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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
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Study of boundary conditions at liquid-vapor interface through irreversible thermodynamics
Validity of Onsager-Casimir reciprocal relations with theoretical framework of macroscopic nonequilibrium thermodynamics
The layer edge states or low energy state (LES) in 2D hybrid organic–inorganic perovskites demonstrate a prolonged carrier lifetime for better performance of optoelectronic devices. However, the fundamental understanding of LES in 2D perovskites is still inconclusive. Herein, a photoluminescence (PL) study of LES in 2D Ruddlesden–Popper perovskites is presented with n = 2 and n = 3 from their cleaved cross sections that are more stable than the natural edge. The PL measurements clearly observe reversible, and irreversible surface relaxations (case I and case II) in three laser intensity ranges, further supported by a PL excitation cycle from low to high laser intensity, and vice versa. The PL wavelength of LES is tunable with laser intensity and blueshifts with increasing laser intensity during irreversible surface relaxation process (case I). Fluorescence lifetime imaging (FLIM) shows that the LES has a longer lifetime than the band-edge emission in the sample without a photodegradation, while the BE lifetime becomes relatively longer in the area with a photodegradation. Furthermore, the presented laser tunable LES and the related irreversible relaxation process provide a new insight that can help improve the photostability in 2D perovskites and understand roles of LESs in optoelectronic device performance.
The principles of thermodynamics in relation to the irreversibility of real processes in nature are examined, taking into account an analogy used by Gibbs to present a picture concerning the time evolution of a complicated dynamical system. The significance of quantum-mechanics relations with respect to irreversibility considerations is explored. It is shown that quantum mechanical uncertainties are not necessarily required to obtain irreversibility.
Separators are generally considered inert components in lithium-ion batteries. In the past, some electroactive polymers have been successfully applied in separator modifications for overcharge protection or as acid scavengers. This study highlights the first use of two “electroactive” carbazole polymers (copolymer 9-phenyl-9H-carbazole-phenyl [PCP] and poly(9-vinylcarbazole) [PVC]), which were each applied separately as coatings on the cathode-facing side of commercial Celgard 2325 separators, respectively, to enhance the cycling performance of 0.3Li 2 MnO 3 ·0.7LiMn 0.5 Ni 0.5 O 2 //graphite (LMR-NM//Gr) full cells through interphase engineering. The team observed an irreversible polymer oxidation process of the carbazole-functionalized polymers—occurring only during the first charge—for the modified separator cells, and the results were confirmed by dQ/dV analysis, cyclic voltammetry measurements, and nuclear magnetic resonance characterizations. During this oxidation, carbazole polymers participate in the process of interphase formation, contributing to the improved cycling performance of LMR-NM//Gr batteries. Particularly, oxidation takes place at voltages of ~4.0 and ~3.5 V when PCP and PVC are used as separator coatings, which is highly irreversible. Further postmortem examinations suggest that the improvements using these modified separators arise from the formation of higher-quality and more inorganic SEI, as well as the beneficial CEI enriched in LixPOyFz. These interphases effectively inhibit the crosstalk effect by reducing TM dissolution.
A theory of fracture mechanics is formulated on the foundation of continuum mechanics. Fracture surface is introduced as an unknown quantity and is incorporated into boundary and initial conditions. Surface energy is included in the global form of energy conservation law and the dissipative mechanism is formulated into constitutive equations which indicate the thermodynamic irreversibility and the irreversibility of fracture process as well.
The objective of this paper is to present an estimate of the second law thermodynamic efficiency of the various units comprising an Environmental Control and Life Support System (ECLSS). The technique adopted here is based on an evaluation of the 'lost work' within each functional unit of the subsystem. Pertinent information for our analysis is obtained from a user interactive integrated model of an ECLSS. The model was developed using ASPEN. A potential benefit of this analysis is the identification of subsystems with high entropy generation as the most likely candidates for engineering improvements. This work has been motivated by the fact that the design objective for a long term mission should be the evaluation of existing ECLSS technologies not only the basis of the quantity of work needed for or obtained from each subsystem but also on the quality of work. In a previous study Brandhorst showed that the power consumption for partially closed and completely closed regenerable life support systems was estimated as 3.5 kw/individual and 10-12 kw/individual respectively. With the increasing cost and scarcity of energy resources, our attention is drawn to evaluate the existing ECLSS technologies on the basis of their energy efficiency. In general the first law efficiency of a system is usually greater than 50 percent. From literature, the second law efficiency is usually about 10 percent. The estimation of second law efficiency of the system indicates the percentage of energy degraded as irreversibilities within the process. This estimate offers more room for improvement in the design of equipment. From another perspective, our objective is to keep the total entropy production of a life support system as low as possible and still ensure a positive entropy gradient between the system and the surroundings. The reason for doing so is as the entropy production of the system increases, the entropy gradient between the system and the surroundings decreases, and the system will gradually approach equilibrium with the surroundings until it reaches the point where the entropy gradient is zero. At this point no work can be extracted from the system. This is called the 'dead state' of the system.
