New insights into VOC oxidation: kinetics and atmospheric impact
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The building block approach is currently used to design composite structures. With this approach, the data from coupon tests is scaled up to determine the design of a structure. Current standard impact tests and methods of relating test data to other structures are not generally understood and are often used improperly. A methodology is outlined for using impact force as a scale parameter for delamination damage for impacts of simple plates. Dynamic analyses were used to define ranges of plate parameters and impact parameters where quasi-static analyses are valid. These ranges include most low velocity impacts where the mass of the impacter is large and the size of the specimen is small. For large mass impacts of moderately thick (0.35 to 0.70 cm) laminates, the maximum extent of delamination damage increased with increasing impact force and decreasing specimen thickness. For large mass impact tests at a given kinetic energy, impact force and hence delamination size depends on specimen size, specimen thickness, boundary conditions, and indenter size and shape. If damage is reported in terms of impact force instead of kinetic energy, large mass test results can be applied directly to other plates of the same size.
The building block approach is currently used to design composite structures. With this approach, the data from coupon tests are scaled up to determine the design of a structure. Current standard impact tests and methods of relating test data to other structures are not generally understood and are often used improperly. A methodology is outlined for using impact force as a scale parameter for delamination damage for impacts of simple plates. Dynamic analyses were used to define ranges of plate parameters and impact parameters where quasi-static analyses are valid. These ranges include most low-velocity impacts where the mass of the impacter is large, and the size of the specimen is small. For large-mass impacts of moderately thick (0.35-0.70 cm) laminates, the maximum extent of delamination damage increased with increasing impact force and decreasing specimen thickness. For large-mass impact tests at a given kinetic energy, impact force and hence delamination size depends on specimen size, specimen thickness, boundary conditions, and indenter size and shape. If damage is reported in terms of impact force instead of kinetic energy, large-mass test results can be applied directly to other plates of the same thickness.
Fossils of the oldest microorganisms exist in 3.5 billion year old rocks and there is indirect evidence that life may have existed 3.8 billion years ago (3.8 Ga). Impacts able to destroy life or interrupt prebiotic chemistry may have occurred after 3.5 Ga. If large impactors vaporized the oceans, sterilized the planets, and interfered with the origination of life, life must have originated in the time interval between these impacts which increased with geologic time. Therefore, the maximum time required for the origination of life is the time that occurred between sterilizing impacts just before 3.8 Ga or 3.5 Ga, depending upon when life first appeared on earth. If life first originated 3.5 Ga, and impacts with kinetic energies between 2 x 10 the the 34th and 2 x 10 to the 35th were able to vaporize the oceans, using the most probable impact flux, it is found that the maximum time required to originate life would have been 67 to 133 million years (My). If life originated 3.8 Ga, the maximum time to originate life was 2.5 to 11 My. Using a more conservative estimate for the flux of impacting objects before 3.8 Ga, a maximum time of 25 My was found for the same range of impactor kinetic energies. The impact model suggests that it is possible that life may have originated more than once.
Absolute age determination of impact cratering events remains difficult and often controversial; a challenge that has resulted in < 50% of known impact craters regarded as accurately and precisely dated. Besides conventional 40Ar/39Ar and U-Pb methods, zircon (U-Th)/He (ZHe) dating of impactites has been applied to large- to medium-sized impact structures. ZHe dates can be fully reset in minutes at 1000°C, which is commonly reached in central sections of the melt sheet, whereas resetting of ZHe at <300°C, which might be encountered near the crater margins or persist in post-impact hydrothermal systems, may take >103-6 years. There is a critical need to quantify the effects of shock-induced microstructures and impact metamorphism on helium diffusion kinetics in well-characterized, variably shocked zircon to further establish the reliability of (U-Th)/He for dating impacts. For this purpose, we investigated suevite and impact melt samples from two impact structures, the Chicxulub multi-ring basin and the Ries complex crater, which enables us to compare zircon helium diffusion kinetics from impact structures with differing sizes, ages, and hydrothermal system longevities. Shock microstructures were characterized by backscattered-electron (BSE) imaging prior to diffusion step-heating fractional release experiments using light-bulb furnace with prograde and retrograde incremental 10°C steps from 250°C to 600°C. Afterward, we characterize the diffusion domain sizes and their interconnectivity within the shocked zircon grains using electron backscatter diffraction (EBSD). We find that zircon with few shock microstructures exhibit no significant deviation from helium diffusion kinetics of undamaged zircon. In contrast, zircon grains with planar deformation features (PDFs) and granular textures classified by BSE and EBSD are characterized by a dramatic decrease in helium retentivity, similar to radiation damaged grains, due to a reduction in the effective domain size and the introduction of interconnected fast diffusion pathways created by shock microstructures. A subset of grains were dated by ZHe after the external morphology of the grains was determined by BSE imaging. The euhedral grains yielded a weighted mean age within the uncertainty of the accepted impact ages, whereas the grains with PDFs or granular textures exhibited younger ages. Thus, these diffusion experiments and ZHe dates suggest that the dramatic decrease in domain size likely renders shocked grains more susceptible to impact-induced hydrothermal resetting and subsequent overprinting. Hence, characterization of shock microstructures is critical for determining accurate impact ages using ZHe methods especially when applied to previously unconstrained craters. The thermochronometer also offers the opportunity to determine the magnitude and duration of post-impact hydrothermal circulation.
