IRREVERSIBLE PROCESSES IN PLASMAS IN A STRONG MAGNETIC FIELD
Irreversible processes in plasmas in a strong magnetic field
PLASMA↗
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Global and Regional Entropy Production by Radiation Estimated from Satellite Observations
Vertical profiles of shortwave and longwave irradiances computed with satellite-derived cloud properties and temperature and humidity profiles from reanalysis are used to estimate entropy production. Entropy production by shortwave radiation is computed by the absorbed irradiance within layers in the atmosphere and by the surface divided by their temperatures. Similarly, entropy production by longwave radiation is computed by emitted irradiance to space from layers in the atmosphere and surface divided by their temperatures. Global annual mean entropy production by shortwave absorption and longwave emission to space are, respectively, 0.852 and 0.928 W/sq.mK. With a steady-state assumption, entropy production by irreversible processes within the Earth system is estimated to be 0.076 W/sq.mK and by nonradiative irreversible processes to be 0.049 W/sq.mK. Both global annual mean entropy productions by shortwave absorption and longwave emission to space increase with increasing shortwave absorption (i.e., with decreasing the planetary albedo). The increase of entropy production by shortwave absorption is, however, larger than the increase of entropy production by longwave emission to space. The result implies that global annual mean entropy production by irreversible processes decreases with increasing shortwave absorption. Input and output temperatures derived by dividing the absorbed shortwave irradiance and emitted longwave irradiance to space by respective entropy production are, respectively, 282 and 259 K, which give the Carnot efficiency of the Earth system of 8.5%.
Seiji Kato↗
Large-cell Monte Carlo renormalization of irreversible growth processes
Monte Carlo sampling is applied to a recently formulated direct-cell renormalization method for irreversible, disorderly growth processes. Large-cell Monte Carlo renormalization is carried out for various nonequilibrium problems based on the formulation dealing with relative probabilities. Specifically, the method is demonstrated by application to the 'true' self-avoiding walk and the Eden model of growing animals for d = 2, 3, and 4 and to the invasion percolation problem for d = 2 and 3. The results are asymptotically in agreement with expectations; however, unexpected complications arise, suggesting the possibility of crossovers, and in any case, demonstrating the danger of using small cells alone, because of the very slow convergence as the cell size b is extrapolated to infinity. The difficulty of applying the present method to the diffusion-limited-aggregation model, is commented on.
Nakanishi, H.↗
Crack layer theory
A damage parameter is introduced in addition to conventional parameters of continuum mechanics and consider a crack surrounded by an array of microdefects within the continuum mechanics framework. A system consisting of the main crack and surrounding damage is called crack layer (CL). Crack layer propagation is an irreversible process. The general framework of the thermodynamics of irreversible processes are employed to identify the driving forces (causes) and to derive the constitutive equation of CL propagation, that is, the relationship between the rates of the crack growth and damage dissemination from one side and the conjugated thermodynamic forces from another. The proposed law of CL propagation is in good agreement with the experimental data on fatigue CL propagation in various materials. The theory also elaborates material toughness characterization.
Chudnovsky, A.↗
Crack layer theory
A damage parameter is introduced in addition to conventional parameters of continuum mechanics and consider a crack surrounded by an array of microdefects within the continuum mechanics framework. A system consisting of the main crack and surrounding damage is called crack layer (CL). Crack layer propagation is an irreversible process. The general framework of the thermodynamics of irreversible processes are employed to identify the driving forces (causes) and to derive the constitutive equation of CL propagation, that is, the relationship between the rates of the crack growth and damage dissemination from one side and the conjugated thermodynamic forces from another. The proposed law of CL propagation is in good agreement with the experimental data on fatigue CL propagation in various materials. The theory also elaborates material toughness characterization.
Chudnovsky, A.↗
The remarkable inefficiency of stratocumulus
Marine stratocumulus clouds play a central role in Earth's climate system by reflecting incoming solar radiation and exerting a strong cooling effect. Their organization into open and closed mesoscale cellular morphologies can be thought of as an example of bistable dynamics driven by aerosol–cloud interactions and mesoscale processes. From the perspective of non-equilibrium thermodynamics, these structures are an example of a far-from-equilibrium open system that continuously produces and exports entropy. While entropy production has been studied in idealized deep convective systems, it has not yet been quantified for shallow clouds. Here, we compute and decompose the internal entropy production of open- and closed-cell stratocumulus using an ensemble of large-eddy simulations. We show that the overall entropy production of stratocumulus is low, reflecting the limited vertical extent and corresponding reduced ability to utilize the energy fluxes at the system's boundaries. Moist processes dominate the overall irreversibility, which, combined with their low entropy production, leads to a mechanical efficiency about an order of magnitude smaller than in deep convective systems. Although the dominant irreversible processes differ between open- and closed-cell regimes, the distributions of total entropy production largely overlap across the ensemble, limiting the ability to distinguish the dynamics of individual cases based solely on total entropy production.