Despite the broad interest in Al-doped lithium lanthanum zirconium oxide (LLZO), the wide range of reported ionic conductivities suggests that the effect of processing parameters on the resulting phase purity and bulk conductivity is not well-understood. Here, in this work, we synthesized six separate series of LLZO with variations in Al concentration, Li excess, Li addition order, Li source, densification method, and mother powder to determine the effect on the composition, phase purity, density, and bulk conductivity. We found that a wider range of compositions (6.08–7.61 mol of Li and 0.06–0.23 mol of Al) than previously reported can result in cubic phase stability and that nearly all elements (Li, Al, Zr, and La) are lost to the MgO crucible during calcination and sintering. The manner in which different elements are lost is affected by the processing parameters. We observed that Al-doped LLZO shows great compositional flexibility in stabilizing the cubic phase, offering an explanation for the range of electrochemical performance metrics reported in the literature.
The amounts of volatiles incorporated in the Martian regolith by photostimulated oxidation weathering of Fe(2+)-bearing minerals are estimated. The process of photostimulated oxidation weathering is described, and it is noted that all the necessary constituents for this process are present on Mars. The rates at which oxygen and hydrogen are irreversibly removed from the Martian atmosphere by the present process are determined, irreversible and reversible water losses are considered, and the loss of CO2 by carbonate formation is shown to be irreversible. The results suggest that photostimulated oxidation weathering has irreversibly consumed 100 to 100,000 g/sq cm of H2O and 10 to 10,000 g/sq cm of CO2, assuming a uniform rate over geologic time. It is concluded that if the amounts of H2O and CO2 actually removed by photostimulated oxidation are close to the upper limits of the present estimates, then that process may have had a major effect in limiting the amount of H2O and CO2 trapped in the regolith and polar caps.
This paper presents (Lagrangian) variational formulations for single and multicomponent semi-compressible fluids with both reversible (entropy-conserving) and irreversible (entropy-generating) processes. Semi-compressible fluids are useful in describing low-Mach dynamics, since they are soundproof. These models find wide use in many areas of fluid dynamics, including both geophysical and astrophysical fluid dynamics. Specifically, the Boussinesq, anelastic and pseudoincompressible equations are developed through a unified treatment valid for arbitrary Riemannian manifolds, thermodynamic potentials and geopotentials. By design, these formulations obey the 1st and 2nd laws of thermodynamics, ensuring their thermodynamic consistency. This general approach extends and unifies existing work, and helps clarify the thermodynamics of semi-compressible fluids. To further this goal, evolution equations are presented for a wide range of thermodynamic variables: entropy density s, specific entropy η, buoyancy b, temperature T, potential temperature θ and a generic entropic variable χ; along with a general definition of buoyancy valid for all three semicompressible models and arbitrary geopotentials. Finally, the elliptic equation for the pressure perturbation (the Lagrange multiplier that enforces semi-compressibility) is developed for all three equation sets in the case of reversible dynamics, and for the Boussinesq/anelastic equations in the case of irreversible dynamics; and some discussion is given of the difficulty in formulating it for the pseudoincompressible equations with irreversible dynamics.
In this research, detection of trimethoprim (TMP) was carried out using a nanostructured zinc oxide nanoparticle-modified carbon paste electrode (ZnO/CPE) with an anionic surfactant and sodium dodecyl sulphate (SDS) with the help of voltametric techniques. The electrochemical nature of TMP was studied in 0.2 M pH 3.0 phosphate-buffer solution (PBS). The developed electrode displayed the highest peak current compared to nascent CPE. Effects of variation in different parameters, such as pH, immersion time, scan rate, and concentration, were investigated. The electrode process of TMP was irreversible and diffusion controlled with two electrons transferred. The effective concentration range (8.0 × 10 -7 M–1.0 × 10 -5 M) of TMP was obtained by varying the concentration with a lower limit of detection obtained to be 2.58 × 10 -8 M. In addition, this approach was effectively employed in the detection of TMP in pharmaceutical dosages and samples of urine with the excellent recovery data, suggesting the potency of the developed electrode in clinical and pharmaceutical sample analysis.
