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At least 793 records · Page 44

Creep and fracture of dispersion-strengthened materials

The creep and fracture of dispersion strengthened materials is reviewed. A compilation of creep data on several alloys showed that the reported values of the stress exponent for creep varied between 3.5 and 100. The activation energy for creep exceeded that for lattice self diffusion in the matrix in the case of some materials and a threshold stress behavior was generally reported in these instances. The threshold stress is shown to be dependent on the interparticle spacing and it is significantly affected by the initial microstructure. The effect of particle size and the nature of the dispersoid on the threshold stress is not well understood at the present time. In general, most studies indicate that the microstructure after creep is similar to that before testing and very few dislocations are usually observed. It is shown that the stress acting on a dispersoid due to a rapidly moving dislocation can exceed the particle yield strength of the G sub p/1000, where G sub p is the shear modulus of the dispersoid. The case when the particle deforms is examined and it is suggested that the dislocation creep threshold stress of the alloy is equal to the yield strength of the dispersoid under these conditions. These results indicate that the possibility that the dispersoid creep threshold stress is determined by either the particle yield strength or the stress required to detach a dislocation from the dispersoid matrix interface. The conditions under which the threshold stress is influenced by one or the other mechanism are discussed and it is shown that the particle yield strength is important until the extent of dislocation core relaxation at the dispersoid matrix interface exceeds about 25 pct. depending on the nature of the particle matrix combination. Finally, the effect of grain boundaries and grain morphology on the creep and fracture behavior of dispersoid strengthened alloys is examined.

Raj, Sai V.↗

Density Functional Tight Binding Insights into Plasmonic Silver–Platinum Nanoparticles and Alloys for Enhanced Photocatalysis

Developing accurate and efficient Slater-Koster (SK) tight-binding parameter sets is essential for quantum plasmonic studies of alloyed metal nanoparticles, as conventional time dependent density functional theory (TD-DFT) calculations are computationally prohibitive for larger clusters. In this work, we develop and validate density functional tight binding (DFTB) parameter sets for both ground state (GS-SK) and excited state (ES-SK) calculations to study the structural, electronic, and optical properties of silver (Ag), platinum (Pt), and Ag–Pt nanoalloys. Our investigation of the ground state properties demonstrates that the GS-SK parameters enable DFTB to closely reproduce the electronic structures of platinum clusters with diverse sizes and geometries – showing qualitative agreement with DFT for density of states (DOS) profiles and energy levels. The ES-SK parameters accurately describe excited-state properties compared to TD-DFT reference calculations, including the broad, featureless absorption profiles of Pt that are dominated by interband transitions. Using the ES-SK parameters within a real-time TD-DFTB framework, we compute size-dependent optical absorption spectra of Ag, Pt and Ag-Pt nanocubes containing up to 1099 atoms (size ∼4.18 nm). A detailed study of Ag–Pt and Pt-Ag core–shell nanoparticles shows quenching of the Ag plasmon resonance even at monolayer coverage for Ag-Pt, but not for Pt-Ag. We also show how to define submonolayer Ag-core Pt-shell cubic structures that have similar optical properties to those generated experimentally for much larger particles, which offers potential for describing plasmon-enhanced photocatalysis. Collectively, the GS-SK and ES-SK parameter sets provide an accurate, computationally efficient approach for modeling the complex optical and electronic behavior of noble–transition metal nanostructures and their alloys.

