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At least 55 records · Page 3

Giant elastocaloric effect at low temperatures in TmVO 4 and implications for cryogenic cooling

Adiabatic decompression of paraquadrupolar materials has significant potential as a cryogenic cooling technology. We focus on TmVO 4 , an archetypal material that undergoes a continuous phase transition to a ferroquadrupole-ordered state at 2.15 K. Above the phase transition, each Tm ion contributes an entropy of k B ln 2 due to the degeneracy of the crystal electric field groundstate. Owing to the large magnetoelastic coupling, which is a prerequisite for a material to undergo a phase transition via the cooperative Jahn–Teller effect, this level splitting, and hence the entropy, can be readily tuned by externally induced strain. Using a dynamic technique in which the strain is rapidly oscillated, we measure the adiabatic elastocaloric response of single-crystal TmVO 4 , and thus experimentally obtain the entropy landscape as a function of strain and temperature. The measurement confirms the suitability of this class of materials for cryogenic cooling applications and provides insight into the dynamic quadrupole strain susceptibility.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Incoherent nonadiabatic to coherent adiabatic transition of electron transfer in colloidal quantum dot molecules

Electron transfer is a fundamental process in chemistry, biology, and physics. One of the most intriguing questions concerns the realization of the transitions between nonadiabatic and adiabatic regimes of electron transfer. Using colloidal quantum dot molecules, we computationally demonstrate how the hybridization energy (electronic coupling) can be tuned by changing the neck dimensions and/or the quantum dot sizes. This provides a handle to tune the electron transfer from the incoherent nonadiabatic regime to the coherent adiabatic regime in a single system. We develop an atomistic model to account for several states and couplings to the lattice vibrations and utilize the mean-field mixed quantum-classical method to describe the charge transfer dynamics. Here, we show that charge transfer rates increase by several orders of magnitude as the system is driven to the coherent, adiabatic limit, even at elevated temperatures, and delineate the inter-dot and torsional acoustic modes that couple most strongly to the charge transfer dynamics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Elastocaloric signatures of symmetric and antisymmetric strain-tuning of quadrupolar and magnetic phases in DyB 2 C 2

The adiabatic elastocaloric effect measures the temperature change of a given system with strain and provides a thermodynamic probe of the entropic landscape in the temperature-strain space. Here, we demonstrate that the DC bias strain-dependence of AC elastocaloric effect allows decomposition of the latter into symmetric (rotation-symmetry-preserving) and antisymmetric (rotation-symmetry-breaking) strain channels, using a tetragonal f -electron intermetallic DyB 2 C 2 —whose antiferroquadrupolar order breaks local fourfold rotational symmetries while globally remaining tetragonal—as a showcase example. We capture the strain evolution of its quadrupolar and magnetic phase transitions using both singularities in the elastocaloric coefficient and its jumps at the transitions, and the latter we show follows a modified Ehrenfest relation. We find that antisymmetric strain couples to the underlying order parameter in a biquadratic (linear-quadratic) manner in the antiferroquadrupolar (canted antiferromagnetic) phase, which are attributed to a preserved (broken) global tetragonal symmetry, respectively. The broken tetragonal symmetry in the magnetic phase is further evidenced by elastocaloric strain-hysteresis and optical birefringence. Additionally, within the staggered quadrupolar order, the observed elastocaloric response reflects a quadratic increase of entropy with antisymmetric strain, analogous to the role magnetic field plays for Ising antiferromagnetic orders by promoting pseudospin flips. Our results demonstrate AC elastocaloric effect as a compact and incisive thermodynamic probe into the coupling between electronic degrees of freedom and strain in free energy, which holds the potential for investigating and understanding the symmetry of a wide variety of ordered phases in broader classes of quantum materials.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Modeling of Reactor Design and Optimization for Scale-Up of the Catalyxx Process for Ethanol Conversion to Higher Alcohol Biofuels

