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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 289 records · Page 16
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Assessment of asymmetrical rheological behavior of cementitious material for 3D printing application

Among the multiplicity of construction methods based on digital concrete technologies, the most common one remains the extrusion-based process. Two opposed strategies have been developed in order to print a concrete structure using extrusion: the first one emphasizes the ease-of-pumping of material which is massively accelerated to ensure the stability of the structure, when leaving the extruder; the second one uses a firm mortar able to sustain the own weight of the structure during the printing, without requiring any accelerator. Both methods have their pros and cons and don't imply the same rheological requirements. Most of the recent literature assumes that both types of material (fluid and firm) follow the same trend of behavior and obey to the Von Mises plasticity criterion, while it has been demonstrated that firm cement-based materials can exhibit a pressure dependent behavior. Moreover, rheological study is mainly based on shear rheometry, while the extrusion-based printing process requires a description of the rheological behavior in compression to predict the global stability of the structure, and in tension to prevent cracks formation. This paper investigates the fresh behavior of cement paste and mortar under different solicitations (shear, compression, tension) for different water to cement ratios. The analysis of these results allows to describe the transition between a ductile fluid material (symmetrical in tension and compression) that obeys to a Von Mises plasticity criterion, and a brittle and firm material (asymmetrical in tension and compression) that requires a pressure dependent plasticity criterion in order to predict its strength under a given solicitation.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Predicting fracture behavior in single crystal nickel using a coupled crystal plasticity phase field damage approach

Understanding the fracture behavior of single crystal metals is critical for predicting material performance under mechanical loading. Here, in this study, we investigate the fracture characteristics of single crystal nickel tensile bars using a crystal plasticity coupled phase field damage (CP-PFD) model. Experimental tensile tests were conducted on 15 specimens spanning five crystallographic orientations and three thickness variants per orientation. The results revealed two distinct fracture modes: brittle fractures with 45-degree angled surfaces and ductile fractures characterized by significant necking. The CP-PFD model successfully replicated these fracture behaviors, demonstrating strong agreement with experimental observations. The model effectively predicted the strain at which necking and fracture occurred, as well as the orientation-dependent fracture mechanisms. By comparing experimental and simulated fracture surfaces, we establish the CP-PFD model as a robust tool for predicting single crystal behavior and damage evolution. This work provides insight into the microstructural dependence of fracture behavior and establishes a predictive framework for modeling orientation-dependent damage evolution in single-crystal nickel.

Crystal plasticity↗
DOE OSTI2026

From observation to replication: machine-learning-driven quantification and replication of fine-scale fish kinematics and behavior

Long-term quantification of fish behavior is essential for aquatic ecology, wildlife telemetry, and biomechanical device development. However, the observation duration required to obtain reliable behavioral and kinematic metrics remains unclear, and few tools exist to physically reproduce natural swimming motion for controlled experimentation. We address these challenges by developing a generalizable framework that models behavioral reliability (Spearman–Brown reliability index) as a function of observation duration and derives metric-specific monitoring thresholds. Using juvenile white sturgeon (Acipenser transmontanus) as a case study, we demonstrate that the minimum duration needed for reliable estimates varies substantially across kinematic features: to exceed a reliability of 0.8, total distance traveled requires 12 days, average curvature (mm?¹) 15 days, tail-beat frequency (Hz) 8 days, and average speed (body length/s) 17 days. We further bridge digital analysis and physical testing by developing a hardware-in-the-loop simulator that reconstructs machine-learning-derived swimming kinematics with high fidelity (correlation coefficient 0.98–0.99, RMSE 1.22–1.27 mm over a 5-minute segment). This platform enables realistic, repeatable motion stimuli for evaluating aquatic sensing technologies and bio-integrated devices under controlled conditions. Together, these contributions provide a scalable approach for designing long-term behavioral studies and a data-driven connection between ecological observation and robotic experimentation.

Hwang, SungJoo↗
DOE OSTI2022

Replicating HCCI-like autoignition behavior: What gasoline surrogate fidelity is needed?