54 ENVIRONMENTAL SCIENCES↗
Inelastic relaxation processes in amorphous sodium silicates
During fracture amorphous oxides exhibit irreversible processes, including inelastic and nonrecoverable relaxation effects in the process zone surrounding the crack tip. Here, classical molecular dynamics simulations were used with a reactive forcefield to evaluate inelastic relaxation processes in five amorphous sodium silicate compositions. Overall, the 20% Na 2 O-SiO 2 (NS20) composition exhibited the most inelastic relaxation, followed by the 15% Na 2 O-SiO 2 (NS15) composition, the 25% Na 2 O-SiO 2 (NS25) composition, and finally the 10% (NS10) and 30% (NS30) Na 2 O-SiO 2 compositions. Coordination analysis of the Na + ions identified that during inelastic relaxation the Na+ ions were increasingly coordinated by nonbridging oxygens (NBOs) for the NS10 and NS15 compositions, which was supported by radial analysis of the O-Na-O bond angles surrounding the crack tip. Across the sodium silicate compositional range, two different inelastic relaxation mechanism were identified based on the amount of bridging oxygens (BOs) and NBOs in the Na+ ion coordination shell. At lower (NS10) and higher (NS30) sodium compositions, the entire structured relaxed toward the crack tip. In contrast at intermediate sodium concentrations (NS20) the Na + ion migrates toward the crack tip separately from the network structure. By developing a fundamental understanding of how modified silica systems respond to static stress fields, we will be able to predict how varying amorphous silicate systems exhibit slow crack growth.
36 MATERIALS SCIENCE↗
microRNAs (miR 9, 124, 155 and 224) transdifferentiate mouse macrophages to neurons
Highlights: • miR 9, miR 124 and miR155 could reprogramme macrophages to mature neurons. • miR-induced neuronal reprogramming involves stem cell-like intermediate phenotype. • miR 9, miR 124 and miR155 could also reprogramme CD133+ stem cells to mature neurons. Development is an irreversible process of differentiating the undifferentiated cells to functional cells. Brain development involves generation of cells with varied phenotype and functions, which is limited during adulthood, stress, damage/degeneration. Cellular reprogramming makes differentiation reversible process with reprogramming somatic/stem cells to alternative fate with/without stem cells. Exogenously expressed transcription factors or small molecule inhibitors have driven reprogramming of stem/somatic cells to neurons providing alternative approach for pre-clinical/clinical testing and therapeutics. Here in, we report a novel approach of microRNA (miR)- induced trans-differentiation of macrophages (CD11b high) to induced neuronal cells (iNCs) (neuronal markershigh- Nestin, Nurr1, Map2, NSE, Tubb3 and Mash1) without exogenous use of transcription factors. miR 9, 124, 155 and 224 successfully transdifferentiated macrophages to neurons with transient stem cell-like phenotype. We report trans differentiation efficacy 18% and 21% with miR 124 and miR 155. in silico(String 10.0, miR gator, mESAdb, TargetScan 7.0) and experimental analysis indicate that the reprogramming involves alteration of pluripotencygenes like Oct4, Sox2, Klf4, Nanog and pluripotency miR, miR 302. iNCs also shifted to G0 phase indicating manipulation of cell cycle by these miRs. Further, CD133+ intermediate cells obtained during current protocol could be differentiated to iNCs using miRs. The syanpsin{sup +} neurons were functionally active and displayed intracellular Ca{sup +2} evoke on activation. miRs could also transdifferentiate bone marrow-derived macrophages and peripheral blood mononuclear cells to neuronal cells. The current protocol could be employed for direct in vivo reprogramming of macrophages to neurons without teratoma formation for transplantation and clinical studies.
