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At least 1,045 records · Page 58

Small experiments for the maturation of orbital cryogenic transfer technologies

The no-vent method is a promising approach to handling the problems of low-g venting during propellant transfer. A receiver tank is first cooled to remove thermal energy from the tank wall and the resultant vapor vented overboard. The nozzles mix the incoming liquid and residual vapor in the tank maintaining a thermodynamic state which allows the tank to fill with liquid without venting. Ground based testing at NASA Lewis Research Center (LeRC) has demonstrated the no-vent fill process and attempted to bound its low-gravity performance. But, low-gravity testing is required to validate the method. As an alternative to using a dedicated spacecraft for validation, several small scale experiments to study no-vent fill in low-g were formulated. Cost goals quickly limited the search to two possibilities: a secondary payload on the space shuttle, or a small scale sounding rocket experiment. The key issues of small scale experimentation are discussed, and a conceptual design of a sounding rocket experiment with liquid hydrogen for studying the fill process is presented.

Chato, David J.↗

Compatibility of potential reinforcing ceramics with Ni and Fe aluminides

There is a great deal of interest in the possible utilization of intermetallic compounds in advanced high temperature gas turbine engines. These compounds exhibit a variety of promising properties, including reasonable strength, high melting points, relatively low densities, and good corrosion resistance. However, in general, they also show limited ductilities and toughness, and less than optimum creep strengths at elevated temperatures. In addition, in applications involving advanced gas turbine engines, it is often necessary for candidate materials to have large elastic moduli. The present study is part of a program whose objective is to identify a high temperature fiber reinforced composite. The approach adopted was to fabricate laboratory samples of the combinations of materials considered by Misra, in order to determine the extent to which the thermodynamic calculations can predict phase stability. As many of the ceramic phases considered are not currently available in fiber form, they were added as particulates to the alloy matrices. The ways in which the materials were produced and evaluated are described.

Clark, William A. T.↗

A non-LTE model for the Jovian methane infrared emissions at high spectral resolution

High resolution spectra of Jupiter in the 3.3 micrometer region have so far failed to reveal either the continuum or the line emissions that can be unambiguously attributed to the nu(sub 3) band of methane (Drossart et al. 1993; Kim et al. 1991). Nu(sub 3) line intensities predicted with the help of two simple non-Local Thermodynamic Equilibrium (LTE) models -- a two-level model and a three-level model, using experimentally determined relaxation coefficients, are shown to be one to three orders of magnitude respectively below the 3-sigma noise level of these observations. Predicted nu(sub 4) emission intensities are consistent with observed values. If the methane mixing ratio below the homopause is assumed as 2 x 10(exp -3), a value of about 300 K is derived as an upper limit to the temperature of the high stratosphere at microbar levels.

Halthore, Rangasayi N.↗

Factors Affecting the Evolution of Hurricane Erin and the Distributions of Hydrometeors: Role of Microphysical Processes

Fine-resolution simulations of Hurricane Erin 2001 are conducted using the Penn State University/National Center for Atmospheric Research mesoscale model version 3.5 to investigate the role of thermodynamic, boundary layer and microphysical processes in Erin's growth and maintenance, and their effects on the horizontal and vertical distributions of hydrometeors. Through comparison against radar, radiometer, and dropsonde data collected during the Convection and Moisture Experiment 4, it is seen that realistic simulations of Erin are obtained provided that fine resolution simulations with detailed representations of physical processes are conducted. The principle findings of the study are as follows: 1) a new iterative condensation scheme, which limits the unphysical increase of equivalent potential temperature associated with most condensation schemes, increases the horizontal size of the hurricane, decreases its maximum rainfall rate, reduces its intensity, and makes its eye more moist; 2) in general, microphysical parameterization schemes with more categories of hydrometeors produce more intense hurricanes, larger hydrometeor mixing ratios, and more intense updrafts and downdrafts; 3) the choice of coefficients describing hydrometeor fall velocities has as big of an impact on the hurricane simulations as does choice of microphysical parameterization scheme with no clear relationship between fall velocity and hurricane intensity; and 4) in order for a tropical cyclone to adequately intensify, an advanced boundary layer scheme (e.g., Burk-Thompson scheme) must be used to represent boundary layer processes. The impacts of varying simulations on the horizontal and vertical distributions of different categories of hydrometeor species, on equivalent potential temperature, and on storm updrafts and downdrafts are examined to determine how the release of latent heat feedbacks upon the structure of Erin. In general, all simulations tend to overpredict precipitation rate and hydrometeor mixing ratios. The ramifications of these findings for quantitative precipitation forecasts (QPFs) of tropical cyclones are discussed.