This work seeks to characterize the fidelity needed in a gasoline surrogate with the intent to replicate the complex autoignition behavior exhibited within advanced combustion engines, and specifically Homogeneous Charge Compression Ignition (HCCI). A low-temperature gasoline combustion (LGTC) engine operating in HCCI mode and a rapid compression machine (RCM) are utilized to experimentally quantify fuel reactivity, through autoignition and preliminary heat release characteristics. Fuels considered include a research grade E10 U.S. gasoline (RD5-87), three multi-component surrogates (PACE-1, PACE-8, PACE-20), and a binary surrogate (PRF88.4). Each fuel was studied at lean/HCCI-like conditions covering a wide range of temperatures and pressures that are representative of naturally aspirated to high boost engine operation. Detailed chemical kinetic modeling is also undertaken using a recently updated gasoline surrogate kinetic model to simulate the RCM experiments and to provide chemical insight into surrogate-to-surrogate differences. The LGTC engine experiments demonstrate nearly identical reactivity between PACE-20 and RD5-87 across studied conditions, while faster phasing is seen for both PACE-1 and PACE-8 due to their stronger intermediate- and low-temperature heat release (ITHR/LTHR) at naturally aspirated and boosted conditions, respectively. The RCM experiments reveal typical low-temperature, negative temperature coefficient (NTC) and intermediate-temperature autoignition behaviors at all pressure conditions for RD5-87, which are qualitatively reproduced by all surrogates. Quantitative discrepancies in both autoignition and preliminary heat release are observed for all surrogates, while their ability to replicate RD5-87 autoignition behavior follows the order of PACE-20 > PACE-1 > PACE-8 > PRF88.4. Excellent mapping is obtained between the LGTC engine and the RCM, where the engine pressure-time trajectories can be characterized by the regimes represented by the RCM autoignition isopleths. The kinetic model performs commendably when simulating both autoignition and preliminary heat release of PACE-20, while typically overpredicting ignition delay times for PACE-1, PACE-8 and PRF88.4 at high-pressure and low-temperature/NTC conditions. Sensitivity and rate of production (ROP) analyses highlight surrogate-to-surrogate differences in the governing chemical kinetics where n-pentane initiates rapid OH branching at a faster rate and an earlier timing for PACE-20 than iso-pentane does for PACE-1 and PACE-8, making it computationally more reactive than the other surrogates. The current study highlights the need to include non-standardized properties, such as the lean/HCCI-like autoignition characteristics, in addition to ASTM properties (e.g., RON, MON) as metrics of fuel reactivity and targets to be matched when formulating high-fidelity surrogates that fully capture gasoline advanced combustion behavior such as HCCI-like autoignition.

42 ENGINEERING↗
DOE OSTI2022

Creep behavior of an additively manufactured 9Cr steel in the as-built condition

Limited studies have evaluated the creep behavior of additively manufactured (AM) ferritic-martensitic (FM) steels. This work investigated the creep behavior of a 9Cr FM steel fabricated by powder blown directed energy deposition (DED) technique. Here, the creep testing at 550–650 °C and 150 MPa for the specimens along the deposition direction in the as-built condition, together with corresponding microstructural characterization, revealed a threshold temperature between 600 and 625 °C, below which the steel has creep resistance comparable with Grade 91 cross-welds and noticeably greater than 9Cr-1Mo steel. The threshold temperature distinguishes the creep behavior in two regimes differentiated in creep activation energy, creep deformation, and failure mechanism. Unlike the creep rupture surface ~45° from the loading direction when tested above the threshold temperature, the creep rupture for testing below the threshold temperature resembles type IV failure in the cross-welds of ferritic steels. The DED-induced layer structure in the as-built steel played a significant role on the change of creep behavior.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Modification of lithium electrodeposition behavior by variation of electrode distance

Developing a better understanding and control over the lithium electrodeposition behavior will assist with the commercial application of lithium metal anodes for rechargeable batteries. Despite intensive research over the past decade, our understanding of the deposition of lithium is limited. Here a new observation on the effect of distance between the working electrode and the counter electrode for electrochemical lithium deposition behavior is reported. From this fundamental investigation of distance, the high lithium ion concentration regions formed by release of lithium ions from the counter electrode modify the lithium deposition behavior on the working electrode, resulting in the generation of non-uniform lithium dendrites with a thick diversely composed surface film. Alternatively, increasing the distance between the electrodes results in the deposition of a spherical lithium morphology with a thin LiF rich surface film. Here, this fundamental study provides a deeper understanding of correlation between lithium deposition behavior and electrode separation and provides insight to inhibit lithium dendrite formation.

