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At least 955 records · Page 53

A combined kinetic Monte Carlo and phase field approach to model thermally activated dislocation motion

In this work, a kinetic Monte Carlo (KMC) scheme is integrated into a phase field dislocation dynamics (PFDD) model to account for thermal activation. While the implementation is general and could be applied to many different thermally activated processes, we apply the model to simulate a dislocation transmitting through an interface. Two cases are analyzed: a dislocation transmitting through a strong interface, and a dislocation transmitting through a more realistic grain boundary in tungsten. In conclusion, results and trends for both cases are discussed in detail, and ultimately show that the combined KMC-PFDD algorithm is effective in capturing thermally activated dislocation processes.

36 MATERIALS SCIENCE↗

Biophysical Characterization of a Disabled Double Mutant of Soybean Lipoxygenase: The “Undoing” of Precise Substrate Positioning Relative to Metal Cofactor and an Identified Dynamical Network

Soybean lipoxygenase (SLO) has served as a prototype for understanding the molecular origin of enzymatic rate accelerations. The double mutant (DM) L546A/L754A is considered a dramatic outlier, due to the unprecedented size and near temperature-independence of its primary kinetic isotope effect, low catalytic efficiency, and elevated enthalpy of activation. To uncover the physical basis of these features, we herein apply three structural probes: hydrogen–deuterium exchange mass spectrometry, room-temperature X-ray crystallography and EPR spectroscopy on four SLO variants (wild-type (WT) enzyme, DM, and the two parental single mutants, L546A and L754A). DM is found to incorporate features of each parent, with the perturbation at position 546 predominantly influencing thermally activated motions that connect the active site to a protein–solvent interface, while mutation at position 754 disrupts the ligand field and solvation near the cofactor iron. However, the expanded active site in DM leads to more active site water molecules and their associated hydrogen bond network, and the individual features from L546A and L754A alone cannot explain the aggregate kinetic properties for DM. Lastly, using recently published QM/MM-derived ground-state SLO-substrate complexes for WT and DM, together with the thorough structural analyses presented herein, we propose that the impairment of DM is the combined result of a repositioning of the reactive carbon of linoleic acid substrate with regard to both the iron cofactor and a catalytically linked dynamic region of protein.

59 BASIC BIOLOGICAL SCIENCES↗

Ligand dissociation mediated charge transfer observed at colloidal W18O49 nanoparticle interfaces.

Understanding charge transfer dynamics through the ligand shell of colloidal nanoparticles has been an important pursuit in solar energy conversion. While charge transport through ligand shells of nanoparticle films has been studied intensely in static dry and electrochemical systems, its influence on charge transfer kinetics in dispersed colloidal systems has received relatively less attention. This work reports the oxidation of amine passivated tungsten oxide nanoparticles by an organically soluble tris-(1,10-phenanthroline) iron(III) derivative. By following the rate of this oxidation optically via the production of the ferroin derivative under various reaction conditions and particle derivatizations, we are able to show that the fluxional ligand shells on dispersed, colloidal nanoparticles provide a separate and more facile pathway for charge transfer, in which the rate-limiting step for charge transfer is the ligand dissociation. Since such ligand shells are frequently required for nanoparticle stability, this observation has significant implications for colloidal nanoparticle photocatalysis.