McFarquhar, Greg M.↗

Thermoradiative Conversion for Space Power Systems

The thermoradiative cell is a new method for converting heat energy to electrical power, first detailed by Strandberg in 2015. The cell is structurally similar to a photovoltaic cell, in that it is a p-n junction semiconductor device, but thermodynamically operates in the reverse direction, converting the thermal dark current into electrical power by utilizing the recombination radiation from thermally-generated electron hole pairs to radiate waste heat to space. This technology may have application for space missions in converting thermal energy produced by a radioisotope source or from a nuclear reactor into power. The power and efficiency can be calculated as a function of bandgap in the detailed-balance case (the Shockley-Queisser limit), in which all of the thermal emissivity of the cell is due to the recombination of thermally generated electron-hole pairs, and all other recombination losses are ignored. The current produced is directly proportional to the recombination radiation, and thus the more thermally generated pairs, the higher the current. The voltage is proportional to the external bias. These two constraints allow optimization of the optimum bias point for maximum power, and allow calculation of the efficiency at maximum power point. Unlike photovoltaic cells, the maximum power operating point is not the same as the maximum efficiency point, and higher efficiency can be achieved at a higher (negative) bias in the ideal case. Incorporating non-ideal losses, however, shifts the maximum efficiency point toward lower bias. Since a thermoradiative cell operates by radiating directly to space, the current produced by a themoradiative cells will increase with the Stefan-Boltzman radiative efficiency; roughly the fourth power of the temperature. Thus, in contrast to a photovoltaic converter, the power produced is highest at high operating temperatures. Likewise, in contrast to conventional thermal conversion, high radiator temperature increases, rather than decreases the efficiency. Thus, the thermoradiative conversion may fill a mission niche in which small radiator size is required. The basic operation will be summarized, applications to space power discussed, and the requirements for further research outlined.

Photovoltaic Cell↗

Finite-temperature many-body perturbation theory for anharmonic vibrations: Recursions, algebraic reduction, second-quantized reduction, diagrammatic rules, linked-diagram theorem, finite-temperature self-consistent field, and general-order algorithm

A unified theory is presented for finite-temperature many-body perturbation expansions of the anharmonic vibrational contributions to thermodynamic functions, i.e., the free energy, internal energy, and entropy. The theory is diagrammatically size-consistent at any order, as ensured by the linked-diagram theorem proved in this study, and, thus, applicable to molecular gases and solids on an equal footing. It is also a basis-set-free formalism, just like its underlying Bose–Einstein theory, capable of summing anharmonic effects over an infinite number of states analytically. It is formulated by the Rayleigh–Schrödinger-style recursions, generating sum-over-states formulas for the perturbation series, which unambiguously converges at the finite-temperature vibrational full-configuration-interaction limits. Two strategies are introduced to reduce these sum-over-states formulas into compact sum-over-modes analytical formulas. One is a purely algebraic method that factorizes each many-mode thermal average into a product of one-mode thermal averages, which are then evaluated by the thermal Born–Huang rules. Canonical forms of these rules are proposed, dramatically expediting the reduction process. The other is finite-temperature normal-ordered second quantization, which is fully developed in this study, including a proof of thermal Wick’s theorem and the derivation of a normal-ordered vibrational Hamiltonian at finite temperature. The latter naturally defines a finite-temperature extension of size-extensive vibrational self-consistent field theory. These reduced formulas can be represented graphically as Feynman diagrams with resolvent lines, which include anomalous and renormalization diagrams. Two order-by-order and one general-order algorithms of computing these perturbation corrections are implemented and applied up to the eighth order. The results show no signs of Kohn–Luttinger-type nonconvergence.