SPR↗

Viscous flow properties and hydrodynamic diameter of phenothiazine-based redox-active molecules in different supporting salt environments

We report viscous flow properties of a redox-active organic molecule, N-(2-(2-methoxyethoxy)ethyl)phenothiazine (MEEPT), a candidate for non-aqueous redox flow batteries, and two of its radical cation salts. A microfluidic viscometer enabled the use of small sample volumes in determining viscosity as a function of shear rate and concentration in the non-aqueous solvent, acetonitrile, both with and without supporting salts. All solutions tested show Newtonian behavior over shear rates of up to 30 000 s−1, which was rationalized by scaling arguments for the diffusion-based relaxation time of a single MEEPT molecule without aggregation. Neat MEEPT is flowable but with a large viscosity (412 mPa⋅s at room temperature), which is ∼1000 times larger than that of acetonitrile. MEEPT solutions in acetonitrile have low viscosities; at concentrations up to 0.5 M, the viscosity increases by less than a factor of two. From concentration-dependent viscosity measurements, molecular information was inferred from intrinsic viscosity (hydrodynamic diameter) and the Huggins coefficient (interactions). Model fit credibility was assessed using the Bayesian Information Criterion. It is found that the MEEPT and its charged cations are “flowable” and do not flocculate at concentrations up to 0.5 M. MEEPT has a hydrodynamic diameter of around 8.5 Å, which is almost insensitive to supporting salt and state of charge. This size is comparable to molecular dimensions of single molecules obtained from optimized structures using density functional theory calculations. The results suggest that MEEPT is a promising candidate for redox flow batteries in terms of its viscous flow properties.

Wang, Yilin (ORCID:0000000316102995)↗

Rheological behavior and fiber spinning of polyacrylonitrile (PAN)/Carbon nanotube (CNT) dispersions at high CNT loading

Rheological studies play an important role in polymer processing including fiber spinning. In the current work, rheological behavior has been studied for polyacrylonitrile (PAN)/carbon nanotube (CNT) dispersions in dimethyl formamide (DMF), where CNT loading is as high as 15 wt% of the total solids (polymer + CNT). The presence of CNTs increased the elastic-like and shear thinning behavior of the dispersions. The terminal slope of the log G' versus log G" curve, which was used to characterize the homogeneity of solution or dispersion, is dependent on the CNT concentration but independent of temperature between 0 and 60 °C. PAN/CNT-10 (90 wt% PAN +10 wt% CNT) and PAN/CNT-15 were gel spun at different conditions, with small diameter capillary at high shear rate and large diameter capillary at relatively low shear rate. Additionally, for PAN/CNT-10, fiber spinning with lower molecular weight polymer showed increased continuous jetting time when compared to spinning with higher molecular weight polymer. In addition, the rheological behavior of PAN/cellulose nanocrystal (CNC) dispersion with 20–60 wt% CNC was also compared to that of the PAN/CNT dispersions. PAN/CNC and PAN/CNT share similarities in both rheological behavior and fiber spinning at high filler loading.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

An energy-balance model of glaciation cycles

A one dimensional energy balance model is presented which contains a time lagged albedo to account for the delayed dependence of continental ice sheets on temperature; it also includes a smoothing of temperature gradients in the tropics to account for the effect of the Hadley circulation on the strong flattening of meridional temperature profiles there. The model exhibits finite amplitude, sustained free oscillations; these oscillations are triggered by a change in the insulation parameter and occur in the absence of any external forcing. This model behavior strongly suggests the possibility of an almost-intransitive mechanism playing a role in glaciation cycles. This behavior also occurs on shorter time scales which might be relevant to the interannual variability of the atmosphere.

Ghil, M.↗

Ion‐Specific Interactions Engender Dynamic and Tailorable Properties in Biomimetic Cationic Polyelectrolytes

Abstract Biomaterials such as spider silk and mussel byssi are fabricated by the dynamic manipulation of intra‐ and intermolecular biopolymer interactions. Organisms modulate solution parameters, such as pH and ion co‐solute concentration, to effect these processes. These biofabrication schemes provide a conceptual framework to develop new dynamic and responsive abiotic soft material systems. Towards these ends, the chemical diversity of readily available ionic compounds offers a broad palette to manipulate the physicochemical properties of polyelectrolytes via ion‐specific interactions. In this study, we show for the first time that the ion‐specific interactions of biomimetic polyelectrolytes engenders a variety of phase separation behaviors, creating dynamic thermal‐ and ion‐responsive soft matter that exhibits a spectrum of physical properties, spanning viscous fluids to viscoelastic and viscoplastic solids. These ion‐dependent characteristics are further rendered general by the merger of lysine and phenylalanine into a single, amphiphilic vinyl monomer. The unprecedented breadth, precision, and dynamicity in the reported ion‐dependent phase behaviors thus introduce a broad array of opportunities for the future development of responsive soft matter; properties that are poised to drive developments in critical areas such as chemical sensing, soft robotics, and additive manufacturing.