This report summarizes the results of a collaborative efforts between Oak Ridge National Laboratory (ORNL) and Catalyxx Inc. to investigate scale-up of Catalyxx’s Ethanol upgrading to higher alcohols process. The study was funded by the U.S. Department of Energy (DOE) Bioenergy Technologies Office (BETO) under CRADA (Cooperative Research and Development Agreement) No: NFE-20-08396. The project is part of the Direct Funding Opportunity (DFO) for Computational Science to Enable Bioenergy program which utilized computational toolsets developed by the Consortium for Computational Physics and Chemistry, a multi-laboratory consortium in BETO. The report here summarizes a packed-bed reactor modeling effort spanning the range from lab to industrial scale (from 4 gram to 5-ton catalyst beds), and examining reactor design, process optimization strategies, and suggested design and operating conditions for Catalyxx’s ethanol upgrading plants. The results in this report have been shared in monthly steering meetings and presentations are available in the shared data house owned by Catalyxx. The modeling effort helped to define optimum operation conditions for maximum alcohol selectivity and yield: i.e., temperature control scenarios ranging from adiabatic to isothermal, feed rate, pressure, and inlet H 2 /Ethanol ratio. The modeling results were verified at lab-(4 gram) and pre-pilot (4 kg) scales and has been used to evaluate a 5-ton packed-bed reactor and identify operating conditions to maximize the butanol yield. Special focus was given to understanding mass-transfer effects in the pre-pilot and pilot-scale reactors, over the domain of flow rate, pressure, feed composition, pellet size, shape, porosity, bed voidage, and reactor dimensions (i.e., length/diameter). Modeling was also used to evaluate innovative reactor design concepts such as water removal to improve alcohol selectivity and yield, and a reactor with an additional side inlet to facilitate quenching. These concepts were thoroughly explored, and potential benefits were disclosed. The results in this report are summarized and described qualitatively to protect the IP rights of Catalyxx. The details have been shared with the Catalyxx team in the regular steering meetings. At the end of the project, Catalyxx Inc. announced a successful demonstration of pilot scale operation in Seville, Spain.

02 PETROLEUM↗

Exchange–correlation entropy from the generalized thermal adiabatic connection

Warm dense matter is a highly energetic phase characterized by strong correlations, thermal effects, and quantum mechanical electrons. Thermal density functional theory is commonly used in simulations of this challenging phase, driving the development of temperature-dependent approximations to the exchange–correlation free energy. Approaches using the adiabatic connection formula are well known at zero temperature and have been recently leveraged at non-zero temperatures as well. In this work, a generalized thermal adiabatic connection (GTAC) formula is proposed, introducing a fictitious temperature parameter. This allows extraction of the exchange–correlation entropy S XC using simulated interaction strength scaling. Here, this procedure uses a Hellmann–Feynman approach to express the exchange–correlation entropy in terms of a temperature- and interaction strength-dependent exchange–correlation potential energy. In addition, analysis of S XC as a function of interaction strength suggests new forms for approximations, and GTAC itself offers a new framework for exploring both the exact and approximate interplay of temperature, density, and interaction strength across a wide range of conditions.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

How does negative triangularity mitigate ITG turbulence and transport?

Improved confinement in negative triangularity (NT) experiments is attributed to reduced fluxes driven by micro-turbulence. The physical mechanism of why thermal confinement improves in NT relative to PT is unknown. This study employs gyrokinetic flux tube simulations using the GENE code with local Miller equilibrium to elucidate the physical mechanisms behind the beneficial effects of NT flux surface shapes. The focus is on collisionless ion temperature gradient (ITG) driven turbulence with adiabatic electrons. The kinetic profiles are held fixed across a scan of triangularity values, thus enabling comparisons on a level playing field. The reduced linear growth rates for NT is shown to be due to a reduced eigenmode averaged magnetic drift frequency and a wider, stronger negative local magnetic shear region about the outboard mid-plane. The nonlinear heat flux is lower for NT than that for PT, due to reduced radial correlation length and increased correlation time (τ c ) of fluctuations. These, in turn, are due to a comparatively higher level of self-generated zero-frequency E × B zonal shearing rate ω E in NT as compared to PT. Though the linear zonal potential residual is lower for NT, the nonlinearly generated E × B zonal shearing rate is higher for NT than for PT. This outcome is linked to the distinctive features of the radial wavenumber spectra of the zonal potential and the zonal shearing rate. The dimensionless parameter ω E τ c is suggested as a figure of merit. This is higher for NT than for PT. Thus, the reduced heat diffusivity for NT is linked to increased ω E τ c . Self-generated temperature corrugations (i.e. zonal temperature gradients) are much weaker than the background mean temperature gradient. Nevertheless, temperature corrugations are more pronounced in NT than in PT.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Temperature-dependent elastic constants of thorium dioxide probed using time-domain Brillouin scattering

