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The adsorption of polymer-grafted nanoparticles at interfaces is a problem of fundamental interest in physics and soft materials. This adsorption behavior is governed by the interplay between interaction potentials and entropic effects. Here, we use molecular dynamics simulations and umbrella sampling methods to study the adsorption behavior of a Janus-like homopolymer-grafted nanoparticle at fluid–fluid interfaces. By calculating the potential of the mean force as the particle moves from fluid A to the interface, the adsorption energy Ea can be obtained. When two homopolymer chains with types A and B are grafted to the opposite poles of the particle, Ea shows a scaling behavior with respect to chain length N: Ea ∝ N0.598. This is determined by the interactions between polymers and fluids. The enthalpy dominates, and the entropy effects mainly come from the rotational entropy loss of the polymer-grafted nanoparticle at interfaces, which disfavors the stabilization of particles at interfaces. When the grafted polymer number m is large, the adsorption energy exhibits a linear dependence on m. While the enthalpy dominates the behavior, the entropy becomes significant at a larger chain length of N = 15, where the configurational entropy of the polymer chains dominates the entropy of the system. The globule–coil transition occurs when polymers move from poor solvents to good solvents, increasing the configurational entropy and favoring the stabilization of particles at interfaces. Our study provides novel insights into the stabilization mechanism of polymer-grafted nanoparticles at interfaces and reveals the stabilization mechanism favored by the configurational entropy of grafted polymer chains. [ABSTRACT FROM AUTHOR]

In this work, we studied the nature and dilemma of the inverse magnetocaloric effect using Ni50Mn36In14 magnetic shape memory alloy. In this context, the inverse magnetocaloric effects of Ni50Mn36In14 magnetic shape memory alloy polycrystalline samples were investigated as a function of annealing heat treatments by the thermo-magnetometry method. Two forms of Ni49TiMn36In14 magnetic shape memory alloy were studied: one that predominantly undergoes a magnetic phase transition and the other that exhibits both a magnetic and martensitic phase transition. The magnetic behaviors and magnetocaloric properties of these alloys were analyzed to investigate the competition between magnetic and lattice contributions to the total entropy change. Finally, the mutually contradictory role of magnetic and lattice contributions was demonstrated. [ABSTRACT FROM AUTHOR]

Dynamic heterogeneity is a fundamental characteristic of glasses and undercooled liquids. The heterogeneous nature causes some of the key features of systems' dynamics such as the temperature dependence of nonexponentiality and spatial enthalpy fluctuations. Commonly used phenomenological models such as Tool–Narayanaswamy–Moynihan (TNM) and Kovacs–Aklonis–Hutchinson–Ramos fail to fully capture this phenomenon. Here we propose a model that can predict the temperature-dependent nonexponential behavior observed in glass-forming liquids and glasses by fitting standard differential scanning calorimetry curves. This model extends the TNM framework of structural relaxation by introducing a distribution of equilibrium fictive temperature ( T f e ) that accounts for heterogeneity in the undercooled liquid. This distribution is then frozen at the glass transition to account for the heterogeneous nature of the glass dynamics. The nonexponentiality parameter βKWW is obtained as a function of temperature by fitting the Kohlrauch-Williams-Watts (KWW) equation to the calculated relaxation function for various organic and inorganic undercooled liquids and glasses. The calculated temperature dependent βKWW shows good agreement with the experimental ones. We successfully model the relaxation dynamics far from equilibrium for two silicate systems that the TNM model fails to describe, confirming that temperature dependent nonexponentiality is necessary to fully describe these dynamics. The model also simulates the fluctuation of fictive temperature δTf during isothermal annealing with good qualitative agreement with the evolution of enthalpy fluctuation reported in the literature. We find that the evolution of enthalpy fluctuation during isothermal annealing heavily depends on the cooling rate, a dependence that was not previously emphasized. [ABSTRACT FROM AUTHOR]