Aubrecht, Filip J.↗

Comparison of Machine Learning Approaches for Prediction of the Equivalent Alkane Carbon Number for Microemulsions Based on Molecular Properties

The chemical properties of oils are vital in the design of microemulsion systems. The hydrophilic–lipophilic difference equation used to predict microemulsions’ phase behavior expresses the oils’ physiochemical properties as the equivalent alkane carbon number (EACN). The experimental determination of EACN requires knowledge of the temperature dependence of the microemulsion system and the effects of different surfactant concentrations. Thus, the experimental determination is time-intensive and tedious, requiring days to months for proper separations. Furthermore, the experiments require high purity of chemicals because microemulsions are sensitive to impurities. Our work focuses on the quick and reliable predictions of the EACN with machine learning (ML) models. Due to the immaturity of ML chemical predictions, we compare three graph neural networks (GNNs) and a gradient-boosted tree algorithm, known as XGBoost. The GNNs use the molecular structures represented as simplified molecular-input line-entry system (SMILES) codes for the initial input, which allows us to assess whether geometry optimization is necessary for reliable results. The XGBoost model also begins with the SMILES representations of the molecules but uses molecular descriptors instead of geometry optimizations. As a result, the best model tested (crystal graph convolutional neural network with Merck molecular force field-94) has an error of 1.15 EACN units of the true EACN for unknown data with the errors skewed toward zero and an R² score of 0.9

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Theoretical Study of High Harmonic Generation in Monolayer NbSe 2

High harmonic generation (HHG) is a powerful probe of electron dynamics on attosecond to femtosecond time scales and has been successfully used to detect electronic and structural changes in solid-state quantum materials, including transition-metal dichalcogenides (TMDs). Among TMDs, bulk NbSe 2 exhibits charge density wave (CDW) order below 33 K and becomes superconducting below 7.3 K. Monolayer NbSe 2 also has superconducting and CDW behavior and is therefore interesting as a material whose different structural and electronic properties could be probed via HHG. Here, we predict the HHG response of the pristine 2H and CDW phases of monolayer NbSe 2 using real-time time-dependent density functional theory under the application of a simulated laser pulse excitation. We find that due to the lack of inversion symmetry in both monolayer phases, it is possible to excite even harmonics and that the even harmonics appear as the transverse components of the current response under excitations polarized along the zigzag direction of the monolayer, while odd harmonics arise from the longitudinal current response in all excitation directions. This suggests that the even and odd harmonic responses can be controlled via the polarization of the probing field, opening an avenue for potentially useful applications in optoelectronic devices.

36 MATERIALS SCIENCE↗

Magnetic anisotropy and GGG substrate stray field in YIG films down to millikelvin temperatures