Grauer, David C↗

A Structural and Molecular Approach for the Study Biomarkers

Investigation of the nucleation and growth of crystals in both abiotic and biotic systems is critical to seemingly diverse disciplines of geology, biology, environmental science, and astrobiology. While there are abundant studies devoted to the determination of the structure and composition of inorganic crystals, as well as to the development of thermodynamic and kinetic models, it is only recently that research efforts have been directed towards understanding mineralization in biological systems (i.e., biomineralization). Biomineralization refers to the processes by which living organisms form inorganic solids. Studies of the processes of biomineralization under low temperature aqueous conditions have focused primarily on magnetite forming bacteria and shell forming marine organisms. Many of the biological building materials consist of inorganic minerals (calcium carbonate, calcium phosphate, silica or iron oxide) intricately combined with organic polymers (like proteins). More recently, efforts have been undertaken to explore the nature of biological activities in ancient rocks. In the absence of well-preserved microorganisms or genetic material required for the polmerase chain reaction (PCR) method in molecular phylogenetic studies, using biominerals as biomarkers offers an alternative approach for the recognition of biogenic activity in both terrestrial and extraterrestrial environments. The primary driving force in biomineralization is the interaction between organic and inorganic phases. Thus, the investigation of the ultrastructure and the nature of reactions at the molecular level occurring at the interface between inorganic and organic phases is essential to understanding the processes leading to the nucleation and growth of crystals. It is recognized that crystal surfaces can serve as the substrate for the organization of organic molecules that lead to the formation of polymers and other complex organic molecules, and in discussions of the origins of life, is referred to as organic synthesis on mineral surfaces. Furthermore, it is suggested that the interaction between mineral surfaces and simple organic molecules resulted in the formation of amino acids, RNA, and perhaps other more complex molecules such as proteins. On the other hand, in natural systems, it is recognized that functional groups on cell walls or membranes of microorganisms serve as sites of nucleation and crystallization. The precise replication of biominerals with controlled structure, morphology, size and texture is not confined to higher organisms as it also occurs in primitive prokaryotic cells such as magnetotactic bacteria and cyanobacteria. This suggests that the principal strategies of biomineralization were established early on in the evolutionary history of organisms. It is critical, therefore, to search for common mechanisms within diverse biological systems. One such common factor is the capability for organization and self-assembly. Organic macromolecules such as proteins and lipids can aggregate and polymerize forming membranes or extracellular matrix. At the organic-inorganic interface, several factors such as lattice geometry, polarity, stereochemistry and topography may act in concert to control nucleation and growth of crystals. Although several models have been proposed that discuss the significance of these factors for biomineralization, no comprehensive experimental data are available. In contrast to crystallization in exclusively inorganic systems, the kinetics of reaction and structural relationships between organic and inorganic phases in biominerals or biomimetic material is poorly understood. For example, it is not clear if the concept of epitactic growth (geometrical matching of unit cells at the interface of a secondary crystal growing on a primary crystal) applies to organic-inorganic systems. In contrast to inorganic templates that often have a smooth and rigid surface that promotes epitactic growth, biological substrates are usually rough and result in a large degree of mismatch. It is apparent that factors controlling the reaction at the crystal-matrix interface are strongly dependent upon the nature of the substrate. Therefore, characterization of the assembled organic surface and surface structure of the inorganic phase is crucial to understanding the processes of biomineralization. The focus of our research is the investigation of the processes leading to the nucleation and growth of crystals on both natural and synthetic systems through an interdisciplinary approach that integrates molecular biology, morphology and mineralogy using advanced preparation and analytical techniques. We have studied run-products, particularly magnetite, siderite and other carbonates, that resulted from extracellular biomineralization by extremophiles isolated from a variety of extreme environments ranging from permafrost to hydrothermal vent systems. The results of this study are critical to recognizing biomarkers in terrestrial and extraterrestrial environments.

Thomas-Keprta, Kathie↗

Phloroglucinol–2,6‐Diaminoanthraquinone as a Durable Redox Mediator for Enhancing Conversion Reaction Kinetics in Lithium‐Sulfur Batteries

Abstract Lithium‐sulfur batteries, despite being a promising solution for next‐generation secondary batteries, require substantial efforts to overcome the challenges of sluggish sulfur redox kinetics, polysulfides shuttling, and Li metal instability before achieving practical viability. Conventional strategies that utilize metal catalysts or soluble redox mediators (RMs) are limited by either impractical producing processes or unsatisfactory service life. Herein, an electrochemically active organic material, phloroglucinol – 2,6‐diaminoanthraquinone (PG‐DAAQ) is synthesized through a green and facile polymerization process to better resolve these issues. Serving as an RM at the cathode, PG‐DAAQ exhibits enduring redox activity within the sulfur operating potential window, leading to enhanced redox kinetics and sulfur utilization. Remarkably, even without any metal elements, PG‐DAAQ exhibits an excellent affinity to polysulfides, thereby suppressing the shuttling and facilitating the formation of a more favorable solid‐electrolyte interface to stabilize Li deposition at the anode. As a result, Li‐S cells employing PG‐DAAQ show significantly enhanced cycling and rate performances than the control cells. Even with a low electrolyte‐to‐sulfur ratio of 6, pouch cells with PG‐DAAQ deliver a reversible discharge capacity of 821 mA h g −1 after 100 cycles at a C/10 rate.