25 ENERGY STORAGE↗
DOE OSTI2025

Self-regulating behavior of hybrid membrane systems as demonstrated in an element-scale forward osmosis-reverse osmosis hybrid system

Hybrid membrane systems can be difficult to design due to the requisite flow rate matching between up- and downstream unit operations. In this work, we use a forward osmosis-reverse osmosis (FO-RO) hybrid system to demonstrate how some membrane systems can exhibit self-regulating behavior due to osmotic coupling. This can reduce the need for complex control systems for flow balancing. We show this behavior using a module-scale test bed that can mimic the behavior of larger scale operations. The system shows permeate flow rate near-convergence between the FO and RO modules after startup or when perturbed by a change in RO module pressure. The behavior of this hybrid system demonstrates that some membrane operations can exploit osmotic interdependence, rather than expensive control systems, to achieve steady state operation.

Debottlenecking↗
DOE OSTI2022

A layered 2D computational framework: Theory and applications to nuclear fuel behavior

Nuclear fuel performance computer codes have been developed over the last 50 years to analyze fuel behavior under various operating conditions. Traditionally, these codes used quasi-two-dimensional (also commonly known as 1.5D) representations of the fuel rod, which model the rod using a set of one-dimensional axisymmetric models that represent the behavior at specific axial positions on the rod. Modern fuel performance codes have the ability to investigate full three-dimensional (3D) effects and couple to other physics-based codes for true multiphysics simulations. However, with increasing complexity comes increasing computational costs. Many phenomena of interest involve azimuthally-varying behavior that cannot be represented using the aforementioned quasi-two-dimensional approach, but do not require the use of a full 3D model. To efficiently address these problems, there is a need for a computational framework that provides a compromise between the quasi-two-dimensional and full 3D models. In this paper, we present a new quasi-three-dimensional approach that represents the fuel as a set of 2D planar models that represent the behavior of the fuel cross-section at various axial positions. Presented here are the theory behind the methodology, test cases to illustrate proper implementation, and practical applications of its use in the BISON fuel performance code for a variety of cases in nuclear fuel analysis, such as fuel fracture, axial fuel relocation, and cladding distension and oxidation.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2021

A review of rare earth elements and yttrium in coal ash: Content, modes of occurrences, combustion behavior, and extraction methods

Rare earth elements and yttrium (REY) have attracted considerable attention over the last decade because of their vital roles in clean energy, consumer product, national defense and security applications, among other uses. Due to the retention of REY during coal burning, coal combustion ash is considered as potential alternative sources for REY. Understanding the content, speciation, retention and/or transformation behavior of REY during coal combustion not only expands our knowledge of the combustion behavior of the trace elements in coal, but also provides basis for modeling REY partitioning during coal combustion and for developing economically viable REY recovery technologies. This review makes a critical summary of recent progress in the study of REY in coal ash. The contents and the extraction potentials of REY in coal ash derived from 15 major coal-producing countries worldwide were summarized and evaluated. Various analytical methods for determining REY bulk contents and speciation, together with the solid sample pretreatment, analytical accuracy and precision, advantages and disadvantages were summarized and compared. Modern analytical approaches combined indirect methods (e.g., sequential extraction) shed light on the physical distribution, mineralogy, and the chemical state of REY in coal ash. Three types of REY occurrences in coal ash, including Si-Al glassy association, discrete minerals or compounds, and organic association (bound with unburned carbon) were defined in the review. The glassy association can be further divided into REY minerals closely bound to glass phases and dispersed throughout the glassy structure. REY partitioning in various emission streams, the size distribution, and their enrichment behavior in coal ash were discussed. Additionally, thermal behavior and transformation of various REY forms in coal during combustion process, including organic-associated REY, REY phosphates, REY carbonates, clay-bound REY and among others were summarized. Two possible retention mechanisms of REY by aluminosilicate glass at boiler temperature were proposed: the incorporation of the individual REY phases into the glass as inclusions and the diffusion of REY phases throughout Si-Al glass structures in the melting process. Feed coal mineral types, mineral-mineral associations, boiler conditions, and other factors control the retention process. After coal combustion, the speciation of REY in fly ash may be modified by the reactions of REY phases with flue gas components. Further, an overview of REY transformation mechanisms during coal combustion was deeply discussed. Finally, current extraction techniques for REY recovery from coal combustion ash were introduced. Future outlooks and research problems were also identified.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Relationships between maternally-transferred mercury and hatchling development, behavior, and survival in the American alligator ( Alligator mississippiensis )