Abstract Quantum magnonics investigates the quantum-mechanical properties of magnons, such as quantum coherence or entanglement for solid-state quantum information technologies at the nanoscale. The most promising material for quantum magnonics is the ferrimagnetic yttrium iron garnet (YIG), which hosts magnons with the longest lifetimes. YIG films of the highest quality are grown on a paramagnetic gadolinium gallium garnet (GGG) substrate. The literature has reported that ferromagnetic resonance (FMR) frequencies of YIG/GGG decrease at temperatures below 50 K despite the increase in YIG magnetization. We investigated a 97 nm-thick YIG film grown on 500 μm-thick GGG substrate through a series of experiments conducted at temperatures as low as 30 mK, and using both analytical and numerical methods. Our findings suggest that the primary factor contributing to the FMR frequency shift is the stray magnetic field created by the partially magnetized GGG substrate. This stray field is antiparallel to the applied external field and is highly inhomogeneous, reaching up to 40 mT in the center of the sample. At temperatures below 500 mK, the GGG field exhibits a saturation that cannot be described by the standard Brillouin function for a paramagnet. Including the calculated GGG field in the analysis of the FMR frequency versus temperature dependence allowed the determination of the cubic and uniaxial anisotropies. We find that the total crystallographic anisotropy increases more than three times with the decrease in temperature down to 2 K. Our findings enable accurate predictions of the YIG/GGG magnetic systems behavior at low and ultralow millikelvin temperatures, crucial for developing quantum magnonic devices.

Serha, Rostyslav O.↗

Time-temperature-stress dependence of boron fiber deformation

The time-dependent deformation of boron fibers over the temperature range from -190 to 800 C is studied by flexural stress relaxation and flexural internal friction techniques on 203-micron diam specimen fibers commercially produced by chemical vapor deposition (CVD) on a 13-micron tungsten substrate. It is shown that up to at least 800 C all nonelastic behavior observed during axial deformation of CVD boron fibers can be explained solely by anelastic mechanisms and that although creep strains are small, boron fiber anelasticity can produce significant mechanical effects which would otherwise be neglected under the elastic approximation. Relations are obtained to demonstrate the considerable effects of anelasticity on such fiber/composite properties as modulus, creep, creep recovery, stress relaxation, and damping capacity. For an elastic-core/anelastic-sheath model, boron fibers on tungsten substrates are shown to have predictable fracture stresses for time-temperature conditions ranging from impact to long-time stress rupture. Possible techniques for altering these stresses are discussed.

Dicarlo, J. A.↗

Life prediction of thermomechanical fatigue using total strain version of strainrange partitioning (SRP): A proposal

A method is proposed (without experimental verification) for extending the total strain version of Strainrange Partitioning (TS-SRP) to predict the lives of thermomechanical fatigue (TMF) cycles. The principal feature of TS SRP is the determination of the time-temperature-waveshape dependent elastic strainrange versus life lines that are added subsequently to the classical inelastic strainrange versus life lines to form the total strainrange versus life relations. The procedure is based on a derived relation between failure and flow behavior. Failure behavior is represented by conventional SRP inelastic strainrange versus cyclic life relations, while flow behavior is captured in terms of the cyclic stress-strain response characteristics. Stress-strain response is calculated from simple equations developed from approximations to more complex cyclic constitutive models. For applications to TMF life prediction, a new testing technique, bithermal cycling, is proposed as a means for generating the inelastic strainrange versus life relations. Flow relations for use in predicting TMF lives would normally be obtained from approximations to complex thermomechanical constitutive models. Bithermal flow testing is also proposed as an alternative to thermomechanical flow testing at low strainranges where the hysteresis loop is difficult to analyze.

Saltsman, James F.↗

Discrete event simulation tool for analysis of qualitative models of continuous processing systems

An artificial intelligence design and qualitative modeling tool is disclosed for creating computer models and simulating continuous activities, functions, and/or behavior using developed discrete event techniques. Conveniently, the tool is organized in four modules: library design module, model construction module, simulation module, and experimentation and analysis. The library design module supports the building of library knowledge including component classes and elements pertinent to a particular domain of continuous activities, functions, and behavior being modeled. The continuous behavior is defined discretely with respect to invocation statements, effect statements, and time delays. The functionality of the components is defined in terms of variable cluster instances, independent processes, and modes, further defined in terms of mode transition processes and mode dependent processes. Model construction utilizes the hierarchy of libraries and connects them with appropriate relations. The simulation executes a specialized initialization routine and executes events in a manner that includes selective inherency of characteristics through a time and event schema until the event queue in the simulator is emptied. The experimentation and analysis module supports analysis through the generation of appropriate log files and graphics developments and includes the ability of log file comparisons.