Lai, Tianxing↗

Development and Elucidation of Superior Turnover Rates and Selectivity of Supported Molecular Catalysts

Abstract Supported molecular catalysts consist of nanomaterials immobilized on a solid support. Important factors that control catalyst properties (reactivity, product selectivity, and stability) include the structure and compositions of both nanomaterials and supports. This review focuses on recent studies of supported molecular catalysts with controlled activity and selectivity in our group. We will first introduce the development of previously unexplored supported molecular catalysts. We will demonstrate the controllable selectivity of catalysts based on acidified mesoporous silica, metal‐organic frameworks (MOFs), hydrogen‐activated tungsten oxides, and noble metal doped Mn x O y /Na 2 WO 4 catalyst supported on mesoporous silica. We will then discuss advanced characterization techniques under reaction conditions, which offer mechanistic explanations of activity and selectivity of supported molecular catalysts. The applications of chemical transient kinetics (CTK) analysis, ambient pressure X‐ray photoelectron spectroscopy (APXPS), and sum‐frequency generation vibrational spectroscopy (SFG‐VS) are discussed. Next, we will describe new insights into catalysis at the nanoparticle‐support interfaces, which are catalytic environments unique to supported molecular catalysts. Examples include reactions at oxide‐metal interfaces and alcohol oxidation reactions at solid–gas and solid–liquid interfaces. Lastly, we will discuss heterogenized homogeneous catalysts and heterogenized enzyme catalysts as future directions of supported molecular catalysts.

Ye, Rong↗

Influence of TiO{sub 2} Nanoparticles on the Crystallization Behaviour and Tensile Properties of Biodegradable PLA and PCL Nanocomposites

This paper investigated the influence of TiO{sub 2} nanoparticles on the morphologies, as well as crystallization behaviour and kinetics, of neat PLA and PCL, and of these polymers in different PLA/PCL blends. We used transmission electron microscopy to evaluate the morphologies of the systems, while the crystallization behaviour and kinetics were investigated through differential scanning calorimetry (DSC). In addition to standard and modulated (StepScan) DSC analyses, the self-nucleation temperatures of neat PCL and PCL in the different nanocomposites were determined, followed by a self-nucleation and annealing thermal fractionation analysis of PCL crystallization and an Avrami isothermal kinetic analysis of PCL crystallization and PLA cold crystallization. We found that the nanoparticles were well dispersed, but only in the PLA phase of the blends, with only a few on the interface or in the PCL phase. They did nucleate and accelerate, and influence the mechanism of, the PCL crystallization in neat PCL, but had little influence on PCL crystallization in the blends. They strongly influenced the rate of cold crystallization of PLA, but had little influence on this parameter in the blends. The tensile properties were also determined, and changes in these properties could be related to the morphologies of the systems.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Conformal high-entropy oxide coatings enable fast and durable surface oxygen reactions

Developing active and durable air electrodes for efficient oxygen reactions is challenging for protonic ceramic cells (PCCs), especially at temperatures below 550°C. Here, in this study, we report a rationally designed conformal coating with a high-entropy PrNi 0.2 Mn 0.2 Co 0.2 Fe 0.2 Cu 0.2 O 3−δ (PNMCFC) perovskite structure on the surface of a state-of-the-art PrBaCo 2 O 5+δ (PBC) air electrode. The formed hybrid air electrode (PNMCFC-PBC) shows faster surface oxygen kinetics and a more stable phase structure in high-humidity air than the bare PBC electrode. Further density functional theory calculations suggest that the conformal coating mitigates Ba segregation at the interface and improves oxygen-related reactions, enhancing overall stability and electrocatalytic performance. The cells with the developed hybrid electrodes show encouraging electrochemical performance at 550°C: a polarization resistance of 0.72 Ω cm 2 , a peak power density of 1.30 W cm −2 , an electrolysis current density of −1.36 A cm −2 at 1.3 V, and reasonable operating stabilities (∼200 h at 550°C).