A Near Earth object impacting into Earth's atmosphere may produce damaging effects at the surface due to airblast, thermal pulse, or kinetic impact in the form of meteorites. At large sizes (greater than many tens of meters), the damage is amplified by the hypersonic impact of these large projectiles moving with cosmic velocity, leaving explosively produced craters. However, much more common is simple "kinetic" damage caused by the impact of smaller meteorites moving at terminal speeds. As of this date a handful of instances are definitively known of people or structures being directly hit and/or damaged by the kinetic impact of meteorites. Meteorites known to have struck humans include the Sylacauga, Alabama fall (1954) and the Mbale meteorite fall (1992). Much more common is kinetic meteorite damage to cars, buildings, and even a post box (Claxton, Georgia - 1984). Historical accounts indicate that direct kinetic damage by meteorites may be more common than recent accounts suggest (Yau et al., 1994). In this talk we will examine the contemporary meteorite flux and estimate the frequency of kinetic damage to various structures, as well as how the meteorite flux might affect the rate of human casualties. This will update an earlier study by Halliday et al (1985), adding variations expected in meteorite flux with latitude (Le Feuvre and Wieczorek, 2008) and validating these model predictions of speed and entry angle with observations from the NASA and SOMN fireball networks. In particular, we explore the physical characteristics of bright meteors which may be used as a diagnostic for estimating which fireballs produce meteorites and hence how early warning of such kinetic damage may be estimated in advance through observations and modeling.
A Near Earth object impacting into Earth's atmosphere may produce damaging effects at the surface due to airblast, thermal pulse, or kinetic impact in the form of meteorites. At large sizes (>many tens of meters), the damage is amplified by the hypersonic impact of these large projectiles moving with cosmic velocity, leaving explosively produced craters. However, much more common is simple "kinetic" damage caused by the impact of smaller meteorites moving at terminal speeds. As of this date a handful of instances are definitively known of people or structures being directly hit and/or damaged by the kinetic impact of meteorites. Meteorites known to have struck humans include the Sylacauga, Alabama fall (1954) and the Mbale meteorite fall (1992). Much more common is kinetic meteorite damage to cars, buildings, and even a post box (Claxton, Georgia - 1984). Historical accounts indicate that direct kinetic damage by meteorites may be more common than recent accounts suggest (Yau et al., 1994). In this talk we will examine the contemporary meteorite flux and estimate the frequency of kinetic damage to various structures, as well as how the meteorite flux might affect the rate of human casualties. This will update an earlier study by Halliday et al (1985), adding variations expected in meteorite flux with latitude (Le Feuvre and Wieczorek, 2008) and validating these model predictions of speed and entry angle with observations from the NASA and SOMN fireball networks. In particular, we explore the physical characteristics of bright meteors which may be used as a diagnostic for estimating which fireballs produce meteorites and hence how early warning of such kinetic damage may be estimated in advance through observations and modelling.
Calculations are made to determine the sizes of stony and iron meteoroids which could penetrate the atmosphere of Venus and cause hypervelocity impact craters on the planet's surface. Using scaling relationships based on kinetic energy, impact crater size is related to meteoroid size. Finally, it is determined that the smallest impact craters that might exist on Venus are on the order of 150 to 300 meters in diameter.