Herein we report the adiabatic elastic constants of single-crystal thorium dioxide over a temperature range of 77–350 K. Time-domain Brillouin scattering, an all-optical, non-contact picosecond ultrasonic technique, is used to generate and detect coherent acoustic phonons that propagate in the bulk perpendicular to the surface of the crystal. These coherent acoustic lattice vibrations have been monitored in two hydrothermally grown single-crystal thorium dioxide samples along the (100) and (311) crystallographic directions. The three independent elastic constants of the cubic crystal (C 11 , C 12 , and C 44 ) are determined from the measured bulk acoustic velocities. The longitudinal wave along the (100) orientation provided a direct measurement of C 11 . Measurement of C 44 and C 12 was achieved by enhancing the intensity of quasi-shear mode in a (311) oriented crystal by adjusting the polarization angle relative to the crystal axes. We find the magnitude of softening of the three elastic constants to be ~2.5% over the measured temperature range. Good agreement is found between the measured elastic constants with previously reported values at room temperature, and between the measured temperature-dependent bulk modulus with calculated values. We find that semi-empirical models capturing lattice anharmonicity adequately reproduce the observed trend. We also determine the acoustic Grüneisen anharmonicity parameter from the experimentally derived temperature-dependent bulk modulus and previously reported temperature-dependent values of volumetric thermal expansion coefficient and heat capacity. This work presents measurements of the temperature-dependent elasticity in single-crystal thorium dioxide at cryogenic temperature and provides a basis for testing ab initio theoretical models and evaluating the impact of anharmonicity on thermophysical properties.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Continuous symmetry breaking in a two-dimensional Rydberg array

Spontaneous symmetry breaking underlies much of our classification of phases of matter and their associated transitions. The nature of the underlying symmetry being broken determines many of the qualitative properties of the phase; this is illustrated by the case of discrete versus continuous symmetry breaking. Indeed, in contrast to the discrete case, the breaking of a continuous symmetry leads to the emergence of gapless Goldstone modes controlling, for instance, the thermodynamic stability of the ordered phase. Here, we realize a two-dimensional dipolar XY model that shows a continuous spin-rotational symmetry using a programmable Rydberg quantum simulator. We demonstrate the adiabatic preparation of correlated low-temperature states of both the XY ferromagnet and the XY antiferromagnet. In the ferromagnetic case, we characterize the presence of a long-range XY order, a feature prohibited in the absence of long-range dipolar interaction. In conclusion, our exploration of the many-body physics of XY interactions complements recent works using the Rydberg-blockade mechanism to realize Ising-type interactions showing discrete spin rotation symmetry.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Disentangling the effects of non-adiabatic interactions upon ion self-diffusion within warm dense hydrogen

Warm dense matter is a material state in the region of parameter space connecting condensed matter to classical plasma physics. In this intermediate regime, we investigate the significance of non-adiabatic electron-ion interactions upon ion dynamics. To disentangle non-adiabatic from adiabatic electron-ion interactions, we compare the ion self-diffusion coefficient from the non-adiabatic electron force field computational model with an adiabatic, classical molecular dynamics simulation. A classical pair potential developed through a force-matching algorithm ensures the only difference between the models is due to the electronic inertia. Here, we implement this new method to characterize non-adiabatic effects on the self-diffusion of warm dense hydrogen over a wide range of temperatures and densities. Ultimately we show that the impact of non-adiabatic effects is negligible for equilibrium ion dynamics in warm dense hydrogen.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Measurements of the thermal and ionization state of the intergalactic medium during the cosmic afternoon