Owing to their ability for fast switching and the large property contrast between the crystalline and amorphous states that permits multi-level data storage, in-memory computing and neuromorphic computing, the investigation of phase change materials (PCMs) remains a highly active field of research. Yet, the continuous increase in electrical resistance (called drift) observed in the amorphous phase has so far hindered the commercial implementation of multi-level data storage. It was recently shown that the resistance drift is caused by aging-induced structural relaxation of the glassy phase, which is accompanied by a simultaneous decrease in enthalpy and fictive temperature. This implies that resistance is related to enthalpy relaxation. While the resistance is known to drift even at room temperature and below, evidence for enthalpy relaxation at room temperature in amorphous PCMs is still missing. Here, we monitor changes in enthalpy induced by long-term room-temperature aging in a series of PCMs. Our results demonstrate the simultaneity of resistance drift and enthalpy relaxation at room temperature, and thus provide further insights into the mechanism of resistance drift and its possible remediation. [ABSTRACT FROM AUTHOR]

The glass transition (Tg) behavior and enthalpy recovery of polystyrene nanorods within an anodic aluminum oxide (AAO) template (supported nanorods) and after removal from AAO (unsupported nanorods) is studied using Flash differential scanning calorimetry. Tg is found to be depressed relative to the bulk by 20 ± 2 K for 20 nm-diameter unsupported polystyrene (PS) nanorods at the slowest cooling rate and by 9 ± 1 K for 55 nm-diameter rods. On the other hand, bulk-like behavior is observed in the case of unsupported 350 nm-diameter nanorods and for all supported rods in AAO. The size-dependent Tg behavior of the PS unsupported nanorods compares well with results for ultrathin films when scaled using the volume/surface ratio. Enthalpy recovery was also studied for the 20 and 350 nm unsupported nanorods with evolution toward equilibrium found to be linear with logarithmic time. The rate of enthalpy recovery for the 350 nm rods was similar to that for the bulk, whereas the rate of recovery was enhanced for the 20 nm rods for down-jump sizes larger than 17 K. A relaxation map summarizes the behavior of the nanorods relative to the bulk and relative to that for the 20 nm-thick ultrathin film. Interestingly, the fragility of the 20 nm-diameter nanorod and the 20 nm ultrathin film are identical within the error of measurements, and when plotted vs departure from Tg (i.e., T − Tg), the relaxation maps of the two samples are identical in spite of the fact that the Tg is depressed 8 K more in the nanorod sample. [ABSTRACT FROM AUTHOR]

The glassy state of zeolitic imidazolate frameworks (ZIFs) has shown great potential for energy-related applications, including solid electrolytes. However, their thermal conductivity (κ), an essential parameter influencing thermal dissipation, remains largely unexplored. In this work, using a combination of experiments, atomistic simulations, and lattice dynamics calculations, we investigate κ and the underlying heat conduction mechanism in ZIF glasses with varying ratios of imidazolate (Im) to benzimidazolate (bIm) linkers. The substitution of bIm for Im tunes the node–linker couplings but exhibits only a minor impact on the average diffusivity of low-frequency lattice modes. On the other hand, the linker substitution induces significant volume expansion, which, in turn, suppresses the contributions from lattice vibrations to κ, leading to decreased total heat conduction. Furthermore, spatial localization of internal high-frequency linker vibrations is promoted upon substitution, reducing their mode diffusivities. This is ascribed to structural deformations of the bIm units in the glasses. Our work unveils the detailed influences of linker substitution on the dual heat conduction characteristics of ZIF glasses and guides the κ regulation of related hybrid materials in practical applications. [ABSTRACT FROM AUTHOR]