Reduced models for approximating the impact of kinetic electron behavior on the transport of thermal energy and magnetic field are investigated. The thermal flux limiter has improved agreement with Vlasov–Fokker–Planck data when a harmonic form is used that adjusts the electron mean free path to account for electron–electron collisions; these results apply to both unmagnetized and magnetized plasmas. Once a magnetic field is incorporated, the mean free path should also be modified using the electron gyroradius. A flux limiter on Nernst advection of magnetic fields is also required; a form that limits Nernst by the same fraction as the thermal heat-flow best reproduces kinetic simulations. A flux limiter form for the cross terms (Righi–Leduc and cross-gradient-Nernst) is also suggested. Hohlraum simulations relevant to fusion experiments on the National Ignition Facility are found to be sensitive to all of these details.
The safety issue has been raised with regards to potential molten metal detachments from the weld pool and cold filler wire during electron beam welding in space. This investigation was undertaken to evaluate if molten metal could detach and come in contact with astronauts and burn through the fabric of the astronauts' Extravehicular Mobility Unit (EMU) during electron beam welding in space. Molten metal detachments from either the weld/cut substrate or weld wire could present harm to a astronaut if the detachment was to burn through the fabric of the EMU. Theoretical models were developed to predict the possibility and size of the molten metal detachment hazards during the electron beam welding exercises at Low Earth Orbit (LEO). The primary molten metal detachment concerns were those cases of molten metal separation from the metal surface due to metal cutting, weld pool splashing, entrainment and release of molten metal due to filler wire snap-out from the weld puddle, and molten metal accumulation and release from the end of the weld wire. Some possible ways of obtaining molten metal drop detachments would include an impulse force, or bump, to the weld sample, cut surface, or filler wire. Theoretical models were developed for these detachment concerns from principles of impact and kinetic energies, surface tension, drop geometry, surface energies, and particle dynamics. The surface tension represents the force opposing the liquid metal drop from detaching whereas the weight of the liquid metal droplet represents a force that is tending to detach the molten metal drop. Theoretical calculations have indicated that only a small amount of energy is required to detach a liquid metal drop; however, much of the energy of an impact is absorbed in the sample or weld plate before it reaches the metal drop on the cut edge or surface. The tendency for detachment is directly proportional to the weld pool radius and metal density and inversely proportional to the surface tension of the liquid metal. For a detachment the initial kinetic energy of the weld pool with respect to the plate has to exceed the energy to form the extra surface required for the detachment of the pool. The difficulty is in transferring the energy from the point of impact through the plate and sample to the cut edge. It is likely that not all of the kinetic energy is available for detaching the pool; some may be sequestered in weld pool oscillations. The coefficient of restitution for the collision will be lower than one if irreversible deformation, for example plastic flow deformation, takes place during the collision. Thus determining the amount of energy from an impact that actually reaches the molten metal droplet is critical. Various molten metal detachment scenarios were tested experimentally in an enclosed vacuum chamber using the Ukrainian Universal Hand Tool, an electron beam welder designed for space welding. The experimental testing was performed in a 4 ft. X 4 ft. vacuum chamber at Marshall Space Flight Center, evacuated to vacuum levels of at least 50 microTorr, and also some welding garment material was utilized to observe the effect of the molten metal detachments on the material. A "carillon" apparatus consisting of four pendulum hammer strikers, each weighing approximately 3.65 lbs, raised to predetermined specific heights was used to apply an impact force to the weld sample/plate during electron beam welding and cutting exercises. The strikers were released by switching on an electric motor to rotate a pin holding wires retaining the strikers at desired heights. The specimens were suspended so as to be free to respond to the blows with a sudden velocity increment. The specimens were mounted on a hinged plate for minimizing effective mass with the option to fasten it down so as to raise its effective mass closer to that anticipated for an actual space welding scenario. Measurements were made of the impact energy and the horizontal fling distances of the detached metal drops. It was not particularly easy to generate the detachments for this experiment. This document presents the details of the theoretical modeling effort and a summary of the experimental effort to measure molten metal drop detachments from terrestrial electron beam welding in the enclosed vacuum chamber. The results of the experimental effort have shown that molten metal detachments can occur from the sample/weld plate only if a sufficiently large impact force is applied to the weld plate. A "weld pool detachment parameter" was determined to indicate whether detachment would occur. Detachment can be either full or partial (dripping), Partial detachment means that the weld pool detached from one side of the liquid-solid boundary so as to leave a hole at the puddle site but remained attached over part of the liquid-solid boundary and dripped down the plate with no fully detached material detected. Full detachment, however, does not necessarily mean that the whole pool fully detached; in some cases only a smaller portion of the pool detached, the remainder dripping down the plate. The weld pool detachment parameter according to theory and according to the empirical data allows a determination of whether full detachments might occur. Theoretical calculations indicated titanium alloy would be the most difficult from which to detach molten metal droplets followed by stainless steel and then by aluminum. The experimental results were for the most part consistent with the theoretical analysis and predictions. The above theory is applicable to other situations as desired for assessing the potential for molten metal detachments.