Mercury is a toxic and pervasive environmental contaminant that can be transferred from mother to offspring during development. Consequences of maternally-transferred mercury have been observed in vertebrate taxa, including reduced clutch viability, reduced offspring size, and behavioral alterations. These sublethal effects have been assumed to decrease survivorship, though this is seldom assessed. Here, we examined how maternally-transferred mercury interacts with incubation temperature to influence reproductive success, offspring behavior, and subsequent survival in the American alligator (Alligator mississippiensis). We collected nine clutches of eggs from a mercury contaminated reservoir on the Savannah River Site, South Carolina, and incubated eggs at either female- or male-promoting temperatures. Clutch-averaged mercury in egg yolk was high relative to other studies in crocodilians and ranged from 0.248 to 0.554 ppm compared to 0.018–0.052 ppm at a site with low levels of mercury contamination; mercury levels in hatchling blood ranged from 0.090 to 0.490 ppm ($\overline{x}$= 0.240 ppm, n = 158). We found few, mostly negligible correlations between life history traits and mercury but noted a positive relationship with egg mass, possibly mediated by correlated maternal effects such as resource provisioning. Incubation temperature exerted strong effects on hatchling phenotypes, with warmer, male-promoting temperatures producing larger and bolder hatchlings. Presumptive females, produced from cooler incubation temperatures, spent more time in warm areas during behavior trials. Hatchlings were released 10–15 days post-hatch and surveyed over eight months to assess survival. Survivorship was positively correlated with hatchling size and negatively correlated with proportional time spent in warm areas. Presumptive females had much lower survival, and overall survivorship for the eight-month period was 0.185–0.208, depending on the modelling approach. Finally, our study suggests that, within the range of concentrations we observed, incubation temperature has a stronger effect on offspring behavior and survival than maternally-transferred mercury pollution in American alligators.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2026

Sliding friction and wear behavior of nuclear graphite in high temperature inert environment: Influence of contact load, speed and temperature

Repeated dynamic interactions of graphitic components in pebble-bed gas-cooled nuclear reactors can cause abrasive wear-induced pebble surface damage, generate hazardous fine graphite debris, and alter fuel circulation dynamics due to changes in friction behavior. Comprehensive tribological characterization of nuclear graphitic materials in conditions relevant to reactor operation is needed to assess reactor long-term safety and performance. This work reports sliding friction and wear behavior of self-mated nuclear graphite ET-10 at various elevated temperatures (650 °C and 750 °C), sliding speeds (1 and 10 mm/s) and contact loads (20 and 40 N) in a controlled argon environment. The results revealed nonmonotonic frictional behavior with a higher running-in coefficient of friction (COF) followed by a lower steady-state COF, as a result of transition from two-body abrasion to three-body abrasion along with formation of a tribofilm. A key finding of this work is the sensitivity of the running-in COF to experimental conditions; maximum running-in values were lower at either elevated temperature (0.52–0.54) or reduced sliding speed (0.51–0.54). Conversely, the steady-state COF remained invariant at approximately 0.3 across all tested parameters. Transmission electron microscopy revealed a 0.5–2.0 μm thick nanocrystalline tribofilm that was thought to be formed by the compaction of the graphitic wear debris on the contact surface during the sliding process. The nanocrystalline nature of the tribofilm was further confirmed by Raman spectroscopy. As a result, the combination of tribological testing and morphological characterization provided a mechanistic understanding of the frictional behavior of nuclear graphite upon sliding.

