the Hydrophobicity, Mechanical and Optical Properties of HfO2/Mo/HfO2 Multilayer Films

We report on the super-hydrophobicity and tunable and optical and mechanical properties of transparent HfO2(50 nm)/Mo(20 nm)/HfO2(50 nm) multilayer films facilitated by engineering the ceramic-metal interface microstructure. A comparative study of nano-columnar and glassy (dense) structured HfO2/Mo/HfO2 multilayer films demonstrate the remarkable effect of interface structure on their hydrophobicity and mechanical properties. The nano-columnar structured multilayer films exhibit the dominance over the glassy structured stack in terms of their enhanced characteristics, namely the mechanical characteristics, anti-reflection behavior, visible transmittance, and hydrophobicity. While hydrophobicity is derived from the combined effect of hierarchical surface roughness and nano-columnar structure of the top and bottom Hf-oxide ceramic layers, the enhanced mechanical response is derived from the columnar structure of Mo metallic interlayer vertically aligned with overall multilayer stack. The combination of super-hydrophobicity and enhanced mechanical properties of optically transparent HfO2/Mo/HfO2 multilayer films through HfO2-Mo interface structure control as demonstrated in this work may provide a pathway to further tune the efficiency and in the optimization of architectures for energy-saving applications.

EFFICIENT GLASS WINDOWS, ELECTRICAL-PROPERTIES, TH↗

Use of an Open Port Sampling Interface Coupled to Electrospray Ionization for the On-Line Analysis of Organic Aerosol Particles

A simple design for an open port sampling interface coupled to electrospray ionization (OPSI-ESI) is presented for the analysis of organic aerosols. The design uses minimal modifications to a Bruker electrospray (ESI) emitter to create a continuous flow, self-aspirating open port sampling interface. Considerations are presented for introducing aerosol to the open port sampling interface including aerosol gas flow and solvent flow rates. The device has been demonstrated for use with an aerosol of nicotine as well as aerosol formed in the pyrolysis of biomass. Upon comparison with extractive electrospray ionization (EESI), this device has similar sensitivity with increased reproducibility by nearly a factor of three. The device has the form factor of a standard Bruker/Agilent ESI emitter and can be used without any further instrument modifications. .

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Heterostructured nano-catalysts with efficient metal-oxide interfaces unlock high-performance direct methanol protonic ceramic fuel cells

Direct methanol protonic ceramic fuel cells (PCFCs) are attractive due to their low cost, convenient storage, and high volumetric energy density, as well as their suitability for transportation. However, the poor coking tolerance of conventional nickel-based anodes leads to their susceptibility to severe carbon deposition and significant deactivation after long-term exposure to hydrocarbons. Herein, we report a nano-catalyst of Ce 0.6 Ni 0.2 Cu 0.2 O 2 with a heterogeneous structure that is spontaneously reduced into a Ce 0.6 Ni 0.2-x Cu 0.2-x O 2-δ (CeNCO) oxide framework interfaced with a nano NiCu alloy (denoted as NC/CeNCO) under operating conditions, as confirmed by analyses of X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, and transmission electron microscopy. A Ni-BaCe 0.7 Y 0.06 Yb 0.06 Zr 0.06 Hf 0.06 Gd 0.06 O 3-δ anode-supported PCFC employing the NC/CeNCO metal-oxide catalyst achieved a peak power density of 1.11 W cm −2 and operational stability of about 100 h at 700 °C when fueled by 35 % CH 3 OH-15 % H 2 O-50 % N 2 . In conclusion, the enhanced performance and coking resistance are attributed to the efficient interfaces of Ni, Cu, and ceria-based oxide in NC/CeNCO for CH 3 OH reforming, as confirmed by analyses of electrochemical performance and Raman spectroscopy with density functional theory calculations, revealing that these interfaces can enhance CH 3 OH activation and promote efficient OH-mediated carbon removal via COH intermediates.