74 ATOMIC AND MOLECULAR PHYSICS↗

Mechanistic Study of the Li–Air Battery with a Co 3 O 4 Cathode and Dimethyl Sulfoxide Electrolyte

The lithium–air battery, a powerful competitor to replace the traditional lithium-ion battery, has attracted increasing attention due to its extremely high theoretical energy density. However, its development is limited by the cathode and electrolyte properties, which should include high stability, conductivity, and electrocatalytic properties in oxygen-rich environments. Here, we employ a systematic first-principles study of Li–O 2 discharge and charge reactions on the Co 3 O 4 -based cathode with the assistance of dimethyl sulfoxide (DMSO) electrolyte. The structure, stability, and electronic properties of different surface reconstructions of the Co 3 O 4 (100) facet are investigated. In addition, the mechanisms and thermodynamic overpotentials of multi-step reactions between Li + /e – and O 2 are provided, where lithium suboxide products (Li 2 O 2 or Li 3 O 2 ) are formed on the different Co 3 O 4 (100) terminations. The solvation shell of Li + components in explicit DMSO solvent is investigated through ab initio molecular dynamics simulations. In general, we find that the Co 3 O 4 (100)-O (oxidized) surface is the most stable one under standard conditions, and the stable Li + solvation structure is found in a tetrahedral Li(DMSO) 4 + shell in the DMSO-based electrolyte. Moreover, in the system of the Co 3 O 4 (100)-O cathode and DMSO electrolyte, the solution model pathway is energetically favorable for the Li–O 2 discharge reaction. It provides a low constant overpotential of 0.17 V during a long-term discharging process, thus causing the final toroid Li 2 O 2 formation on the cathode. During the charging process, an overpotential of 0.36 V is required to rapidly decompose Li 2 O 2 .

25 ENERGY STORAGE↗

Quasi‐Steady State Supersaturation: Do High Values Derived From ESCAPE Represent Real High Supersaturations and the Potential for Condensational Invigoration?

Deep convective clouds were intensively sampled during the Experiment of Sea Breeze Convection, Aerosols, Precipitation, and Environment (ESCAPE) with coordinated flights of the NRC Convair-580 and SPEC Learjet. A total of 219 updraft core segments were sampled over coastal Texas and Louisiana under diverse meteorological conditions. Median updraft properties included widths of ∼1 km, velocities of 4.8 m s −1 , droplet number concentrations of ∼400 cm −3 , and liquid water contents of 0.9 g m −3 . The limitations of using the quasi-steady state approximation to derive supersaturations were explored. Supersaturation (S QSS ) estimated from in situ observations under a quasi-steady state assumption averaged 0.4% but occasionally exceeded 2%, with values >1% (high supersaturations) identified as statistical outliers. Two case studies illustrated the conditions linked to high supersaturations. In a storm over the Gulf, median core S QSS reached 2.46% in the developing stage compared to 2.17% in the mature stage under similar thermodynamic conditions. In a storm over coastal Louisiana, S QSS peaked near 11% within a 13.7-m s −1 updraft, accompanied by predominantly supercooled liquid droplets at −13°C and exceptionally low diameter concentrations of 0.29 mm cm −3 . Bootstrap analysis of all sampled cores showed that high supersaturations are most probable in cold and mixed-phase regimes with moderate to strong updrafts and are strongly influenced by vertical velocity and droplet number concentrations. In conclusion, while extreme supersaturations (∼10%) were rare, their occurrence underscores the need for targeted multiplatform observations to resolve their spatiotemporal variability and assess their potential role in deep convective invigoration.

54 ENVIRONMENTAL SCIENCES↗

Quantization effects in semiconductor nanostructures and singlet fission in molecular chromophores for photovoltaics and solar fuels

Hot carriers in semiconductors are electrons and/or holes that have energies greater than carriers that reside at the top and bottom of the conduction and valence bands, respectively; the latter carriers are in equilibrium with the lattice and have a temperature equal to the lattice (ambient) temperature. Hot carriers are created in semiconductors upon the absorption of photons with energies greater than the bandgap. The excess energy above the bandgap energy is in the form of kinetic energy. The hot carriers can cool to the lattice temperature via electron–phonon scattering and establish separate Boltzmann distributions for electrons and holes at the band edges. Thus, upon cooling, the excess kinetic energy of the hot carriers is transformed into heat and is unavailable to be converted into electrical or chemical free energy in a solar photon-converting cell. This hot-carrier cooling process significantly limits the maximum possible power conversion efficiency (PCE) of the free energy of solar photons into electrical free energy or chemical free energy in chemical bonds of fuels. However, if hot-carrier cooling can be slowed such that the hot carriers can be extracted before cooling to create higher photovoltages, or utilized to create additional electron-hole pairs through carrier multiplication, then beneficial use can be made of the excess energy of hot carriers and the maximum thermodynamic PCE can be dramatically increased. Quantization effects in semiconductor nanostructures, unique properties of some bulk semiconductors, and exciton multiplication in both semiconductors and molecular chromophores that undergo singlet fission have shown a path forward for potential dramatic increases in the PCEs of solar photons into electricity and solar fuels. The status, history, and future promise of the science and technology of these future approaches for different types of photovoltaic cells and cells for solar fuels will be discussed.