Friction↗
DOE OSTI2022

Emerging Electrochemical Techniques for Probing Site Behavior in Single-Atom Electrocatalysts

Single-atom catalysts (SACs) have aroused tremendous interest over the past decade, particularly in the community of energy and environment-related electrocatalysis. A rapidly growing number of recent publications have recognized it as a promising candidate with maximum atomic utilization, distinct activity, and selectivity in comparison to bulk catalysts and nanocatalysts. However, the complexity of localized coordination environments and the dispersion of isolated sites lead to significant difficulties when it comes to gaining insight into the intrinsic behavior of electrocatalytic reactions. Furthermore, the low metal loadings of most SACs make conventional ensemble measurements less likely to be accurate on the subnanoscale. Thus, it remains challenging to probe the activity and properties of individual atomic sites by available commercial instruments and analytical methods. In spite of this, continuing efforts have lately focused on the development of advanced measurement methodologies, which are very useful to the fundamental understanding of SACs. There have recently been a number of in situ/operando techniques applied to SACs, such as electron microscopy, spectroscopy, and other analysis methods, which support relevant functions to identify the active sites and reaction intermediates and to investigate the dynamic behavior of localized structures of the catalytic sites. This Account aims to present recent electrochemical probing techniques which can be used to identify single-atomic catalytic sites within solid supports. First, we describe the basic principles of molecular probe methods for the study and analysis of electrocatalytic site behavior. In particular, the in situ probing technique enabled by surface interrogation scanning electrochemical microscopy (SISECM) can measure the active site density and kinetic rate with high resolution. An alternative electrochemical probing technique is further demonstrated on the basis of single-entity electrochemistry, which allows the unique electrochemical imaging of the size and catalytic rate of single atoms, molecules, and clusters. Next, the merits and limitations of different electrochemical techniques are then discussed, along with perspectives for future prospects. Apart from this, we further showcase the powerful capability of emerging electrochemical probing techniques for determining significant effects and properties of SACs for various electrocatalytic reactions, including oxygen reduction and evolution, hydrogen evolution, and nitrate reduction. Overall, electrochemical techniques with atomic resolution have greatly increased opportunities for observing, measuring, and understanding the surface and interface chemistry during energy conversion. In the future, it is anticipated that the development of electrochemical probing techniques will be advanced with innovative perspectives on the behavior and features of SACs. We hope that this Account can contribute in several ways to promoting the fundamental knowledge and technical progress of emerging electrochemical measurements for studying SACs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Mechanistic Study of Controlled Zinc Electrodeposition Behaviors Facilitated by Nanoscale Electrolyte Additives at the Electrode Interface