30 DIRECT ENERGY CONVERSION↗

Dynamic Wettability Alteration of Calcite, Silica and Illite Surfaces in Subsurface Environments: A Case Study of Asphaltene Self-Assembly at Solid Interfaces

A basic understanding of dynamic wettability alteration at complex solid interfaces in varying fluidic environments representative of the subsurface environments is essential for engineering field-scale strategies to enhance energy recovery while reducing environmental impacts. In this study, we characterize dynamic wettability alteration at solid surfaces (e.g., calcite, silica and illite) resulting from the self-assembly and adsorption of polyaromatic macromolecules known as asphaltenes in heptane and toluene solvents at 200 bar and 313 K using classical molecular dynamics simulations. These conditions are chosen to be representative of the subsurface environments. On adding asphaltenes, the equilibrium contact angles on calcite, silica and illite surfaces which are in the range of 25–34° increased to 69–79°. The adsorption and self-assembly of asphaltene molecules on the solid surfaces and the accumulation on water/hydrocarbon interfaces reduces the spreading distances of water molecules and enhances the hydrophobicity of the solid surfaces. Moreover, the accumulation of asphaltene molecules at the water/liquid hydrocarbon interfaces results in a reduction of the interfacial tension of water/heptane and water/toluene, thus stabilizing the water droplet. The enhanced surface hydrophobicity contributes to the formation of layered structures of heptane and toluene close to the solid surfaces and reduces the self-diffusivities of these molecules close to the surface.

42 ENGINEERING↗

Traction-separation response of bilayer graphene interfaces: The role of an intercalated single atomic layer of water molecules and hydroxyl groups

Molecular dynamics simulations of the normal and shear traction-separation response of dry and wet bilayer graphene interfaces were performed. The influence of a single, atomic layer of water molecules sandwiched between graphene layers and hydroxyl functionalization on one or both layers were investigated. Hydroxyl groups provided a shielding effect during normal separation while favoring stick-slip friction under sliding conditions. The single, atomic layer of water molecules confined between hydrophilic and asymmetric hydrophobic/hydrophilic surfaces was found to ease sliding friction. The mechanisms arose from the balance between the attractive and repulsive graphene/water interactions through bridges of single water molecules between the two surfaces and the structure of the water monolayer under confinement for which an out-of-plane water/water hydrogen bond network could not be developed. The single, atomic layer of water molecules reduced the sliding friction the most when both surfaces were hydrophilic and lowered the sliding friction of the asymmetric hydrophobic/hydrophilic interfaces to that when both surfaces were hydrophobic. An optimal hydroxyl surface coverage of less than 10% may exist for efficient water lubrication, with diminishing effect with increasing number of hydroxyl groups. Finally, the findings offer a design strategy for assembling bilayer graphene interfaces with tailored friction and sliding contact properties.

36 MATERIALS SCIENCE↗

First-Principles study of interface capture of Ni during high-temperature oxidation of NiCr alloys

The formation of precipitated phases of less reactive metals within an oxide scale during alloy oxidation can disrupt its structural integrity, significantly compromising the protective function of the oxide. To better understand this phenomenon, it is crucial to investigate the atomic-level diffusion mechanisms that drive precipitate formation. In this study, we employ first-principles calculations to examine the diffusion and aggregation of Ni atoms across the NiCr/Cr 2 O 3 interface during the high-temperature oxidation of NiCr alloys. Our results reveal that, in the absence of Cr vacancies, Ni atoms predominantly remain within the NiCr substrate, with minimal migration toward the Cr 2 O 3 layer. However, when Cr vacancies are present at both the NiCr/Cr 2 O 3 interface and within the Cr 2 O 3 bulk, Ni atoms exhibit a strong propensity to migrate from the NiCr substrate into the Cr 2 O 3 bulk, where they aggregate into Ni-rich regions with a corundum structure. This study provides valuable atomic-level insights into the diffusion and aggregation of less-reactive metals at the alloy/oxide interface, enhancing our understanding of solute capture and its contribution to the degradation of oxidation resistance in alloys.

Chen, Jianmin [Xiangtan University (China)] (ORCID↗

Visualization of the surface distribution of photocatalytic activity at the anatase/rutile TiO2 interface using X-ray photoelectron emission microscopy

We applied X-ray photoelectron emission microscopy (XPEEM) to visualize the surface distribution of photocatalytic activity at the anatase/rutile (A/R) interface of titanium dioxide. Acetic acid was adsorbed on the surface, and its decomposition and desorption reactions under ultraviolet light irradiation were monitored by observing C 1s spectra, enabling direct observation of the spatial distribution of photocatalytic activity. Complementary crystal structure information was obtained using spatially resolved low-energy electron diffraction, low-energy electron microscopy, X-ray absorption spectroscopy, and micro-focused Raman spectroscopy. Comparison with these structural data allowed for the evaluation of the photocatalytic activity as a function of the distance from the A/R interface. The activity is enhanced in the vicinity of the interface and gradually decreases toward both the anatase and rutile regions. These results demonstrate that XPEEM is an effective technique for spatially resolved mapping of photocatalytic activity, which has\\r\\npreviously been inaccessible using conventional characterization techniques.

