ON THE ANALYSIS OF LINEAR PYROLYSIS EXPERIMENTS
Linear pyrolysis experiments - fluid mechanics - equations for pyrolysis rate determinations - solid propellant combustion
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Linear pyrolysis experiments - fluid mechanics - equations for pyrolysis rate determinations - solid propellant combustion
Large-aperture, wide-angle, broad-band infrared spectrometer compact and light in weight. Based on double-pass version of Schmidt optical system that acts as both collimator and camera. Because optical system contained in piece of solid glass, it is mechanically and thermally stable. System made of water-free fused silica to minimize absorption of infrared radiation. Although in principle made from single, solid piece, in practice made in two pieces cemented together. Fabrication easier and simpler if more cemented surfaces used so each optical surface grounded and polished like single lens element.
Understanding the chemo-mechanical behaviors of electrodes, particularly at the electrode/electrolyte interfaces, is critical for improving the performance of all-solid-state batteries. However, due to the instability of electrolyte materials under ambient conditions, such characterizations are challenging, particularly for sulfide-based all-solid-state batteries. Herein, by combining time-of-flight secondary-ion mass spectroscopy (ToF-SIMS) and in-SEM nanoindentation measurements, a systematic quantitative investigation of the chemo-mechanical behaviors of pyrene-4,5,9,10-tetraone (PTO) /Li 6 PS 5 Cl composite cathodes is carried out. Chemical and quantitative mechanical information of the composite cathode were collected with high spatial resolution after developing and implementing an air-free characterization protocol. By directly connecting the Young’s modulus and hardness with the Li distribution in the composite cathode, a comprehensive chemo-mechanical mapping of the PTO/ Li 6 PS 5 Cl composite cathode has been established. Furthermore, this work improves our knowledge of the critical chemo-mechanical phenomena that occur at the cathode/electrolyte interfaces in all-solid-state batteries.
Abstract Designing stable Li metal and supporting solid structures (SSS) is of fundamental importance in rechargeable Li‐metal batteries. Yet, the stripping kinetics of Li metal and its mechanical effect on the supporting solids (including solid electrolyte interface) remain mysterious to date. Here, through nanoscale in situ observations of a solid‐state Li‐metal battery in an electron microscope, two distinct cavitation‐mediated Li stripping modes controlled by the ratio of the SSS thickness ( t ) to the Li deposit's radius ( r ) are discovered. A quantitative criterion is established to understand the damage tolerance of SSS on the Li‐metal stripping pathways. For mechanically unstable SSS ( t / r < 0.21), the stripping proceeds via tension‐induced multisite cavitation accompanied by severe SSS buckling and necking, ultimately leading to Li “trapping” or “dead Li” formation; for mechanically stable SSS ( t / r > 0.21), the Li metal undergoes nearly planar stripping from the root via single cavitation, showing negligible buckling. This work proves the existence of an electronically conductive precursor film coated on the interior of solid electrolytes that however can be mechanically damaged, and it is of potential importance to the design of delicate Li‐metal supporting structures to high‐performance solid‐state Li‐metal batteries.
When a separating body is viewed as a nonequilibrium thermodynamic process, the full thermodynamic nature of the surface energy induced by crack propagation becomes apparent. Within such a general framework it is no longer possible to view the surface energy as a material constant. For the self-propagating crack the induced surface energy is shown to depend explicitly on the square of the crack propagation speed. It is also shown that a separating body produces entropy even though the mechanical response of the solid may be elastic. The introduction of surface quantities such as surface energy into the continuum description of the fracture process forces a major departure from the mechanics appropriate to the nonseparating body. Local equations of balance are no longer obtainable as derived consequences of postulated global balance equations. They must instead be imposed as separate additional postulates.
The metallurgy and materials communities have long understood and exploited fundamental links between chemical and structural ordering in metallic solids to tailor their mechanical properties. We extend these ideas to include prediction of the nanocrystalline strength limit in high-entropy alloys and intermetallic compounds, where a breakdown occurs in the classical Hall-Petch strengthening behavior. The highest reported strength achievable through alloying has rapidly climbed and given rise to new classifications of materials with extraordinary properties, with a notable case being nanocrystalline metals. High-entropy alloys (chemically disordered, concentrated solid solutions) and intermetallic compounds are two boundary cases of how tailored order can be used to manipulate mechanical behavior. Here, we show that the complex electronic-structure mechanisms governing the peak strength of alloys and pure metals can be reduced to a few physically meaningful parameters based on their atomic arrangements and used – with no fitting parameters – to predict the maximum strength of these materials. This includes a generalized energy-based accounting for the degree of structural and chemical ordering that allows for rapid and reasonably accurate prediction of peak strength (validated in the nanocrystalline limit) as a function of temperature. Predictions of maximum strength based on the activation energy (with all materials properties derived from DFT calculations or experiments) for a stress-driven transition to an amorphous state is shown to accurately describe the breakdown in Hall-Petch behavior at the smallest crystallite sizes for pure metals, intermetallic compounds, high-entropy alloys, and metallic glasses. Further, this activation energy is also shown to be directly proportional to interstitial electronic charge density, which is a good predictor of ductility, stiffness (moduli), and phase stability in high-entropy alloys and solid metals generally. The proposed framework suggests the possibility of coupling ordering and intrinsic strength to mechanisms like dislocation nucleation, hydrogen embrittlement, and transport properties, such as through correlations between the activation energies for amorphization with stacking-fault and grain boundary energies. It additionally opens the prospect for greatly accelerated structural materials design and development to address materials challenges limiting more sustainable and efficient use of energy.