Nanoparticle organic hybrid materials (NOHMs) are liquid-like materials composed of an inorganic core to which a polymeric canopy is ionically tethered. NOHMs have unique properties including negligible vapor pressure, high oxidative thermal stability, and the ability to bind to reactive species of interest due to the tunability of their polymeric canopy. This makes them promising multifunctional materials for a wide range of energy and environmental technologies, including electrolyte additives for electrochemical energy storage (e.g., flow batteries) and the electrochemical conversion of CO 2 to chemicals and fuels. Due to their unique transport behaviors in fluid systems, an understanding of the near-electrode surface behavior of NOHMs in electrolyte solutions and their effect on electrochemical reactions is still lacking. In this work, the complexation of zinc (Zn) by NOHMs with an ionically tethered polyetheramine canopy (HPE) (NOHM-I-HPE) was studied using attenuated total reflectance Fourier transform infrared and Carbon-13 nuclear magnetic resonance spectroscopy. Additionally, various electrochemical techniques were employed to discern the role of NOHM-I-HPE during zinc electrodeposition, and the results were compared to those of the electrochemical system containing untethered HPE polymers. Our findings confirmed that NOHM-I-HPE and HPE reversibly complex zinc in the aqueous electrolyte. NOHM-I-HPE and HPE were found to block some of the electrode active sites, reducing the overall current density during electrodeposition, while facilitating the formation of smooth zinc deposits, as revealed by surface imaging and diffraction techniques. Observed variations in the current density responses and the degree of passivation created by the NOHM-I-HPE and HPE adsorbed on the electrode surface revealed that their different packing behaviors at the electrode–electrolyte interface influence the zinc deposition mechanism. The presence of the nanoparticle and ordering offered by the NOHMs as well as the structured conformation of the polymeric canopy allowed the formation of void spaces and free volumes for enhanced transport behaviors. Furthermore, these findings provided insights into how structured electrolyte additives such as NOHMs can allow for advancements in electrolyte design for controlled deposition of metal species from energy-dense electrolytes or for other electrochemical reactions.

25 ENERGY STORAGE↗
DOE OSTI2023

Microscopic Origins of the Nonlinear Behavior of Particle-Filled Rubber Probed with Dynamic Strain XPCS

The underlying microscopic response of filler networks in reinforced rubber to dynamic strain is not well understood due to the experimental difficulty of directly measuring filler network behavior in samples undergoing dynamic strain. This difficulty can be overcome with in situ X-ray photon correlation spectroscopy (XPCS) measurements. The contrast between the silica filler and the rubber matrix for X-ray scattering allows us to isolate the filler network behavior from the overall response of the rubber. This in situ XPCS technique probes the microscopic breakdown and reforming of the filler network structure, which are responsible for the nonlinear dependence of modulus on strain, known in the rubber science community as the Payne effect. These microscopic changes in the filler network structure have consequences for the macroscopic material performance, especially for the fuel efficiency of tire tread compounds. In this work, we elucidate the behavior with in situ dynamic strain XPCS experiments on industrially relevant, vulcanized rubbers filled (13 vol %) with novel air-milled silica of ultrahigh-surface area (UHSA) (250 m 2 /g). The addition of a silane coupling agent to rubber containing this silica causes an unexpected and counterintuitive increase in the Payne effect and decrease in energy dissipation. For this rubber, we observe a nearly two-fold enhancement of the storage modulus and virtually equivalent loss tangent compared to a rubber containing a coupling agent and conventional silica. Interpretation of our in situ XPCS results simultaneously with interpretation of traditional dynamic mechanical analysis (DMA) strain sweep experiments reveals that the debonding or yielding of bridged bound rubber layers is key to understanding the behavior of rubber formulations containing the silane coupling agent and high-surface area silica. These results demonstrate that the combination of XPCS and DMA is a powerful method for unraveling the microscale filler response to strain which dictates the dynamic mechanical properties of reinforced soft matter composites. With this combination of techniques, we have elucidated the great promise of UHSA silica when used in concert with a silane coupling agent in filled rubber. Such composites simultaneously exhibit large moduli and low hysteresis under dynamic strain.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Crystallizing Atomic Xenon in a Flexible MOF to Probe and Understand Its Temperature-Dependent Breathing Behavior and Unusual Gas Adsorption Phenomenon

Flexible metal–organic frameworks (MOFs) hold great promise as smart materials for specific applications such as gas separation. These materials undergo interesting structural changes in response to guest molecules, which is often associated with unique adsorption behavior not possible for rigid MOFs. Understanding the dynamic behavior of flexible MOFs is crucial yet challenging as it involves weak host–guest interactions and subtle structural transformation not only at the atomic/molecular level but also in a nonsteady state. Here we report an in-depth study on the adsorbate- and temperature-dependent adsorption in a flexible MOF by crystallizing atomic gases into its pores. Mn(ina)2 shows an interesting temperature-dependent response toward noble gases. Its nonmonotonic, temperature-dependent adsorption profile results in an uptake maximum at a temperature threshold, a phenomenon that is unusual. Full characterization of Xe-loaded MOF structures is performed by in situ single-crystal and synchrotron X-ray diffraction, IR spectroscopy, and molecular modeling. The X-ray diffraction analysis offers a detailed explanation into the dynamic structural transformation and provides a convincing rationalization of the unique adsorption behavior at the molecular scale. The guest and temperature dependence of the structural breathing gives rise to an intriguing reverse of Xe/Kr adsorption selectivity as a function of temperature. The presented work may provide further understanding of the adsorption behavior of noble gases in flexible MOF structures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Interface microstructure effects on dynamic failure behavior of layered Cu/Ta microstructures