25 ENERGY STORAGE↗

Designer interface peptide grafts target estrogen receptor alpha dimerization

The nuclear transcription factor estrogen receptor alpha (ERα), triggered by its cognate ligand estrogen, regulates a variety of cellular signaling events. ERα is expressed in 70% of breast cancers and is a widely validated target for anti-breast cancer drug discovery. Administration of anti-estrogen to block estrogen receptor activation is still a viable anti-breast cancer treatment option but anti-estrogen resistance has been a significant bottle-neck. Dimerization of estrogen receptor is required for ER activation. Blocking ERα dimerization is therefore a complementary and alternative strategy to combat anti-estrogen resistance. Dimer interface peptide “I-box” derived from ER residues 503–518 specifically blocks ER dimerization. Recently using a comprehensive molecular simulation we studied the interaction dynamics of ERα LBDs in a homo-dimer. Based on this study, we identified three interface recognition peptide motifs LDKITDT (ERα residues 479–485), LQQQHQRLAQ (residues 497–506), and LSHIRHMSNK (residues 511–520) and reported the suitability of using LQQQHQRLAQ (ER 497–506) as a template to design inhibitors of ERα dimerization. Stability and self-aggregation of peptide based therapeutics poses a significant bottle-neck to proceed further. In this study utilizing peptide grafted to preserve their pharmacophoric recognition motif and assessed their stability and potential to block ERα mediated activity in silico and in vitro. The Grafted peptides blocked ERα mediated cell proliferation and viability of breast cancer cells but did not alter their apoptotic fate. We believe the structural clues identified in this study can be used to identify novel peptidometics and small molecules that specifically target ER dimer interface generating a new breed of anti-cancer agents. - Highlights: • Designer peptide grafts retain core molecular recognition motif during MD simulations. • Designer peptide grafts with Poly-ALA helix form stable complexes with estrogen receptor in silico. • Inhibitor peptides significantly decrease estrogen induced cell proliferation of ER positive breast cancer cells in vitro.

60 APPLIED LIFE SCIENCES↗

High-Order Mesh Morphing for Boundary and Interface Fitting to Implicit Geometries

Here, we propose a method that morphs high-order meshes such that their boundaries and interfaces coincide/align with implicitly defined geometries. Our focus is particularly on the case when the target surface is prescribed as the zero isocontour of a smooth discrete function. Common examples of this scenario include using level set functions to represent material interfaces in multimaterial configurations, and evolving geometries in shape and topology optimization. The proposed method formulates the mesh optimization problem as a variational minimization of the sum of a chosen mesh-quality metric using the Target-Matrix Optimization Paradigm (TMOP) and a penalty term that weakly forces the selected faces of the mesh to align with the target surface. The distinct features of the method are use of a source mesh to represent the level set function with sufficient accuracy, and adaptive strategies for setting the penalization weight and selecting the faces of the mesh to be fit to the target isocontour of the level set field. We demonstrate that the proposed method is robust for generating boundary- and interface-fitted meshes for curvilinear domains using different element types in 2D and 3D.

97 MATHEMATICS AND COMPUTING↗

Constrained optimization framework for interface-aware sub-scale dynamics discrete closure model for multimaterial cells in Lagrangian cell-centered hydrodynamics