60 APPLIED LIFE SCIENCES↗
Thermally regenerative hydrogen/oxygen fuel cell power cycles
Two innovative thermodynamic power cycles are analytically examined for future engineering feasibility. The power cycles use a hydrogen-oxygen fuel cell for electrical energy production and use the thermal dissociation of water for regeneration of the hydrogen and oxygen. The TDS (thermal dissociation system) uses a thermal energy input at over 2000 K to thermally dissociate the water. The other cycle, the HTE (high temperature electrolyzer) system, dissociates the water using an electrolyzer operating at high temperature (1300 K) which receives its electrical energy from the fuel cell. The primary advantages of these cycles is that they are basically a no moving parts system, thus having the potential for long life and high reliability, and they have the potential for high thermal efficiency. Both cycles are shown to be classical heat engines with ideal efficiency close to Carnot cycle efficiency. The feasibility of constructing actual cycles is investigated by examining process irreversibilities and device efficiencies for the two types of cycles. The results show that while the processes and devices of the 2000 K TDS exceed current technology limits, the high temperature electrolyzer system appears to be a state-of-the-art technology development. The requirements for very high electrolyzer and fuel cell efficiencies are seen as determining the feasbility of the HTE system, and these high efficiency devices are currently being developed. It is concluded that a proof-of-concept HTE system experiment can and should be conducted.
Morehouse, J. H.↗
Hidden domain boundary dynamics toward crystalline perfection
A central paradigm of nonequilibrium physics concerns the dynamics of heterogeneity and disorder, impacting processes ranging from the behavior of glasses to the emergent functionality of active matter. Understanding these complex mesoscopic systems requires probing the microscopic trajectories associated with irreversible processes, the role of fluctuations and entropy growth, and the timescales on which nonequilibrium responses are ultimately maintained. Approaches that illuminate these processes in model systems may enable a more general understanding of other heterogeneous nonequilibrium phenomena, and potentially define ultimate speed and energy cost limits for information processing technologies. Here, we apply ultrafast single-shot X-ray photon correlation spectroscopy to resolve the nonequilibrium, heterogeneous, and irreversible mesoscale dynamics during a light-induced phase transition in a (PbTiO 3 ) 16 /(SrTiO 3 ) 16 superlattice. Such ferroelectric superlattice systems are a useful platform to study phase transitions and topological dynamics due to their high degree of tunability. This provides an approach for capturing the nucleation of the light-induced phase, the formation of transient mesoscale defects at the boundaries of the nuclei, and the eventual annihilation of these defects, even in systems with complex polarization topologies. We identify a nonequilibrium correlation response spanning >10 orders of magnitude in timescales, with multistep behavior similar to the plateaus observed in supercooled liquids and glasses. We further show how the observed time-dependent long-time correlations can be understood in terms of stochastic and non-Markovian dynamics of domain walls, encoded in waiting-time distributions with power-law tails. This work defines possibilities for probing the nonequilibrium and correlated dynamics of disordered and heterogeneous media.
36 MATERIALS SCIENCE↗
Optimizing thermodynamic trajectories using evolutionary and gradient-based reinforcement learning
Here using a model heat engine, we show that neural-network-based reinforcement learning can identify thermodynamic trajectories of maximal efficiency. We consider both gradient and gradient-free reinforcement learning. We use an evolutionary learning algorithm to evolve a population of neural networks, subject to a directive to maximize the efficiency of a trajectory composed of a set of elementary thermodynamic processes; the resulting networks learn to carry out the maximally efficient Carnot, Stirling, or Otto cycles. When given an additional irreversible process, this evolutionary scheme learns a previously unknown thermodynamic cycle. Gradient-based reinforcement learning is able to learn the Stirling cycle, whereas an evolutionary approach achieves the optimal Carnot cycle. Our results show how the reinforcement learning strategies developed for game playing can be applied to solve physical problems conditioned upon path-extensive order parameters.
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
Solar wind: Internal parameters driven by external source
A new concept interpreting solar wind parameters is suggested. The process of increasing twofold of a moving volume in the solar wind (with energy transfer across its surface which is comparable with its whole internal energy) is a more rapid process than the relaxation for the pressure. Thus, the solar wind is unique from the point of view of thermodynamics of irreversible processes. The presumptive source of the solar wind creation - the induction electric field of the solar origin - has very low entropy. The state of interplanetary plasma must be very far from the thermodynamic equilibrium. Plasma internal energy is contained mainly in non-degenerate forms (plasma waves, resonant plasma oscillations, electric currents). Microscopic oscillating electric fields in the solar wind plasma should be about 1 V/m. It allows one to describe the solar wind by simple dissipative MHD equations with small effective mean free path (required for hydrodynamical description), low value of electrical conductivity combined with very big apparent thermal conductivity (required for observed solar wind acceleration). These internal parameters are interrelated only due to their origin: they are externally driven. Their relation can change during the interaction of solar wind plasma with an obstacle (planet, spacecraft). The concept proposed can be verified by the special electric field measurements, not ruining the primordial plasma state.