An effective and sensitive measurement of the depth of a deactivated or dead layer can be obtained from the relative attenuation of the 22.162 KeV and 87.9 KeV X-rays emitted by Cd 109. The alpha-particles emitted by Am 241 are also useful in measuring dead layers less than 25 microns. The properties and temporal development of dead layers are discussed in detail. The rate of growth of a deal layer is closely related to the ambient humidity, and the damage to the crystal is irreversible by any known process. The dead layer can be minimized by polishing all crystal surfaces and by keeping the crystal in a vacuum or a dry atmosphere. Since a dead layer seriously inhibits the response of a crystal to X-rays of energies below approximately 20 keV, CsI(Na) detectors should not be used at these energies unless precautions are taken to ensure that no dead layer forms.
Carbamate formation and exchange catalysts enable efficient polyurethane (PU) manufacturing, as well as emerging recycling and reprocessing methods for PU thermosets. Zirconium β-diketonate complexes, such as Zr acetylacetonate [Zr(acac) 4 ], are effective alternatives to toxic organotin catalysts that have been used for PU reprocessing. Here, we report that Zr(acac) 4 undergoes a thermally activated process in the PU network during reprocessing that transforms it into a more active carbamate exchange catalyst. This process is associated with the irreversible loss of acetylacetonate ligands and is not observed for the more sterically hindered Zr 2,2,6,6-tetramethyl-3,5-heptanedione [Zr(tmhd) 4 ] complex. Crossover experiments between PU thermoplastics indicated enhanced carbamate exchange after the thermal activation of Zr(acac) 4 in the presence of one of the PUs, whereas a sample of Zr(acac) 4 activated in the absence of the PU had no catalytic activity. Thermal gravimetric analysis suggested that this process is associated with the loss of one protonated acac ligand. Stress relaxation analysis of PU thermosets indicated a distinct change in the characteristic relaxation time associated with the thermal activation of Zr(acac) 4 at temperatures above 140 °C; no such change was observed for samples reprocessed using Zr(tmhd) 4 . Density functional theory and molecular experiments suggest that irreversible ligand exchange of acac with alkoxide or carbamate reduces the activation energy for urethane formation and reversion. Furthermore, the Zr(acac) 4 catalyst activated in the presence of a PU’s polyol precursor provided more porous and less dense PU foams compared to those made using the unactivated Zr(acac) 4 catalyst. Furthermore, these findings are important for developing improved PU synthesis and recycling processes. Thermally activating a catalyst during reprocessing may provide more nuanced control of the in-use and reprocessing characteristics of PU thermosets.
The performance of the MHD energy bypass air-breathing engine for high-speed propulsion is analyzed in this investigation. This engine is a specific type of the general class of inverse cycle engines. In this paper, the general relationship between engine performance (specific impulse and specific thrust) and the overall total pressure ratio through an engine (from inlet plane to exit plane) is first developed and illustrated. Engines with large total pressure decreases, regardless of cause or source, are seen to have exponentially decreasing performance. The ideal inverse cycle engine (of which the MHD engine is a sub-set) is then demonstrated to have a significant total pressure decrease across the engine; this total pressure decrease is cycle-driven, degrades rapidly with energy bypass ratio, and is independent of any irreversibility. The ideal MHD engine (inverse cycle engine with no irreversibility other than that inherent in the MHD work interaction processes) is next examined and is seen to have an additional large total pressure decrease due to MHD-generated irreversibility in the decelerator and the accelerator. This irreversibility mainly occurs in the deceleration process. Both inherent total pressure losses (inverse cycle and MHD irreversibility) result in a significant narrowing of the performance capability of the MHD bypass engine. The fundamental characteristics of MHD flow acceleration and flow deceleration from the standpoint of irreversibility and second-law constraints are next examined in order to clarify issues regarding flow losses and parameter selection in the MM modules. Severe constraints are seen to exist in the decelerator in terms of allowable deceleration Mach numbers and volumetric (length) required for meaningful energy bypass (work interaction). Considerable difficulties are also encountered and discussed due to thermal/work choking phenomena associated with the deceleration process. Lastly, full engine simulations utilizing inlet shock systems, finite-rate chemistry, wall cooling with thermally balanced engine (fuel heat sink), fuel injection and mixing, friction, etc. are shown and discussed for both the MHD engine and the conventional scramjet. The MHD bypass engine has significantly lower performance in all categories across the Mach number range (8 to 12.2). The lower performance is attributed to the combined effects of 1) additional irreversibility and cooling requirements associated with the MHD components and 2) the total pressure decrease associated with the inverse cycle itself.