Abstract Discontinuous solid-solid phase transformations play a pivotal role in determining the properties of rechargeable battery electrodes. By leveraging operando Bragg Coherent Diffractive Imaging (BCDI), we investigate the discontinuous phase transformation in Li x Ni 0.5 Mn 1.5 O 4 within an operational Li metal coin cell. Throughout Li-intercalation, we directly observe the nucleation and growth of the Li-rich phase within the initially charged Li-poor phase in a 500 nm particle. Supported by the microelasticity model, the operando imaging unveils an evolution from a curved coherent to a planar semi-coherent interface driven by dislocation dynamics. Our data indicates negligible kinetic limitations from interface propagation impacting the transformation kinetics, even at a discharge rate of C/2 (80 mA/g). This study highlights BCDI’s capability to decode complex operando diffraction data, offering exciting opportunities to study nanoscale phase transformations with various stimuli.
Degradation of photovoltaic (PV) module encapsulant characteristics that lead to mechanical embrittlement and delamination remains a cause of failure in solar installations. A multiscale reliability model connecting the encapsulant mechanical and fracture properties to the degraded molecular structure and interfacial bonding to adjacent solar cell and glass substrates was previously published. The model, developed primarily for poly(ethylene-co-vinyl acetate) acetate (EVA) encapsulants, remains to be experimentally validated. Determining the degradation and crosslinking kinetics of alternative encapsulants, such as polyolefin elastomer (POE) and EVA/POE/EVA composites (EPE), can generalize the model. In this work, we subject fully cured EVA, POE, and EPE encapsulants to accelerated thermal aging to determine how high temperatures impact reaction kinetics. An increase in gel content (crosslinking) and decrease in crystallinity of the encapsulants under hot-aerobic (90 degrees C, 22% RH) and hot-anaerobic (90 degrees C, sealed in N 2 air) aging were observed, even in the absence of UV and crosslinking initiators. Fourier transform infrared spectroscopy (FTIR)-attenuated total reflectance analysis showed insignificant encapsulant degradation, demonstrating the critical role of UV and moisture in accelerating degradation. Adhesion testing performed on coupon-level specimens (cell/encapsulant/glass laminates) showed decreases in adhesion energy, Gc , from 5000 h of hot-dry (90 degrees C, ~1% RH) and hot-humid (90 degrees C, 60% RH) aging. POE coupons demonstrated the best stability, followed by EPE then EVA. For EVA and POE, hot-humid aged coupons experienced a larger decrease in Gc due to enhanced hydrolytic degradation. Hot-dry aging condition demonstrated that thermal degradation of the interface could be significant even if the encapsulant experiences negligible degradation in the absence of UV and elevated humidity.
Modulating liquid-to-solid transitions and the resulting crystalline structure for tailored properties is much desired. Colloidal systems are exemplary to this end, but the fundamental knowledge gaps in relating the influence of intermolecular interactions to crystallization behavior continue to hinder progress. In this study, we address this knowledge gap by studying nucleation and growth in systems with modified Lennard-Jones potential. Specifically, we study the commonly used 12-6 potential and a softer 7-6 potential. The thermodynamic state point for the study is chosen such that both systems are investigated at the same level of supercooling and pressure. Under these conditions, we find that the nucleation rate for both systems is comparable. Interestingly, the nucleation pathways and resulting crystal structures are different. In the 12-6 system, nucleation and growth occur predominantly through the FCC structure. Softening the potential alters the critical nucleus composition and introduces two distinct nucleation pathways. One pathway predominantly leads to the nucleus with a body-centered cubic (BCC) structure, while the other favors the face-centered cubic (FCC) arrangement. Our study illustrates that polymorph selection can be achieved through modifications to intermolecular interactions without impacting nucleation kinetics. The results have significant implications in designing approaches for polymorph selection and modulating self-assembly mechanisms.