Chertkov, A. D.↗
Hydrogen Dissociation Controls 1-Hexyne Selective Hydrogenation on Dilute Pd-in-Au Catalysts
Increasing the selectivity of the catalytic hydrogenation of alkynes to alkenes is of major importance for the processing of petrochemicals and the production of fine chemicals. Achieving high selectivity for alkene formation at high conversions, however, remains a long-standing challenge in heterogeneous catalysis. Here, the mechanism and origin of the high selectivity of dilute Pd-in-Au catalysts has been studied by a combination of first-principles calculations, microkinetic simulations, and isotopic exchange hydrogenation experiments using Pd 0.04 Au 0.96 nanoparticles embedded in raspberry colloid-templated silica. The Pd is predominantly in the form of isolated atoms, only surrounded by Au atoms, based on prior studies. The simulations indicate that the rate-limiting process for 1-hexyne hydrogenation on Pd monomers in Au(111) is H 2 dissociation, which has a large free energy barrier of 0.86 eV at 363 K and 0.2 bar of H 2 . The C–H bond formation steps, on the other hand, proceed with lower barriers, which contrasts with previous studies of extended Pd catalysts. The microkinetic simulations identify the sizable H 2 dissociation barrier and the small barrier for the hydrogenation of 1-hexyne as key factors that lead to a high selectivity for the production of 1-hexene from 1-hexyne, even at high conversion. The unconventional H 2 dissociation limiting process in combination with the low coverage of weakly bound hydrocarbon intermediates explains the near-zero order of 1-hexyne found experimentally. Furthermore, the partial hydrogenation of 1-hexyne to form 1-hexene is shown to be an irreversible process from our isotopic exchange hydrogenation experiments and is explained by the strongly exothermic nature of the reaction. Diluting active species, like Pd, in a less active host metal, like Au, hence appears promising as a means of tuning the binding energy of reactants and altering reaction profiles, leading to distinct kinetic behavior for an optimal catalytic activity and selectivity. Furthermore, the combination of microkinetic modeling, density functional theory calculations, and isotopic exchange experiments is thus demonstrated to be an effective approach to modeling important catalytic phenomena.
1-hexyne↗
Observation of Joule–Thomson photon-gas expansion
In recent years, a self-consistent optical thermodynamic framework has emerged that offers a systematic methodology to understand, harness and exploit the complex collective dynamics of multimode nonlinear systems. These developments now allow consideration of a series of longstanding problems in optics, including the prospect of funnelling the entire power flowing in a multimode system into its ground state, for which no methodology currently exists. Here, we demonstrate an all-optical Joule-Thomson expansion process mediated by photon-photon interactions whereby the temperature of the optical gas drops abruptly to zero. Our experiments in various configurations of coupled multicore nonlinear waveguide arrangements illustrate how light undergoing expansion-induced cooling can be channelled from arbitrary input states into the fundamental mode with near-unity efficiency. We show that the stability of the post-expansion state is ensured through an irreversible process of energy conversion. The all-optical thermodynamic phenomena explored in this study may enable innovative techniques where various uncorrelated but identical sources are merged into a unified spatially coherent state, offering a route for direct beam combining.
Kirsch, Marco S. (ORCID:0000000342798228)↗
A phase-field fracture formulation for generalized standard materials: The interplay between thermomechanics and damage
Accurately modeling fracture of ductile materials poses open challenges in the field of computational mechanics due to the multiphysics nature of their failure processes. Integrating the interplay between thermodynamics and damage into ductile fracture models is vital for predicting critical failure modes. Here, in this paper, we develop a versatile phase-field (PF) framework for modeling ductile fracture, taking into account finite-strain elasto-plasticity. The framework stems from a variational formulation of constitutive relations for generalized standard materials (GSMs), whose response is described by a Helmholtz free energy and a dissipation pseudo-potential. Its variational structure is based on a minimum principle for a functional that expresses the sum of power densities for reversible and irreversible processes. By minimizing this functional with a constraint on a von Mises yield function, we derive the evolution equation for the equivalent plastic strain and an associative flow rule. This constrained optimization problem is analytically solved for a wide class of thermo-viscoplasticity models. The key innovations of the current work include (i) a cubic plastic degradation function that accounts for a non-vanishing damage-dependent yield stress, (ii) closed-form expressions of the Helmholtz free energy and dissipation pseudo-potential for three thermo-viscoplasticity models, (iii) an extended Johnson–Cook plasticity model with a nonlinear hardening law, and (iv) a plastic work heat source that depends on the plastic degradation function and a variable Taylor–Quinney (TQ) coefficient. The capabilities of the proposed framework are tested with the aid of four ductile fracture problems, including the Sandia Fracture Challenge. In each of these problems, we examine the evolution of relevant field variables such as the PF order parameter, the equivalent plastic strain, the temperature, and the internal power dissipation density, in addition to the overall structural response quantified by the force–displacement curve. These numerical studies demonstrate that the proposed framework effectively represents ductile fracture, yielding computational results that exhibit good agreement with experimental data.