14 SOLAR ENERGY↗

Toward first principles-based simulations of dense hydrogen

Accurate knowledge of the properties of hydrogen at high compression is crucial for astrophysics (e.g., planetary and stellar interiors, brown dwarfs, atmosphere of compact stars) and laboratory experiments, including inertial confinement fusion. There exists experimental data for the equation of state, conductivity, and Thomson scattering spectra. However, the analysis of the measurements at extreme pressures and temperatures typically involves additional model assumptions, which makes it difficult to assess the accuracy of the experimental data rigorously. On the other hand, theory and modeling have produced extensive collections of data. They originate from a very large variety of models and simulations including path integral Monte Carlo (PIMC) simulations, density functional theory (DFT), chemical models, machine-learned models, and combinations thereof. At the same time, each of these methods has fundamental limitations (fermion sign problem in PIMC, approximate exchange–correlation functionals of DFT, inconsistent interaction energy contributions in chemical models, etc.), so for some parameter ranges accurate predictions are difficult. Recently, a number of breakthroughs in first principles PIMC as well as in DFT simulations were achieved which are discussed in this review. Here we use these results to benchmark different simulation methods. We present an update of the hydrogen phase diagram at high pressures, the expected phase transitions, and thermodynamic properties including the equation of state and momentum distribution. Furthermore, we discuss available dynamic results for warm dense hydrogen, including the conductivity, dynamic structure factor, plasmon dispersion, imaginary-time structure, and density response functions. We conclude by outlining strategies to combine different simulations to achieve accurate theoretical predictions that are based on first principles.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Electrochemical Separation of Ag 2 S and Cu 2 S from Molten Sulfide Electrolyte

The production of precious metals from Cu-rich sources such as ore products or secondary sources is slow and complex largely due to limited solubility in aqueous electrolytes. This results in sequential processing with various electrolytes and chemistries, where first Cu is electrorefined, followed by Ag, followed by Au and the platinum group metals. These are separate processes, often conducted in separate electrorefining and electrowinning facilities. The chemical properties of molten sulfides, and their ability to operate at a temperature where liquid metal cathodes are used, suggest the possibility of an alternative, streamlined processing route for Cu and precious metals. Unfortunately, little thermodynamic or electrochemical information is available regarding the behavior of Cu and precious metal sulfides in molten sulfide electrolytes. Herein, the relative activity of the Cu 2 S-Ag 2 S pseudobinary dissolved in a BaS-La 2 S 3 supporting electrolyte is measured at 1523 K. It was found that the supporting electrolyte favors mixing with Ag 2 S over Cu 2 S. Molten sulfide electrolysis of Cu and Ag was conducted, with results in good agreement with the thermodynamic model. It is found that the Ag-Cu cathode chemistry will influence the electrochemical selectivity in the Ag-Cu-Ba-La-S system.

25 ENERGY STORAGE↗

Limit on rotational energy available to excite Jovian aurora

There is a fundamental relationship between the power that is extracted from Jupiter's rotation to drive magnetospheric processes and the rate at which mass is injected into the Io plasma torus. Half of this power is consumed by bulk motion of the plasma and the other half represents an upper limit on the energy from rotation available for dissipation and in particular to excite the Jovian aurora. Since the rotation of the planet is the only plausible source of energy, the power inferred from the observed auroral intensities requires a plasma injection rate of 2.6 x 10 to the 29th AMU/sec or greater. This in turn leads to a residence time of a torus particle of 48 days or less. These results raise doubts about the applicability of equilibrium thermodynamics to the determination of plasma parameters in the Io torus.