In this paper, we present the new discrete optimization-based interface-aware sub-scale dynamics (IA-SSD) closure model for multimaterial cells for Lagrangian cell-centered hydrodynamics. For the multimaterial cell, the kinematic and thermodynamic properties (e.g., velocity, density, pressure and internal energy) will typically vary between the materials. The discrete closure model is responsible for an accurate update of the thermodynamic states of the individual material components in the multimaterial cell, and for determining the nodal forces that move the vertices of the cell. The IA-SSD closure model consists of two stages — a bulk stage followed by a sub-scale stage. During the bulk stage, the total change in the volume of the cell, total force applied to the cell, and total work done on the cell are distributed between the materials to update their volume, velocity and total energy. This distribution is performed using volume fractions of the materials. During the second stage, sub-scale interactions of the materials inside the multimaterial cell are taken into account. At this stage, information about the topology of the materials inside the multimaterial cell is used, allowing the orientations of internal interfaces to be included in the model. Each material interacts in a pair-wise fashion with the materials with which it has a common boundary. The interactions are based on the solution of the acoustic Riemann problem between each pair of materials and are limited using physically justified constraints: positivity of volume, positivity of internal energy, and controlled rate of pressure relaxation. To determine the values of the limiter coefficients, a constrained-optimization framework is employed using a quadratic objective function with linear constraints. It is a first-of-its kind application of constrained optimization to develop discrete closure models in a more rigorous fashion. The pair-wise interaction between materials is essentially one dimensional in the direction that is normal to interface. Finally, for this reason, we demonstrate in this paper the performance of our new model on one dimensional numerical examples.

97 MATHEMATICS AND COMPUTING↗

Targeting the SH2-Kinase Interface in Bcr-Abl Inhibits Leukemogenesis

Chronic myelogenous leukemia (CML) is caused by the constitutively active tyrosine kinase Bcr-Abl and treated with the tyrosine kinase inhibitor (TKI) imatinib. However, emerging TKI resistance prevents complete cure. Therefore, alternative strategies targeting regulatory modules of Bcr-Abl in addition to the kinase active site are strongly desirable. Here, we show that an intramolecular interaction between the SH2 and kinase domains in Bcr-Abl is both necessary and sufficient for high catalytic activity of the enzyme. Disruption of this interface led to inhibition of downstream events critical for CML signaling and, importantly, completely abolished leukemia formation in mice. Furthermore, disruption of the SH2-kinase interface increased sensitivity of imatinib-resistant Bcr-Abl mutants to TKI inhibition. An engineered Abl SH2-binding fibronectin type III monobody inhibited Bcr-Abl kinase activity both in vitro and in primary CML cells, where it induced apoptosis. This work validates the SH2-kinase interface as an allosteric target for therapeutic intervention.

59 BASIC BIOLOGICAL SCIENCES↗

Gibbs adsorption equation for planar fluid–fluid interfaces: Invariant formalism

Here, the fundamental underpinnings of the Gibbs adsorption equation (GAE) are enunciated including sundry choices for the location of the zero-volume dividing surface. Comparison is made to the finite-volume thermodynamic analyses of Guggenheim and Hansen. Given that Gibbs phase rule is properly invoked, only invariant surface properties appear in the GAE. In the framework of invariant surface properties, both the zero-volume (Gibbs) and the finite-volume (Guggenheim) treatments of the surface phase give identical results for the GAE, validating the thermodynamic generality and rigor of the expression. Application of the GAE is made to strong and weak electrolytes, to electrified interfaces (Lippmann equation), and to surface complexation. Usefulness of the GAE in molecular simulation of interfaces is outlined. Special attention is paid to the seminal contributions of Fainerman and Miller in applying molecular-thermodynamic interfacial-layer models toward predicting adsorption behavior at fluid/fluid interfaces. Conversion of adsorption isotherms into two-dimensional interfacial-tension equations of state via the GAE is highlighted. Confusion over interpretation of the Gibbs adsorption equation arises primarily because of imprecise meaning for adsorbed amounts. Once invariant adsorptions are confirmed and utilized, the Gibbs adsorption equation yields identical results for Gibbs zero-volume surface thermodynamics and for Guggenheim finite-volume surface thermodynamics.

Dividing surface↗

Dynamic stability of a crude oil/brine interface: Effect of anion type

The chemical composition of the aqueous phase plays an essential role in water-based enhanced-oil recovery processes. The aqueous phase ionic profile affects the snap-off response of a crude oil-brine system by linking it to the brine-crude oil interfacial rheology. In this work, we focus on the effect of the anion on the snap-off response. To this end, a sample of crude oil from the Minnelusa Sandstone formation in Wyoming was selected, and several aqueous solutions were prepared with salts containing sodium cation and different anions (chlorides, sulfates, and phosphates) at two ionic strength values, 0.6 M and 6 mM, as cases of high- and low-salinity water. Interfacial tension, interfacial viscoelasticity and interface stability were analyzed as functions of aging time using pendant drop, dilatational rheology, and liquid bridge techniques, respectively. Here the results show that solutions with higher ionic strength led to the formation of more rigid interfaces, i.e. higher elastic modulus, and faster formation kinetics. In the low-salinity regime, solutions with polyvalent anions produce more viscoelastic interfaces at faster rates than solutions with monovalent anions. Finally, an excellent correlation (R 2 greater than 0.97) between the relative stability of the interfacial film, predicted in liquid bridge tests, and the ratio of interfacial tension and interfacial elastic modulus was found.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structure and Dynamics of Forsterite-scCO2/H2O Interfaces as a Function of Water Content