We perform the first measurement of the thermal and ionization state of the intergalactic medium (IGM) across 0.9 < z < 1.5 using 301 Ly α absorption lines fitted from 12 archival Hubble Space Telescope Space Telescope Imaging Spectrograph quasar spectra. We employ the machine-learning-based inference method that uses joint Doppler parameter–column density (⁠b-N HI ⁠) distributions obtained from Ly α forest decomposition. Our results show that the Γ HI photoionization rates, ⁠, agree with recent ultraviolet background synthesis models, with log(Γ HI /s -1 ) = $-11.79^{+0.18}_{-0.15}$, $-11.98^{+0.09}_{-0.09}$⁠, and $-12.32^{+0.10}_{-0.12}$⁠, at z = 1.4, 1.2, and 1, respectively. We obtain the IGM temperature at the mean density, T 0 ⁠, and the adiabatic index, γ⁠, as [log(T 0 /K), γ] = $[4.13^{+0.12}_{-0.10}, 1.34^{+0.10}_{-0.15}]$, $[3.79^{+0.11}_{-0.11}, 1.70^{+0.09}_{-0.09}]$, and $[4.12^{+0.15}_{-0.25}, 1.34^{+0.21}_{-0.26}]$ at z = 1.4⁠, 1.2, and 1. Our measurements of T 0 at z = 1.4 and 1.2 are consistent with the trend predicted from previous z < 3 temperature measurements and theoretical expectations, where the IGM cools down after $He\tiny{II}$ reionization in the absence of any non-standard heating. However, our T 0 measurement at z = 1 unexpectedly high IGM temperature. Given the relatively large uncertainty in these measurements, where σ T$_0$ ~ 5000 K, mostly emanating from the limited size of our data set, we cannot conclude whether the IGM cools down as expected. Lastly, we generate mock data sets to test the constraining power of future measurement with larger data sets. The results demonstrate that, with redshift path-length Δz ~ 2 for each redshift bin, three times the current data set, we can constrain the T 0 of IGM within 1500 K, which would be sufficient to constrain the IGM thermal history at z < 1.5 conclusively.

79 ASTRONOMY AND ASTROPHYSICS↗

A Predictive Transient Model of the TREAT-SIRIUS Experiments

To support experiments modeling and transient analysis of the NASA-sponsored SIRIUS experiments in the Transient Reactor Test Facility (TREAT), an innovative predictive transient model has been developed to simulate various transient experiments. The developed model is based on a new approach that utilizes steady-state Monte Carlo calculations along with a surrogate model based on polynomial regression to determine the core reactivity. The reactivity is supplied to an exact point kinetics model that determines the reactor power, and it is coupled to an adiabatic feedback model to determine the fuel average temperature. In this work, the newly developed model is introduced along with validation test results considering SIRIUS-1 experiments at different power levels. The initial test results show a very good agreement with experimental data at different power levels, which indicates that the model can be used to predict the power of other transient tests.

42 ENGINEERING↗

Lagrangian and Eulerian Supersaturation Statistics in Turbulent Cloudy Rayleigh–Bénard Convection: Applications for LES Subgrid Modeling

Abstract Turbulent fluctuations of scalar and velocity fields are critical for cloud microphysical processes, e.g., droplet activation and size distribution evolution, and can therefore influence cloud radiative forcing and precipitation formation. Lagrangian and Eulerian water vapor, temperature, and supersaturation statistics are investigated in direct numerical simulations (DNS) of turbulent Rayleigh–Bénard convection in the Pi Convection Cloud Chamber to provide a foundation for parameterizing subgrid-scale fluctuations in atmospheric models. A subgrid model for water vapor and temperature variances and covariance and supersaturation variance is proposed, valid for both clear and cloudy conditions. Evaluation of phase change contributions through an a priori test using DNS data shows good performance of the model. Supersaturation is a nonlinear function of temperature and water vapor, and relative external fluxes of water vapor and heat (e.g., during entrainment-mixing and phase change) influence turbulent supersaturation fluctuations. Although supersaturation has autocorrelation and structure functions similar to the independent scalars (temperature and water vapor), the autocorrelation time scale of supersaturation differs. Relative scalar fluxes in DNS without cloud make supersaturation PDFs less skewed than the adiabatic case, where they are highly negatively skewed. However, droplet condensation changes the PDF shape response: it becomes positively skewed for the adiabatic case and negatively skewed when the sidewall relative fluxes are large. Condensation also increases correlations between water vapor and temperature in the presence of relative scalar fluxes but decreases correlations for the adiabatic case. These changes in correlation suppress supersaturation variability for the nonadiabatic cases and increase it for the adiabatic case. Implications of this work for subgrid microphysics modeling using a Lagrangian stochastic scheme are also discussed.