While the oceans undoubtly contribute to energy dissipation, it seems implausible that such a small amount (0.02%) of the Earth's mass could play such a dominant role in lunar orbital evolution. An alternate hypothesis assumes that most of the dissipation is associated with solid-body tides. This mechanism is also capable of varying significantly over time for viscoelastic bodies. In such an analysis of orbital evolution, the bodies are modeled as incompressible, Kelvin-Voight solids. While this material is simplistic, it does provide an analytical characterization of solid-body dissipation and the resulting tidal moment. The orbital history of a two body system is traced back in time to develop constraints on the satellite's origin. These constraints suggest the Moon appeared in a significantly inclined orbit at a distance greater than ten Earth radii. This distance is outside of the Roche limit and would appear to alleviate some difficulties associated with capture hypotheses. Small eccentricity at close approach suggests an origin by accretion.
Tissue cells are known to be sensitive to mechanical stresses imposed on them by agitation in bioreactors. The amount of agitation provided in a microcarrier or suspension bioreactor should be only enough to provide effective homogeneity. Three distinct flow regions can be identified in the reactor: bulk turbulent flow, bulk laminar flow and boundary-layer flows. Possible mechanisms of cell damage are examined by analyzing the motion of microcarriers or free cells relative to the surrounding fluid, to each other and to moving or stationary solid surfaces. The primary mechanisms of cell damage appear to result from: (1) direct interaction between microcarriers and turbulent eddies; (2) collisions between microcarriers in turbulent flow; and (3) collisions against the impeller or other stationary surfaces. If the smallest eddies of turbulent flow are of the same size as the microcarrier beads, they may cause high shear stresses on the cells. Eddies the size of the average interbead spacing may cause bead-bead collisions which damage cells. The severity of the collisions increases when the eddies are also of the same size as the beads. Impeller collisions occur when beads cannot avoid the impeller leading edge as it advances through the liquid. The implications of the results of this analysis on the design and operation of tissue culture reactors are discussed.
Friction self-piercing riveting (F-SPR), as a solid-state joining process that generates frictional heat during the process, was utilized to join a 3 T configuration of low-ductility AA7075-AA7075-AA6022 sheets. A multi-step F-SPR process was employed to precisely control the mechanical interlocking and solid-state joining, ensuring a strong joint formation. With control of the plunge depth when the transition from rivet penetration to rivet flaring, two joining conditions were developed to assess mechanical joint integrity: one bearing deep penetration with a smaller interlock, and the other yielding a shallow penetration with a larger interlock. Both strategies met the criteria for a sound rivet joint. Customized lap shear tensile configurations were designed to assess the joint strength at interface between first and second layers, as well as between second and third layers. Both conditions demonstrated great joint strength between the first and second layers, while deeper penetration approach showed stronger solid-state joint, leading to improved joint strength between the second and third layers.
The objective is to determine the mechanism of gas-phase flame spread over solid fuel surfaces in the absence of any buoyancy or externally imposed gas-phase flow. Such understanding can be used to improve the fire safety aspects of space travel by providing information that will allow judicious selections of spacecraft materials and environments to be made. The planned experiment consists of measuring the flame spread rate over thermally thin and thermally thick fuels in a closed container in the low-gravity environment of the Space Shuttle. Measurements consist of flame spread rate and shape obtained from two views of the process as recorded on movie film and surface and gas-phase temperatures obtained from fine-wire thermocouples. The temperature measurements along with appropriate modeling provide information about the gas-to-solid heat flux. Environmental parameters to be varied are the oxygen concentration and pressure.
Throughout the last decade, Computer Aided Design was seen as a Great Promise. Much was accomplished, but that pales in comparison with what was promised. Ultimate achievement has always seemed just a step away. During the era of the early turnkey system, the one step was limited by modeling geometry through a wire frame. Besides being cumbersome to deal with in three dimensions, it was continually shown that a wire frame is ambiguous. This made the modeling of geometry for engineering purposes even more frustrating. The fundamentals of computer aided engineering design rest on the ability to do various analyses. Presently, solid modeling is taking the mechanical engineering CAD world by storm. There are no fewer than 20 solid modeling packages around the world, and more appearing with each vendor show. The question of integration, that is, the combination of elements of the CAD process into unified and easily usable design tools still exists.