P2-type sodium layered transition metal oxides have been intensively investigated as promising cathode materials for sodium-ion batteries (SIBs) by virtue of their high specific capacity and high operating voltage. However, they suffer from problems of voltage decay, capacity fading, and structural deterioration, which hinder their practical application. Therefore, a mechanistic understanding of the cationic/anionic redox activity and capacity fading is indispensable for the further improvement of electrochemical performance. Here, a prototype cathode material of P2-type Na 0.6 Mg 0.3 Mn 0.7 O 2 is comprehensively investigated, which presents both cationic and anionic redox behaviors during the cycling process. By a combination of soft X-ray absorption spectroscopy and electroanalytical methods, we unambiguously reveal that only oxygen redox reaction is involved in the initial charge process, then both oxygen and manganese participate in the charge compensation in the following discharge process. In addition, a gradient distribution of Mn valence state from surface to bulk is disclosed, which could be mainly related to the irreversible oxygen activity during the charge process. Furthermore, we find that the average oxidation state of Mn is reduced upon extended cycles, leading to the noticeable capacity fading. Our results provide deeper insights into the intrinsic cationic/anionic redox mechanism of P2-type materials, which is vital for the rational design and optimization of advanced cathode materials for SIBs.
Growth of nitric acid trihydrate (NAT) particles on background stratospheric aerosols is examined for an isolated air parcel cooled at a uniform rate. During the process of nucleation, the saturation ratio of HNO3 vapor reaches a maximum value between 2 and 15, corresponding to supercooling by 1-4 K. If cooling rates exceed 0.5-1 K/day, small particles of NAT are produced. A major fraction of the available condensation nuclei is activated and removal of HNO3 by gravitational settling is slow. If cooling rates are less than 0.5-1 K/day, the number of aerosols that nucleate is reduced, leading to differential growth of large NAT particles. Observations of 5 micron radius particles in clouds at temperatures above the water frost point may reflect condensation of NAT on ice particles that fall through a column of air as it is cooled. Rapid condensation of HNO3 on ice particles is promoted by the high supersaturation attained during nucleation and maintained during subsequent cooling. This process provides a mechanism for irreversible removal of HNO3.
We apply thermoporoelasticity and a sequentially coupling technique for modeling thermally-driven coupled Thermo-Hydro-Mechanical (THM) processes in tight claystone. A THM benchmark case with a corresponding analytic solution for thermoporoelasticity under a constant heat loading verifies the model. Thereafter, two in situ heating experiments are simulated for model validation: a smaller-scale heating experiment (TED experiment) and a larger-scale experiment (ALC experiment) in Callovo-Oxfordian (COx) claystone at the Meuse/Haute-Marne underground research laboratory in France. The model exhibits good performance to match the observed temperature and pore pressure evolution for the smaller-scale TED experiment. For the larger-scale ALC experiment, general trends of thermal-pressurization are captured in the modeling, but pressure is underestimated at some monitoring points during cool-down. This indicates that the THM response in the field may be affected by the variability of rock's properties or irreversible or time-dependent mechanical processes that are not included in the current thermoporoelastic model. The main contributions of this work are as follows: (1) we verify and validate the numerical simulator, TOUGH-FLAC, to be a valuable coupled THM modeling tool; (2) prove that the laboratory determined material parameters can be used as reference values for upscaling experiments. However, to better identify and quantify THM processes with modeling of in situ tests, more emphasize should be dedicated to obtaining high-quality mechanical deformation data.
The essential role of a well-defined hydrogen-bond network in achieving chemically reversible multiproton translocations triggered by one-electron electrochemical oxidation/reduction is investigated by using pyridylbenzimidazole–phenol models. The two molecular architectures designed for these studies differ with respect to the position of the N atom on the pyridyl ring. In one of the structures, a hydrogen-bond network extends uninterrupted across the molecule from the phenol to the pyridyl group. Experimental and theoretical evidence indicates that an overall chemically reversible two-protoncoupled electron-transfer process (E2PT) takes place upon electrochemical oxidation of the phenol. This E2PT process yields the pyridinium cation and is observed regardless of the cyclic voltammogram scan rate. In contrast, when the hydrogen-bond network is disrupted, as seen in the isomer, at high scan rates (~1000 mV s –1 ) a chemically reversible process is observed with an E 1/2 characteristic of a one-proton-coupled electron-transfer process (E1PT). At slow cyclic voltammetric scan rates (<1000 mV s –1 ) oxidation of the phenol results in an overall chemically irreversible two-proton-coupled electron-transfer process in which the second proton-transfer step yields the pyridinium cation detected by infrared spectroelectrochemistry. In this case, we postulate an initial intramolecular proton-coupled electron-transfer step yielding the E1PT product followed by a slow, likely intermolecular chemical step involving a second proton transfer to give the E2PT product. Insights into the electrochemical behavior of these systems are provided by theoretical calculations of the electrostatic potentials and electric fields at the site of the transferring protons for the forward and reverse processes. Furthermore, this work addresses a fundamental design principle for constructing molecular wires where protons are translocated over varied distances by a Grotthuss-type mechanism.