30 DIRECT ENERGY CONVERSION↗

Influence of annealing parameters on phase evolution and recrystallization kinetics of a Mn-Al-Si alloyed duplex steel

Highlights: • Stacking fault energy calculated for Fe-9.8Mn-7.5Al-1.22Si-0.2C steel is 48.4 mJ/m{sup 2} • Austenite stability decreases with increasing temperature due to higher free energy • Mn{sub 5}(Al,Si)C precipitates evolve with concurrent disappearance of austenite at 1273 K • Decrease in austenite fraction stimulates boundary migration for recrystallization • The maximum value of Avrami exponent ~ 1 implies sluggish recrystallization kinetics - Abstract: In this study, the phase transformation and recrystallization behavior of hot-forged Fe-Mn-Al-Si-C alloyed duplex steel has been investigated in wide ranges of annealing temperatures (973-1273 K) and durations (15–150 min). The recrystallization kinetics has been evaluated employing Johnson-Mehl-Avrami-Kolmogorov model. A limited extent of phase transformation (i.e. duplex to single phase) has been found to take place during annealing in the range of 973-1173 K. However, during annealing at 1273 K, not only the transformation from duplex to ferritic microstructure accelerates, but also recrystallization is initiated in these ferrite grains. The changes in the free energy of the austenite with the annealing temperature play a pivotal role in dictating the stabilization of the corresponding phase. Moreover, the disappearance of the austenitic phase at 1273 K owing to higher free energy is compensated by the formation of Mn-Al-Si rich carbide precipitates. The phase evolution triggered by annealing at 1273 K affects the recrystallization kinetics of each of the phase constituents. A sharp rise in the Avrami exponent (n) value is noticed following annealing at 1273 K, which clearly denotes that the disappearing austenite-ferrite interfaces facilitate the migration of the ferrite boundaries that stimulate recrystallization. In spite of the increasing values of n with the annealing temperature, its maximum value (at 1273 K) remains close to 1. This is a clear indication of the sluggish nature of the recrystallization process in the developed alloy.

36 MATERIALS SCIENCE↗

Microstructure evolution and mechanical properties of Cu/Sn/Ag TLP-bonded joint during thermal aging

Highlights: • The thermal reliability of the Cu/Sn/Ag TLP-bonded joint was investigated through high-temperature storage. • A diffusion reaction occurred at the interface between Cu{sub 3}Sn and Ag{sub 3}Sn during thermal aging. • The mechanism of the Cu{sub 3}Sn/Ag{sub 3}Sn interfacial reaction was investigated from thermodynamics and kinetics. - Abstract: Low-temperature transient liquid phase (TLP) bonding is a promising joining technology for high-temperature electronic devices packaging. However, the effect of thermal aging on the joint microstructure and performance has been rarely studied so far. In this paper, the relationship between microstructural evolution and mechanical property was developed for the Cu/Sn/Ag TLP-bonded joint during 350 °C aging. Experimental results show that an interfacial reaction occurs between the intermetallic compounds (IMCs) of Cu{sub 3}Sn and Ag{sub 3}Sn, which induces that a great amount of Cu{sub 3}Sn particles or wedges embed into the Ag-Sn phase layer. The reaction process is controlled by a volume diffusion of Cu elements from the Cu substrate, and capable of promoting the transformation from Ag{sub 3}Sn into Ag(Sn) solid solution. Cu{sub 41}Sn{sub 11} phase can be formed at the expense of Cu{sub 3}Sn and Cu, of which transformation process is completely achieved after aging for 480 h, and the Cu(Sn) solid solution intimately contacts with the opposite Ag(Sn) solid solution in many areas after aging for 960 h. The joint mechanical property initially declines due to the formation of Cu{sub 41}Sn{sub 11} phase and Cu-Sn IMCs grain coarsening, and then increases because of the complete depletion of Cu{sub 3}Sn and substantial precipitation of Cu(Sn) solid solution. After aging for nearly 1000 h, the joint still maintains a high shear strength of >40 MPa, indicating an excellent thermal reliability.