Constructing a stable solid electrolyte interface (SEI) with high productivity and scalability is essential for the practical application of thin Li metal anodes. Here, in this work, we report a chemical vapor transformation (CVT) strategy in which Li metal is exposed to trimethylaluminum (TMA), inducing a rapid and spontaneous surface reaction that forms a robust, multilayered SEI. In situ quartz crystal microbalance (QCM) and quadrupole mass spectrometry (QMS), combined with ex situ X-ray photoelectron spectroscopy (XPS), UV Raman spectroscopy, and density functional theory (DFT) calculations, reveal that TMA removes the native passivation layer, reacts with Li metal, and drives a coupled bulk-surface transformation involving Li–Al interdiffusion. The resulting SEI exhibits a chemically graded structure consisting of an inner Li–Al alloy and an outer amorphous carbon layer formed via demethylation and ligand-exchange pathways. This modified surface exhibits significantly enhanced stability compared to that of bare Li in electrochemical cycling using liquid and solid-state electrolytes. This work unveils a unique surface-mediated bulk transformation mechanism for lithium metal and establishes CVT as a scalable and fundamentally distinct approach for the interfacial engineering of reactive metals.
Li metal anode is a promising candidate for next-generation energy storage systems and is widely explored in Li-ion and solid-state batteries. Despite its potential, Li metal anodes face instabilities during long-term cycling, especially when paired with NMC or sulfur-based cathodes, where Li is cycled at high capacities of 6-8 mAh/cm2, equivalent to a thickness of 30-40 µm. During such extensive utilization, degradation mechanisms such as excessive solid electrolyte interphase (SEI), dendrites, and dead Li emerge, and ultimately lead to sudden failure and reduced cycle life. The origin of the degradation mechanisms stem from surface heterogeneities introduced during Li foil manufacturing and storage [1, 2]. As cycling progresses, the local heterogeneities propagate, resulting in uneven Li utilization and degradation-prone regions across the electrode [3], which consequently induce performance variations at the cell level. This heterogeneity propagation is particularly pronounced in large-format pouch cells in practical applications, where the surface effects are magnified. Without a clear understanding of the multi-scale heterogeneities and the development of surface homogenization methods, the performance consistency will be compromised, hindering the commercialization of Li metal batteries. In this presentation, we investigate the evolution of surface heterogeneity propagation on commercially available Li foils. We discover that inhomogeneous Li utilization appears as early as the first half-cycle of formation, manifesting as localized clusters and pits. In pouch cell configurations, these features exhibit areal density variations across the electrode on a scale of millimeters. To improve Li utilization homogeneity, a scalable mechanical brushing method is introduced to remove the chemically heterogeneous surface passivation layer. Furtherore, the influence of utilization homogeneity on cell-to-cell consistency is evaluated using 32 Li-NMC811 pouch cells divided into as-received and brushed Li groups. On the brushed Li, clusters and pits are no longer observable, and the cells exhibit significantly improved consistency in discharge capacity trajectories and cycle lifetime. Overall, this study highlights the role of Li surface utilization homogeneity on long-term cycling performance. Our research provides a pathway for improving large-area electrode uniformity and establishing evaluation methods for cell-to-cell consistency, both are key steps toward the commercialization of Li metal batteries and beyond. [1] Otto, Svenja-K., et al. "In-depth characterization of lithium-metal surfaces with XPS and ToF-SIMS: toward better understanding of the passivation layer." Chemistry of Materials 33.3 (2021): 859-867. [2] Hatzell, Kelsey, et al. "Aligning lithium metal battery research and development across academia and industry." Joule (2024). [3] Kim, Sangwook, et al. "Calendar life of lithium metal batteries: Accelerated aging and failure analysis." Energy Storage Materials 65 (2024): 103147.
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The primary loading condition in launch-vehicle barrel sections is axial compression, and it is therefore important to understand the compression behavior of any structures, structural concepts, and materials considered in launch-vehicle designs. This understanding will necessarily come from a combination of test and analysis. However, certain potentially beneficial structures and structural concepts do not lend themselves to commonly used simplified analysis methods, and therefore innovative analysis methodologies must be developed if these structures and structural concepts are to be considered. This paper discusses such an analysis technique for the fluted-core sandwich composite structural concept. The presented technique is based on commercially available finite-element codes, and uses shell elements to capture behavior that would normally require solid elements to capture the detailed mechanical response of the structure. The shell thicknesses and offsets using this analysis technique are parameterized, and the parameters are adjusted through a heuristic procedure until this model matches the mechanical behavior of a more detailed shell-and-solid model. Additionally, the detailed shell-and-solid model can be strategically placed in a larger, global shell-only model to capture important local behavior. Comparisons between shell-only models, experiments, and more detailed shell-and-solid models show excellent agreement. The discussed analysis methodology, though only discussed in the context of fluted-core composites, is widely applicable to other concepts.
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