Malin, Jane T.↗

Nonlinear viscoelastic response of highly filled elastomers under multiaxial finite deformation

A biaxial tester was used to obtain precise biaxial stress responses of highly filled, high strain capability elastomers. Stress-relaxation experiments show that the time-dependent part of the relaxation response can be reasonably approximated by a function which is strain and biaxiality independent. Thus, isochronal data from the stress-relaxation curves can be used to determine the stored energy density function. The complex behavior of the elastomers under biaxial deformation may be caused by dewetting.

Peng, Steven T. J.↗

Lox droplet vaporization in a supercritical forced convective environment

A systematic investigation has been conducted to study the effects of ambient flow conditions (i.e. pressure and velocity) on supercritical droplet gasification in a forced-convective environment. The model is based on the time-dependent conservation equations in axisymmetric coordinates, and accommodates thermodynamic nonidealities and transport anomalies. In addition, an efficient scheme for evaluating thermophysical properties over the entire range of fluid thermodynamic states is established. The analysis allows a thorough examination of droplet behavior during its entire lifetime, including transient gasification, dynamic deformation, and shattering. A parametric study of droplet vaporization rate in terms of ambient pressure and Reynolds number is also conducted.

Hsiao, Chia-Chun↗

Disruption of coronal magnetic field arcades

The ideal and resistive properties of isolated large-scale coronal magnetic arcades are studied using axisymmetric solutions of the time-dependent magnetohydrodynamic (MHD) equations in spherical geometry. We examine how flares and coronal mass ejections may be initiated by sudden disruptions of the magnetic field. The evolution of coronal arcades in response to applied shearing photospheric flows indicates that disruptive behavior can occur beyond a critical shear. The disruption can be traced to ideal MHD magnetic nonequilibrium. The magnetic field expands outward in a process that opens the field lines and produces a tangential discontinuity in the magnetic field. In the presence of plasma resistivity, the resulting current sheet is the site of rapid reconnection, leading to an impulsive release of magnetic energy, fast flows, and the ejection of a plasmoid. We relate these results to previous studies of force-free fields and to the properties of the open-field configuration. We show that the field lines in an arcade are forced open when the magnetic energy approaches (but is still below) the open-field energy, creating a partially open field in which most of the field lines extend away from the solar surface. Preliminary application of this model to helmet streamers indicates that it is relevant to the initiation of coronal mass ejections.

Mikic, Zoran↗

Cold-Point Tropopause Temperature Bias in Reanalyses Modulated By Equatorial Waves

In this reanalysis inter-comparison study, we compare the modeled Cold-point tropopause temperature (CPT from model level data) near the equator to that of multi-mission GNSS-RO within a preliminary time period of 2007-2011. The known reanalysis CPT temperature warm bias is studied relative to the phase of equatorial waves filtered from GNSS-RO at tropopause level. This uncovers a common denominator in the CPT temperature bias behavior in all reanalyses: - When equatorial waves are present, within their cold phase the reanalysis bias is increased by over 1K, i.e. >1K on top of the reanalysis average warm bias. - Within an equatorial wave’s warm phase, the opposite is observed, with the reanalysis CPT temperature bias even being reversed at higher equatorial wave amplitudes, i.e. the modeled CPT becoming too cold in these cases. - With no equatorial wave anomalies present, the reanalysis bias remains at the average reported in previous inter-comparisons that looked at zonal-mean CPT biases. Inertia-Gravity and Mixed Rossby-Gravity waves show this behavior most clearly, Kelvin waves show a similar modulation but with half of the magnitude, and equatorial Rossby wave modulation of CPT reanalysis bias is still apparent but with further decreased magnitude. This hints on a time-space scale-dependence, with medium-smaller-scale and faster equatorial waves influencing CPT reanalysis bias the most. For comparison, the large-scale and slow-moving MJO does not show any of the effects described above. Current work focuses on the data assimilation response of the reanalysis systems, again relative to the equatorial wave’s phases.