36 MATERIALS SCIENCE↗

Resolving the Evolution of Atomic Layer-Deposited Thin-Film Growth by Continuous In Situ X-Ray Absorption Spectroscopy

In situ synchrotron X-ray absorption near-edge structure characterization of thin-film titania growth by atomic layer deposition (ALD) over ZnO nanowires reveals persistent low-coordinated Ti motifs leading to a new picture of ALD growth. Through the design of growth and measurement cycles, Ti K-edge spectral data are continuously recorded so as to characterize the film evolution as a function of ALD cycle number and the surface changes within the time scale of the ALD cycle. A unified set of analysis tools is developed to interpret the time-series of spectral data. A prenucleation stage of growth, a transition region, and then a steady-state growth stage are observed with distinguishable features. Multivariate curve resolution analysis, that is physically constrained, demonstrates two specific spectral components with associated, time-dependent concentrations. The bulk-film component tracks the stages of growth. The surface and interface components, present throughout the stages of growth, reveal a significant coverage of relatively isolated or loosely networked tetrahedrally coordinated Ti atomic motifs. Lastly, spectral signatures for the intra-cycle growth kinetics are reconstructed at a time resolution of ~1 s and demonstrate that the transient Ti motifs on the growing surface stabilize within a few seconds of the Ti precursor pulse.

36 MATERIALS SCIENCE↗

Initiated chemical vapor deposited nanoadhesive for bonding National Ignition Facility's targets

Currently, the target fabrication scientists in National Ignition Facility Directorate at Lawrence Livermore National Laboratory (LLNL) is studying the propagation force resulted from laser impulses impacting a target. To best study this, they would like the adhesive used to glue the target substrates to be as thin as possible. The main objective of this research project is to create adhesive glue bonds for NIF’s targets that are ≤ 1 μm thick. Polyglycidylmethacrylate (PGMA) thin films were coated on various substrates using initiated chemical vapor deposition (iCVD). Film quality studies using white light interferometry reveal that the iCVD PGMA films were smooth. The coated substrates were bonded at 150 °C under vacuum, with low inflow of Nitrogen. Success in bonding most of NIF’s mock targets at thicknesses ≤ 1 μm indicates that our process is feasible in bonding the real targets. Key parameters that are required for successful bonding were concluded from the bonding results. They include inert bonding atmosphere, sufficient contact between the PGMA films, and smooth substrates. Average bond strength of 0.60 MPa was obtained from mechanical shearing tests. The bonding failure mode of the sheared interfaces was observed to be cohesive. Future work on this project will include reattempt to bond silica aerogel to iCVD PGMA coated substrates, stabilize carbon nanotube forests with iCVD PGMA coating, and kinetics study of PGMA thermal crosslinking.

36 MATERIALS SCIENCE↗

Corrosion of Containment Alloys in Molten Salt Reactors and the Prospect of Online Monitoring

The aim of this review is to communicate some essential knowledge of the underlying mechanism of the corrosion of structural containment alloys during molten salt reactor operation in the context of prospective online monitoring in future MSR installations. The formation of metal halide species and the progression of their concentration in the molten salt do reflect containment corrosion, tracing the depletion of alloying metals at the alloy salt interface will assure safe conditions during reactor operation. Even though the progress of alloying metal halides concentrations in the molten salt do strongly understate actual corrosion rates, their prospective 1 st order kinetics followed by near-linearly increase is attributed to homogeneous matrix corrosion. The service life of the structural containment alloy is derived from homogeneous matrix corrosion and near-surface void formation but less so from intergranular cracking (IGC) and pitting corrosion. Online monitoring of corrosion species is of particular interest for molten chloride systems since besides the expected formation of chromium chloride species CrCl 2 and CrCl 3 , other metal chloride species such as FeCl 2 , FeCl 3 , MoCl 2 , MnCl 2 and NiCl 2 will form, depending on the selected structural alloy. The metal chloride concentrations should follow, after an incubation period of about 10,000 hours, a linear projection with a positive slope and a steady increase of <1 ppm per day. During the incubation period metal concentration show 1 st order kinetics and increasing linearly with time. Ideally, a linear increase reflects homogeneous matrix corrosion, while a sharp increase in the metal chloride concentration could set a warning flag for potential material failure within the projected service life, e.g. as result of intergranular cracking or pitting corrosion. Continuous monitoring of metal chloride concentrations can therefore provide direct information about the mechanism of the ongoing corrosion scenario and offer valuable information for a timely warning of prospective material failure.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Truncated Dual-Cap Nucleation Site Development