We present simulations of heat flow relevant to gaspipe experiments on the National Ignition Facility to investigate kinetic effects on transport phenomena. D 2 and neopentane (C 5 H 12 ) filled targets are used to study the laser preheat stage of a MagLIF scheme where an axial magnetic field is sometimes applied to the target. Simulations were done with the radiation-MHD code HYDRA with a collision-dominated fluid model and the SNB nonlocal electron thermal conduction model. Using the SNB model to evolve the electron temperature increased the heat front propagation of neopentane gas targets compared to a local model by limiting radial heat flow. This increases electron temperature near the axis, which decreases laser absorption. We find that the effect of heat flow models on temperature profiles and laser propagation is modest. Beyond the SNB model, we utilize HYDRA to initialize plasma conditions for the Vlasov–Fokker–Planck K2 code. We run K2 until a quasi-steady state is reached and examine the impact of kinetic effects on heat transport. Although axial heat flow is well predicted by fluid models, the fluid model consistently overpredicts radial heat flow up to 150% in regions with the largest temperature gradient of D 2 filled gaspipes. On the other hand, the SNB nonlocal electron conduction model is found to be adequate for capturing kinetic heat flow in gaspipes.
The ARC TM tokamak, a high-field (𝐵 𝑇 = 11.4 T) fusion power plant, under development by Commonwealth Fusion Systems, is studied using a suite of integrated modelling tools to predict its fusion power generation (𝑃𝑓𝑢𝑠), transport and confinement properties. Analysis is based off an ARC operational point scoped first with zero-dimensional (0-D) plasma operational contour (POPCON) modelling to produce 1.13 GW of fusion power. A suite of integrated modelling tools (TRANSP, ASTRA and TORAX) were applied to predict the performance and kinetic profiles of the ARC design point, yielding a range of predicted performance spanning from ∼900 to 1300 MW in rough quantitative agreement with POPCON predictions. The sensitivity of these results to uncertain modelling inputs was probed using scans of pedestal boundary conditions around EPED-predicted values (total pressure and temperature ratios), tungsten concentration and seperatrix density around their nominal assumptions. Pedestal pressure and pedestal top (𝑇 𝑖 /𝑇 𝑒 ) play a large role in 1.5-dimensional performance predictions, able to modify the predicted 𝑃 𝑓𝑢𝑠 by a factor of 2 within reasonable assumptions. High-fidelity core nonlinear gyrokinetic profile predictions, performed using CGYRO (Candy et al. 2016 J. Comput. Phys., vol. 324, pp. 73–93) coupled with the PORTALS (Rodriguez-Fernandez et al. 2024 Nucl. Fusion, vol. 64, 076034; Phys. Plasmas, vol. 31, 2024, 062501) framework, yield substantially lower performance (𝑃 𝑓𝑢𝑠 =677 MW) compared with 0-D and medium-fidelity modelling for nominal assumptions, showing that there is non-negligible uncertainty between models and that future work on SPARC may help resolve discrepancies. Lower overall performance results from significantly reduced volume-averaged densities and temperatures, along with reduced levels of density and temperature peaking. Turbulence and transport are largely dominated by ion temperature gradient across the profile, confirmed by both linear stability and the response of the nonlinear fluxes to changes in gradients, with some impact of kinetic ballooning modes in the deep core. This work represents one of the most complete scoping of potential fusion power plant conditions performed to date. The extensive integrated modelling provides confidence in ARC performance approaching 1 GW, while nonlinear gyrokinetic modelling results in open questions into the physics of density and temperature peaking in fusion-power-plant-relevant operational space. A discussion of results and the role that the SPARC tokamak (Creely et al. 2020 J. Plasma Phys., vol. 86, 865860502) will play in informing ARC design, performance and operation is presented.
Compartmented gas bag landing system with omnidirectional, multiple impact, and kinetic energy dissipation capabilities
Crystallization kinetics and impact tests of glass fiber-epoxy composites