Abstract Structural metallic materials with interfaces of immiscible materials provide opportunities to design and tailor the microstructures for desired mechanical behavior. Metallic microstructures with plasticity contributors of the FCC and BCC phases show significant promise for damage-tolerant applications due to their enhanced strengths and thermal stability. A fundamental understanding of the dynamic failure behavior is needed to design and tailor these microstructures with desired mechanical responses under extreme environments. This study uses molecular dynamics (MD) simulations to characterize plasticity contributors for various interface microstructures and the damage evolution behavior of FCC/BCC laminate microstructures. This study uses six model Cu/Ta interface systems with different orientation relationships that are as- created, and pre-deformed to understand the modifications in the plasticity contributions and the void nucleation/evolution behavior. The results suggest that pre-existing misfit dislocations and loading orientations (perpendicular to and parallel to the interface) affect the activation of primary and secondary slip systems. The dynamic strengths are observed to correlate with the energy of the interfaces, with the strengths being highest for low-energy interfaces and lowest for high-energy interfaces. However, the presence of pre-deformation of these interface microstructures affects not only the dynamic strength of the microstructures but also the correlation with interface energy.

42 ENGINEERING↗
DOE OSTI2022

Particle anisotropy tunes emergent behavior in active colloidal systems

Studies of active particle systems have demonstrated that particle anisotropy can impact the collective behavior of a system, motivating a systematic study. Here, we report a systematic computational investigation of the role of anisotropy in shape and active force director on the collective behavior of a two-dimensional active colloidal system. We find that shape and force anisotropy can combine to produce critical densities both lower and higher than those of disks. Furthermore, we demonstrate that changing particle anisotropy tunes what we define as a “collision efficiency” of inter-particle collisions in leading to motility-induced phase separation (MIPS) of the system. We use this efficiency to determine the relative critical density across systems. Additionally, we observe that local structure in phase-separated clusters is the same as the particle's equilibrium densest packing, suggesting a general connection between equilibrium behavior and non-equilibrium cluster structure of self-propelled anisotropic particles. In engineering applications for active colloidal systems, shape-controlled steric interactions such as those described here may offer a simple route for tailoring emergent behaviors.

42 ENGINEERING↗
DOE OSTI2023

Anti-Arrhenius behavior of electron transfer reactions in molecular dimers

Rates of chemical reactions typically accelerate as the temperature rises, following the Arrhenius law. However, electron transfer reactions may exhibit weak temperature dependence or counterintuitive behavior, known as anti-Arrhenius behavior, wherein reaction rates decrease as temperature increases. Solvent reorganization energy and torsion-induced changes in electronic couplings could contribute to this unusual behavior, but how each contributes to the overall temperature dependence is unclear. One can decelerate the charge recombination process in photogenerated radical pairs or charge-separated states by harnessing this often-overlooked phenomenon. This means that we could achieve long-lived radical pairs without relying on conventional cooling. Using a series of homo molecular dimers, we showed that the degree of torsional hindrance dictates temperature-dependent torsion-induced changes in electronic coupling and, therefore, charge recombination rates. The overall temperature dependence is controlled by how changes in electronic coupling and the temperature-dependent solvent reorganization energy contribute to the rates of charge recombination. Our findings pave the way for rationally designing molecules that exhibit anti-Arrhenius behavior to slow down charge recombination, opening possibilities for applications in energy-related and quantum information technologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