54 ENVIRONMENTAL SCIENCES↗

Seasonally and Regionally Dependent Shifts of the Atmospheric Westerly Jets under Global Warming

A distinct feature of the atmospheric circulation response to increasing greenhouse gas forcing is the poleward shift of the zonal-mean westerly jet. The dynamical mechanisms of the zonal-mean poleward jet shift have been extensively studied in literature. At seasonal/regional scales, however, the westerly jets can shift equatorward, such as in the early-summer Asia–Pacific region, the late-winter America–Atlantic region, and the winter/spring east Pacific. These equatorward jet shifts imply climate impacts distinct from those of the poleward shifts, yet their causes are not well understood. In this work, based on a hierarchy of coupled, prescribed-SST, and aquaplanet simulations, we attribute the seasonal/regional equatorward jet shifts to the enhanced tropical upper-level warming (ETUW), which arises from both the tropical moist adiabat and the enhanced equatorial surface warming. By steepening the meridional temperature gradient in the subtropical upper-to-middle level and assisted by positive eddy feedback, the ETUW increases the zonal wind equatorward of the climatological jet. When the regional/seasonal meridional temperature gradients (or equivalently the westerly jets) are weak and peak close to the tropics, the ETUW effect overcomes the poleward jet-shift mechanisms and leads to the equatorward jet shifts. This climatological-state dependency is consistently seen in the decomposed jet responses to uniform warming and surface warming pattern, and further demonstrated through idealized aquaplanet experiments with designed climatological states. For uniform warming, the ETUW arising from moist adiabat makes the general poleward jet shifts insignificant in the aforementioned favorable regions/seasons. For warming pattern, the ETUW from enhanced equatorial warming drives substantial equatorward jet shifts in these favorable seasons/regions.

54 ENVIRONMENTAL SCIENCES↗

Probing eddy size and its effective mixing length in stably stratified roughness sublayer flows

Stably stratified roughness sublayer flows are ubiquitous yet remain difficult to represent in models and to interpret using field experiments. Here, continuous high-frequency potential temperature profiles from the forest floor up to 6.5 times the canopy height observed with distributed temperature sensing (DTS) are used to link eddy topology to roughness sublayer stability correction functions and coupling between air layers within and above the canopy. The experiments are conducted at two forest stands classified as hydrodynamically sparse and dense. Near-continuous profiles of eddy sizes (length scales) and effective mixing lengths for heat are derived from the observed profiles using a novel conditional sampling approach. The approach utilizes potential temperature isoline fluctuations from a statically stable background state. The transport of potential temperature by an observed eddy is assumed to be conserved (adiabatic movement) and we assume that irreversible heat exchange between the eddy and the surrounding background occurs along the (vertical) periphery of the eddy. This assumption is analogous to Prandtl's mixing-length concept, where momentum is transported rapidly vertically and then equilibrated with the local mean velocity gradient. A distinct dependence of the derived length scales on background stratification, height above ground, and canopy characteristics emerges from the observed profiles. Implications of these findings for (1) the failure of Monin–Obukhov similarity in the roughness sublayer and (2) above-canopy flow coupling to the forest floor are examined. The findings have practical applications in terms of analysing similar DTS data sets with the proposed approach, modelling roughness sublayer flows, and interpreting nocturnal eddy covariance measurements above tall forested canopies.