Eviatar, A.↗

Minimizing Launch Mass for ISRU Processes

The University of Dayton and the Jet Propulsion Laboratory are developing a methodology for estimating the Earth launch mass (ELM) of processes for In-Situ Resource Utilization (ISRU) with a focus on lunar resource recovery. ISRU may be enabling for both an extended presence on the Moon, and for large sample return missions and for a human presence on Mars. To accomplish these exploration goals, the resources recovered by ISRU must offset the ELM for the recovery process. An appropriate figure of merit is the cost of the exploration mission, which is closely related to ELM. For a given production rate and resource concentration, the lowest ELM - and the best ISRU process - is achieved by minimizing capital equipment for both the ISRU process and energy production. ISRU processes incur Carnot limitations and second law losses (irreversibilities) that ultimately determine production rate, material utilization and energy efficiencies. Heat transfer, chemical reaction, and mechanical operations affect the ELM in ways that are best understood by examining the process's detailed energetics. Schemes for chemical and thermal processing that do not incorporate an understanding of second law losses will be incompletely understood. Our team is developing a methodology that will aid design and selection of ISRU processes by identifying the impact of thermodynamic losses on ELM. The methodology includes mechanical, thermal and chemical operations, and, when completed, will provide a procedure and rationale for optimizing their design and minimizing their cost. The technique for optimizing ISRU with respect to ELM draws from work of England and Funk that relates the cost of endothermic processes to their second law efficiencies. Our team joins their approach for recovering resources by chemical processing with analysis of thermal and mechanical operations in space. Commercial firms provide cost inputs for ELM and planetary landing. Additional information is included in the original extended abstract.

England, C.↗

Circumventing thermodynamics to synthesize highly metastable perovskites: nano eggshells of SnHfO 3

Sn(II)-based perovskite oxides, being the subject of longstanding theoretical interest for the past two decades, have been synthesized for the first time in the form of nano eggshell particle morphologies. All past reported synthetic attempts have been unsuccessful owing to their metastable nature, i.e., by their thermodynamic instability towards decomposition to their constituent oxides. A new approach was discovered that finally provides an effective solution to surmounting this intractable synthetic barrier and which can be the key to unlocking the door to many other predicted metastable oxides. A low-melting KSn 2 Cl 5 salt was utilized to achieve a soft topotactic exchange of Sn(II) cations into a Ba-containing perovskite, i.e., BaHfO 3 with particle sizes of ~350 nm, at a low reaction temperature of 200 °C. The resulting particles exhibit nanoshell-over-nanoshell morphologies, i.e., with SnHfO 3 forming as ~20 nm thick shells over the surfaces of the BaHfO 3 eggshell particles. Formation of the metastable SnHfO 3 is found to be thermodynamically driven by the co-production of the highly stable BaCl 2 and KCl side products. Despite this, total energy calculations show that Sn(II) distorts from the A-site asymmetrically and randomly and the interdiffusion has a negligible impact on the energy of the system (i.e., layered vs. solid solution). Additionally, nano eggshell particle morphologies of BaHfO 3 were found to yield highly pure SnHfO 3 for the first time, thus circumventing the intrinsic ion-diffusion limits occurring at this low reaction temperature. In summary, these results demonstrate that the metastability of many theoretically predicted Sn(II)-perovskites can be overcome by leveraging the high cohesive energies of the reactants, the exothermic formation of a stable salt side product, and a shortened diffusion pathway for the Sn(II) cations.

36 MATERIALS SCIENCE↗

Applications of plasma core reactors to terrestrial energy systems

Plasma core reactors offer several new options for future energy needs in addition to space power and propulsion applications. Power extraction from plasma core reactors with gaseous nuclear fuel allows operation at temperatures higher than conventional reactors. Highly efficient thermodynamic cycles and applications employing direct coupling of radiant energy are possible. Conceptual configurations of plasma core reactors for terrestrial applications are described. Closed-cycle gas turbines, MHD systems, photo- and thermo-chemical hydrogen production processes, and laser systems using plasma core reactors as prime energy sources are considered. Cycle efficiencies in the range of 50 to 65 percent are calculated for closed-cycle gas turbine and MHD electrical generators. Reactor advantages include continuous fuel reprocessing which limits inventory of radioactive by-products and thorium-U-233 breeder configurations with about 5-year doubling times.-