36 MATERIALS SCIENCE↗
Li 2 MnO 3 : A Catalyst for a Liquid Cl 2 Electrode in Low‐Temperature Aqueous Batteries
Abstract Li 2 MnO 3 has been contemplated as a high‐capacity cathode candidate for Li‐ion batteries; however, it evolves oxygen during battery charging under ambient conditions, which hinders a reversible reaction. However, it is unclear if this irreversible process still holds under subambient conditions. Here, the low‐temperature electrochemical properties of Li 2 MnO 3 in an aqueous LiCl electrolyte are evaluated and a reversible discharge capacity of 302 mAh g −1 at a potential of 1.0 V versus Ag/AgCl at −78 °C with good rate capability and stable cycling performance, in sharp contrast to the findings in a typical Li 2 MnO 3 cell cycled at room temperature, is observed. However, the results reveal that the capacity does not originate from the reversible oxygen oxidation in Li 2 MnO 3 but the reversible Cl 2 (l)/Cl − (aq.) redox from the electrolyte. The results demonstrate the good catalytic properties of Li 2 MnO 3 to promote the Cl 2 /Cl − redox at low temperatures.
Sui, Yiming↗
In-Situ Observation of the Formation of Laser-Induced Periodic Surface Structures with Extreme Spatial and Temporal Resolution
Irradiation of solid surfaces with intense ultrashort laser pulses represents a unique way of depositing energy into materials. It allows to realize states of extreme electronic excitation and/or very high temperature and pressure and to drive materials close to and beyond fundamental stability limits. As a consequence, structural changes and phase transitions often occur along unusual pathways and under strongly nonequilibrium conditions. Furthermore, due to the inherent multiscale nature—both temporally and spatially—of these irreversible processes, their direct experimental observation requires techniques that combine high temporal resolution with the appropriate spatial resolution and the capability to obtain good quality data on a single pulse/event basis. In this respect, fourth-generation light sources, namely, short wavelength and short pulse free electron lasers (FELs), are offering new and fascinating possibilities. As an example, this chapter will discuss the results of scattering experiments carried out at the FLASH free electron laser at DESY (Hamburg, Germany), which allowed us to resolve laser-induced structure formation at surfaces on the nanometer to submicron length scale and in temporal regimes ranging from picoseconds to several nanoseconds with sub-picosecond resolution.
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
Mimicking associative learning using an ion-trapping non-volatile synaptic organic electrochemical transistor
Associative learning, a critical learning principle to improve an individual’s adaptability, has been emulated by few organic electrochemical devices. However, complicated bias schemes, high write voltages, as well as process irreversibility hinder the further development of associative learning circuits. Here, by adopting a poly(3,4-ethylenedioxythiophene):tosylate/Polytetrahydrofuran composite as the active channel, we present a non-volatile organic electrochemical transistor that shows a write bias less than 0.8 V and retention time longer than 200 min without decoupling the write and read operations. By incorporating a pressure sensor and a photoresistor, a neuromorphic circuit is demonstrated with the ability to associate two physical inputs (light and pressure) instead of normally demonstrated electrical inputs in other associative learning circuits. To unravel the non-volatility of this material, ultraviolet-visible-near-infrared spectroscopy, X-ray photoelectron spectroscopy and grazing-incidence wide-angle X-ray scattering are used to characterize the oxidation level variation, compositional change, and the structural modulation of the poly(3,4-ethylenedioxythiophene):tosylate/Polytetrahydrofuran films in various conductance states. The implementation of the associative learning circuit as well as the understanding of the non-volatile material represent critical advances for organic electrochemical devices in neuromorphic applications.
42 ENGINEERING↗