Molecular dynamics (MD) simulations of forsterite surfaces in contact with supercritical carbon dioxide (scCO2) fluids of varying water content were performed to determine the partition of water between the scCO2 fluid and the mineral surface, the nature of CO2 and H2O bonding at the interface, and the regions of the interface that may be conducive to HxCO3(2-x)- formation. Calculations of the free energy of the associative adsorption of water onto the (010) forsterite surface from the scCO2 phase indicated that the formation of a water film up to three-monolayer thick can be exothermic even for water contents below the water saturation concentration of the scCO2 fluid. In MD simulations of scCO2/H2O mixtures in contact with the (010) forsterite surface, H2O was found to readily displace CO2 at the surface and, therefore, CO2 directly contacted the surface only for water coverages below two monolayers. For thicker water films, a two-monolayer hydration layer formed that CO2 could not penetrate. Simulations of the hydroxylated (010) surface and of the (011) surface suggested that this conclusion can be extended to forsterite surfaces with different surface structures and/or compositions. The density, diffusion, and degree of hydration of CO2 as well as the extent of CO2/H2O mixing at the interface were all predicted to depend strongly on the thickness of the water-rich film, i.e., on the water content of the scCO2 fluid.

58 GEOSCIENCES↗

On the Importance of Metal–Oxide Interface Sites for the Water–Gas Shift Reaction Over Pt/CeO2 Catalysts

The mechanism of water–gas shift reaction at the three-phase boundary of Pt/CeO2 catalysts has been investigated using density functional theory and microkinetic modeling to better understand the importance of metal–oxide interface sites in heterogeneous catalysis. Analysis of a microkinetic model based on parameters obtained from first principles suggests that both the “Redox pathway” and the “Associative carboxyl pathway with redox regeneration” could operate on Pt/CeO2 catalysts. Although (1) only few interfacial Pt atoms are found to be catalytically active at low temperatures due to strong adsorption of CO and (2) interfacial O–H bond breakage is difficult due to the high reducibility of ceria, interface sites are 2–3 orders of magnitude more active than Pt (1 1 1) and stepped Pt surface sites and therefore effectively determine the overall activity of Pt/CeO2. The high activity of Pt/CeO2 interface sites originates from a significantly enhanced water activation and dissociation at interfacial oxygen vacancies.

Environmental Molecular Sciences Laboratory↗

Amorphous iron-(hydr) oxide networks at liquid/vapor interfaces: In situ X-ray scattering and spectroscopy studies

Surface sensitive X-ray reflectivity (XR), fluorescence (XF), and grazing incidence X-ray diffraction (GIXD) experiments were conducted to determine the accumulation of ferric iron Fe (III) or ferrous iron Fe (II) under dihexadecyl phosphate (DHDP) or arachidic acid (AA) Langmuir monolayers at liquid/vapor interfaces. Analysis of the X-ray reflectivity and fluorescence data of monolayers on the aqueous subphases containing FeCl3 indicates remarkably high levels of surface-bound Fe (III) in number of Fe3þ ions per molecule (DHDP or AA) that exceed the amount necessary to neutralize a hypothetically completely deprotonated monolayer (DHDP or AA). These results suggest that nano-scale iron (hydr) oxide complexes (oxides, hydroxides or oxyhydroxides) bind to the headgroups and effectively overcompensate the maximum possible charges at the interface. The lack of evidence of in-plane ordering in GIXD measurements and strong effects on the surface-pressure versus molecular area isotherms indicate that an amorphous network of iron (hydr) oxide complexes contiguous to the headgroups is formed. Similar experiments with FeCl2 generally resulted with the oxidation of Fe (II)–Fe (III) which consequently leads to ferric Fe (III) complexes binding albeit with less iron at the interface. Controlling the oxidation of Fe (II) changes the nature and amount of binding significantly. The implications to biomineralization of iron (hydr) oxides are briefly discussed.

36 MATERIALS SCIENCE↗