Latham, T. S.↗

Small experiments for the maturation of orbital cryogenic transfer technologies

The no-vent fill method is a promising approach to handle the problems of low-g venting during propellant transfer. A receiver tank is first cooled to remove thermal energy from the tank wall and the resultant vapor vented overboard. Then nozzles mix the incoming liquid and residual vapor in the tank maintaining a thermodynamic state which allows the tank to fill with liquid without venting. Ground based testing at NASA Lewis Research Center (LeRC) has demonstrated the no-vent fill process and attempted to bound its low-gravity performance. But, low-gravity testing is required to validate the method. As an alternative to using a dedicated spacecraft for validation the authors have formulated several small scale experiments to study no-vent fill in low-g. Cost goals quickly limited the search to two possibilities: a secondary payload on the Space Shuttle, or a small scale sounding rocket experiment. This paper will discuss the key issues of small scale experimentation and present a conceptual design of a sounding rocket experiment with liquid hydrogen for studying the fill process.

Chato, David J.↗

An approximate theoretical method for modeling the static thrust performance of non-axisymmetric two-dimensional convergent-divergent nozzles

An analytical/numerical method has been developed to predict the static thrust performance of non-axisymmetric, two-dimensional convergent-divergent exhaust nozzles. Thermodynamic nozzle performance effects due to over- and underexpansion are modeled using one-dimensional compressible flow theory. Boundary layer development and skin friction losses are calculated using an approximate integral momentum method based on the classic karman-Polhausen solution. Angularity effects are included with these two models in a computational Nozzle Performance Analysis Code, NPAC. In four different case studies, results from NPAC are compared to experimental data obtained from subscale nozzle testing to demonstrate the capabilities and limitations of the NPAC method. In several cases, the NPAC prediction matched experimental gross thrust efficiency data to within 0.1 percent at a design NPR, and to within 0.5 percent at off-design conditions.

Hunter, Craig A.↗

Probabilistic Multi-Scale, Multi-Level, Multi-Disciplinary Analysis and Optimization of Engine Structures

Aircraft engines are assemblies of dynamically interacting components. Engine updates to keep present aircraft flying safely and engines for new aircraft are progressively required to operate in more demanding technological and environmental requirements. Designs to effectively meet those requirements are necessarily collections of multi-scale, multi-level, multi-disciplinary analysis and optimization methods and probabilistic methods are necessary to quantify respective uncertainties. These types of methods are the only ones that can formally evaluate advanced composite designs which satisfy those progressively demanding requirements while assuring minimum cost, maximum reliability and maximum durability. Recent research activities at NASA Glenn Research Center have focused on developing multi-scale, multi-level, multidisciplinary analysis and optimization methods. Multi-scale refers to formal methods which describe complex material behavior metal or composite; multi-level refers to integration of participating disciplines to describe a structural response at the scale of interest; multidisciplinary refers to open-ended for various existing and yet to be developed discipline constructs required to formally predict/describe a structural response in engine operating environments. For example, these include but are not limited to: multi-factor models for material behavior, multi-scale composite mechanics, general purpose structural analysis, progressive structural fracture for evaluating durability and integrity, noise and acoustic fatigue, emission requirements, hot fluid mechanics, heat-transfer and probabilistic simulations. Many of these, as well as others, are encompassed in an integrated computer code identified as Engine Structures Technology Benefits Estimator (EST/BEST) or Multi-faceted/Engine Structures Optimization (MP/ESTOP). The discipline modules integrated in MP/ESTOP include: engine cycle (thermodynamics), engine weights, internal fluid mechanics, cost, mission and coupled structural/thermal, various composite property simulators and probabilistic methods to evaluate uncertainty effects (scatter ranges) in all the design parameters. The objective of the proposed paper is to briefly describe a multi-faceted design analysis and optimization capability for coupled multi-discipline engine structures optimization. Results are presented for engine and aircraft type metrics to illustrate the versatility of that capability. Results are also presented for reliability, noise and fatigue to illustrate its inclusiveness. For example, replacing metal rotors with composites reduces the engine weight by 20 percent, 15 percent noise reduction, and an order of magnitude improvement in reliability. Composite designs exist to increase fatigue life by at least two orders of magnitude compared to state-of-the-art metals.

Chamis, Christos C.↗