54 ENVIRONMENTAL SCIENCES↗

Thermoelastic Properties of Iron-Rich Ringwoodite and the Deep Mantle Aerotherm of Mars

The Martian mantle is considered to have a higher Fe/Mg ratio than the Earth's mantle. Ringwoodite, γ-(Mg,Fe) 2 SiO 4 , is likely the dominant polymorph of olivine in the core-mantle boundary (CMB) region of Mars. We synthesized anhydrous iron-rich ringwoodite with molar Mg/(Mg + Fe) = 0.44 and determined its thermal equation of state up to 35 GPa and 750 K by synchrotron X-ray diffraction. Using a third order Birch-Murnaghan equation of state, we obtain K T0 = 182 (3) GPa, K' = 4.6 (2), and α 0 = 3.18 (6) × 10 -5 K -1 . Using these results and an updated mineralogical model with an iron-rich composition of Mg/(Mg + Fe) = 0.75 for the Martian mantle, we estimate ~1900 K for the temperature of the D1000 seismic discontinuity inside Mars. The resulting adiabat predicts a warm aerotherm, which could explain the presence of partial melt at the CMB of Mars recently detected with seismic data from the 2019 InSight mission.

58 GEOSCIENCES↗

Thermochemical Nonequilibrium Modeling in a Continuous-Galerkin, Finite-Element Framework

The presented work discusses the implementation, verification, and validation of Park's two-temperature model in a scalable, computational fluid dynamics (CFD) code developed at the US Department of Energy's Oak Ridge National Laboratory (ORNL). The implementation of Park's two-temperature model was verified through 0D test cases involving an adiabatic reactor and a nitrogen thermal bath. The implementation was then validated through comparisons with other validated CFD codes and experimental data on a hypersonic cylinder and double cones. These are standard benchmark test cases for thermochemical non-equilibrium (TCNE) modeling, and all data are shared publicly. The verification and validation results showed that ORNL's in-house CFD code could model complex, high-speed flow problems with and without TCNE modeling. This work is essential for future research involving 3D shock wave/boundary layer interactions (SBLIs).

Nutter, Nicole↗

Free-spray characteristics and spray-wall interactions of methanol on a gasoline direct injector under flash-boiling and non-flash-boiling conditions

Methanol is considered a promising alternative fuel for internal combustion engines (ICEs) due to its high-octane number, fast laminar flame speed, and elevated latent heat of vaporization, all of which support higher compression ratios and improved thermal efficiency. However, its substantial latent heat of vaporization also poses cold-start challenges, such as misfire and fuel film deposition. This study aims to investigate methanol spray morphology and spray-wall interaction using the Spray M injector from the Engine Combustion Network within a constant-pressure flow vessel. A recently developed unified numerical framework capable of modeling both flash and non-flash boiling sprays is validated against experimental liquid volume fraction data acquired via 3-D computed tomography. Here, the results reveal that flash boiling significantly alters the spray morphology, leading to smaller droplets and spray collapse due to enhanced air-entrainment-induced turbulence. Quantitative agreement between experiments and simulations confirms this behavior. Coupled 0-D equilibrium and 3-D computational fluid dynamics analyses show that flash boiling accelerates evaporation and reduces fuel residence time, while non-flash conditions maintain a persistent liquid core more susceptible to wall wetting. Wall temperature diagnostics reveal that spray collapse alters heat transfer patterns by shifting cooling effects. Mixture fraction analysis indicates that evaporation is primarily governed by shear-layer turbulence, though deviations from adiabatic equilibrium mixing emerge under low-turbulence conditions. Finally, increasing fuel, ambient, and wall temperatures reduces wall wetting and film thickness, mitigating cold-start risks. These findings enhance the understanding of methanol sprays’ behavior and support its adoption as a viable, alternative fuel for ICEs.

Engine Combustion Network↗

Onset of Rayleigh-Bénard convection at fuel-ablator interfaces in inertial confinement fusion simulations

Here, we demonstrate the onset of Rayleigh-Bénard convection (RBC) near the fuel-ablator interface of inertial confinement fusion (ICF) implosion simulations for the scenario in which Rayleigh-Taylor or Richtmyer-Meshkov instabilities are suppressed. This convective heating within the cold fuel can degrade the adiabat and therefore performance of ICF implosions even without mixing of fuel and ablator. Our work suggests additional considerations to realize design adiabats in otherwise ideal ICF implosions: first, via control of the temperature differences between ablator and fuel and, second, control of the fuel acceleration which we show has a complex interplay with the RBC dynamics.

Physics - Plasma physics↗