Tropopause↗

The Complexity of the Day-Side X-Line During Southward Interplanetary Magnetic Field

High-resolution global magnetohydrodynamics (MHD) simulations include both meso- and global-scale processes occurring at the magnetopause, which interact to determine the time-dependent orientation of the day-side x-line (DXL). This study demonstrates that the global orientation of the DXL in GAMERA global MHD simulations varies on a time scale of minutes during steady southward interplanetary magnetic field conditions. This behavior manifests in observational data when reconnection outflows indicate that the direction to the x-line is opposite to the prediction from a steady-state model of the reconnection location. Because steady-state models of the DXL do not capture dynamics that are independent of solar wind variations, particularly surface waves and flux transfer events, they represent a time-averaged state of the system.

Brandon Burkholder↗

Template Matching Approach to Signal Prediction

A new approach to signal prediction and prognostic assessment of spacecraft health resolves an inherent difficulty in fusing sensor data with simulated data. This technique builds upon previous work that demonstrated the importance of physics-based transient models to accurate prediction of signal dynamics and system performance. While models can greatly improve predictive accuracy, they are difficult to apply in general because of variations in model type, accuracy, or intended purpose. However, virtually any flight project will have at least some modeling capability at its disposal, whether a full-blown simulation, partial physics models, dynamic look-up tables, a brassboard analogue system, or simple hand-driven calculation by a team of experts. Many models can be used to develop a predict, or an estimate of the next day s or next cycle s behavior, which is typically used for planning purposes. The fidelity of a predict varies from one project to another, depending on the complexity of the simulation (i.e. linearized or full differential equations) and the level of detail in anticipated system operation, but typically any predict cannot be adapted to changing conditions or adjusted spacecraft command execution. Applying a predict blindly, without adapting the predict to current conditions, produces mixed results at best, primarily due to mismatches between assumed execution of spacecraft activities and actual times of execution. This results in the predict becoming useless during periods of complicated behavior, exactly when the predict would be most valuable. Each spacecraft operation tends to show up as a transient in the data, and if the transients are misaligned, using the predict can actually harm forecasting performance. To address this problem, the approach here expresses the predict in terms of a baseline function superposed with one or more transient functions. These transients serve as signal templates, which can be relocated in time and space against the signal background. One then has the ability to reconstruct a signal regardless of the precise timing of the transients. During operation, one applies the actual start times of spacecraft activities as they occur, and produces a reconstructed, accurate predict in real-time. This general approach is valid under two important conditions. First, the transients themselves must be time-invariant. Second, the transients must be reasonably consistent with respect to different operating points. Both of these assumptions are generally valid, but in the case of a complicated system with numerous types of overlapping transients, this approach may not be effective. Fortunately, there tend to be few transients in spacecraft telemetry of sensor quantities or low-level health and status information because these signals rarely reflect multiple different types of operation. Furthermore, if the predict is at least reasonably close to actual operation, the shift either in time, or in the operating point when the transient occurs - is likely to be small. The proposed approach considers three ways to recognize a transient. The first and most reliable is to use a different signal that identifies operating mode - often the transient will be correlated to a change in operating mode, and this change can usually be detected positively from discrete signals in spacecraft telemetry. If there is no useful mode signal, the second option is to identify the transient template by hand, and detect the onset of the transient using a curve-fitting approach. Finally, if one elects not to choose by hand, there is an option for automatic selection. This technique has been applied to sensor data from several JPL missions and industrial applications, demonstrating an improvement in accurate prediction of future behavior and early detection of system problems. This technique is applicable to practically any time-varying, quantitative sensor measurement.

Mackey, Ryan↗