During heterogeneous nucleation within a metastable mushy-zone, several geometries for nucleation site development must be considered. Traditional spherical dual cap and crevice models are compared to a truncated dual cap to determine the activation energy and critical cluster growth kinetics in ternary Fe-Cr-Ni steel alloys. Results of activation energy results indicate that nucleation is more probable at grain boundaries within the solid than at the solid-liquid interface.

Matson, Douglas M.↗

Electromigration kinetics and critical current of Pb-free interconnects

Electromigration kinetics of Pb-free solder bump interconnects have been studied using a single bump parameter sweep technique. By removing bump to bump variations in structure, texture, and composition, the single bump sweep technique has provided both activation energy and power exponents that reflect atomic migration and interface reactions with fewer samples, shorter stress time, and better statistics than standard failure testing procedures. Contact metallurgies based on Cu and Ni have been studied. Critical current, which corresponds to the Blech limit, was found to exist in the Ni metallurgy, but not in the Cu metallurgy. A temperature dependence of critical current was also observed.

36 MATERIALS SCIENCE↗

Investigating electrochemical corrosion at Mg alloy-steel joint interface using scanning electrochemical cell impedance microscopy (SECCIM)

Developing strategies to prevent corrosion at the interface of dissimilar metal alloys is challenging because of the presence of heterogenous distribution of galvanic couples and microstructural features that significantly change the corrosion rate. Devising strategies to mitigate this interfacial corrosion requires quantitative and correlative understanding of its surface electrochemical reaction. In this work, scanning electrochemical cell impedance microscopy (SECCIM) was employed to study location-specific corrosion in the interfacial region of dissimilar alloys, such as AZ31 (magnesium alloy) and DP590 (steel) welded using the Friction-stir Assisted Scribe Technique (FAST) processes. Herein, SECCM and SECCIM were used to perform correlative mapping of the local electrochemical impedance spectroscopic and potentiodynamic polarization to measure the effect of electronic and microstructural changes in the welded interfacial region on corrosion kinetics. Microstructural characterization including scanning electron microscopy and electron backscatter diffraction was performed to correlate changes in microstructural features and chemistry with the corresponding electronic properties that affect corrosion behavior. The variations in corrosion potential, corrosion current density, and electrochemical impedance spectroscopy behavior across the interface provide deeper insights on the interfacial region—which is chemically and microstructurally distinct from both bare AZ31 and DP590 that can help prevent corrosion in dissimilar metal structures.

59 BASIC BIOLOGICAL SCIENCES↗

Model of ASTM Flammability Test in Microgravity: Iron Rods

There is extensive qualitative results from burning metallic materials in a NASA/ASTM flammability test system in normal gravity. However, this data was shown to be inconclusive for applications involving oxygen-enriched atmospheres under microgravity conditions by conducting tests using the 2.2-second Lewis Research Center (LeRC) Drop Tower. Data from neither type of test has been reduced to fundamental kinetic and dynamic systems parameters. This paper reports the initial model analysis for burning iron rods under microgravity conditions using data obtained at the LERC tower and modeling the burning system after ignition. Under the conditions of the test the burning mass regresses up the rod to be detached upon deceleration at the end of the drop. The model describes the burning system as a semi-batch, well-mixed reactor with product accumulation only. This model is consistent with the 2.0-second duration of the test. Transient temperature and pressure measurements are made on the chamber volume. The rod solid-liquid interface melting rate is obtained from film records. The model consists of a set of 17 non-linear, first-order differential equations which are solved using MATLAB. This analysis confirms that a first-order rate, in oxygen concentration, is consistent for the iron-oxygen kinetic reaction. An apparent activation energy of 246.8 kJ/mol is consistent for this model.

Steinberg, Theodore A↗