We study heat exchange in temperature-biased metal–molecule–metal molecular junctions by employing the molecular dynamics simulator LAMMPS. Generating the nonequilibrium steady state with Langevin thermostats at the boundaries of the junction, we show that the average heat current across a gold–alkanedithiol–gold nanojunction behaves physically, with the thermal conductance value matching the literature. In contrast, the full probability distribution function for heat exchange, as generated by the simulator, violates the fundamental fluctuation symmetry for entropy production. We trace this failure back to the implementation of the thermostats and the expression used to calculate the heat exchange. To rectify this issue and produce the correct statistics, we introduce single-atom thermostats as an alternative to conventional many-atom thermostats. Once averaging heat exchange over the hot and cold thermostats, this approach successfully generates the correct probability distribution function, which we use to study the behavior of both the average heat current and its noise. We further examine the thermodynamic uncertainty relation in the molecular junction and show that it holds, albeit demonstrating nontrivial trends. Our study points to the need to carefully implement nonequilibrium molecular dynamics solvers in atomistic simulation software tools for future investigations of noise phenomena in thermal transport. [ABSTRACT FROM AUTHOR]

Both shock and shockless compression experiments were performed on laser powder bed fusion (LPBF) Ti–5Al–5V–5Mo–3Cr (Ti-5553) to peak compressive stresses near 15 GPa. Experiments were performed on the as-built material, containing a purely β (body centered cubic) microstructure, and two differing heat treatments resulting in a dual phase α (hexagonal close packed) and β microstructure. The Hugoniot, Hugoniot elastic limit (HEL), and spallation strength were measured and compared to wrought Ti-6Al-4V (Ti-64). The results indicate the LPBF Ti-5553 Hugoniot response is similar between heat treatments and to Ti-64. The HEL stress observed in the LPBF Ti-5553 was considerably higher than Ti-64, with the as-built, fully β alloy exhibiting the largest values. The spallation strength of the LPBF Ti-5553 was also similar to Ti-64. Clear evidence of initial porosity serving as initiation sites for spallation damage was observed when comparing computed tomography measurements before and after loading. Post-mortem scanning electron microscopy images of the recovered spallation samples showed no evidence of retained phase changes near the spall plane. The spall plane was found to have kinks aligned with the loading direction near areas with large concentrations of twin-like, crystallographic defects in the as-built condition. For the heat-treated samples, the concentrations of twin-like, crystallographic defects were absent, and no preference for failure at the interface between the α and β phases was observed. [ABSTRACT FROM AUTHOR]

We present the study of the structure–dynamics correlation for systems interacting via attractive Lennard-Jones (LJ) and its repulsive counterpart, the Weeks–Chandler–Andersen (WCA) potentials. The structural order parameter (SOP) is related to the microscopic mean-field caging potential. At a particle level, the SOP shows a distribution. Although the two systems have similar pair structures, their average SOP differs. However, this difference alone is insufficient to explain the well known slowing down of the dynamics in the LJ system at low temperatures. The slowing down can be explained in terms of a stronger coupling between the SOP and the dynamics. To understand the origin of this system specific coupling, we study the difference in the microscopic structure between the hard and soft particles. We find that for the LJ system, the structural differences of the hard and soft particles are more significant and have a much stronger temperature dependence compared to the WCA system. Thus, the study suggests that attractive interaction creates more structurally different communities. This broader difference in the structural communities is probably responsible for stronger coupling between the structure and dynamics. Thus, the system specific structure–dynamics correlation, which also leads to a faster slowing down in the dynamics, appears to have a structural origin. A comparison of the predictive power of our SOP with the local energy and two body excess entropy in determining the dynamics shows that in the LJ system, the enthalpy plays a dominant role and in the WCA system, the entropy plays a dominant role, and our SOP can capture both these contributions. [ABSTRACT FROM AUTHOR]

From the perspective of a bond-order-length-strength correlation, we put forward an analytical solution to describe the size, shape, and wall thickness dependency of melting temperature, entropy, and enthalpy for metallic nanostructures. Theoretical reproduction of measurements clarified that (i) when the crystal size reduces, the atomic coordination number lowers, the atomic cohesive energy decreases, and the surface-to-volume ratio increases; (ii) at the same equivalent radius, with the decrease in the number of sides for polyhedral nanoparticles and polygonal nanowires or nanotubes, the melting temperature, entropy, and enthalpy depress; and (iii) the melting temperature, entropy, and enthalpy of nanotubes are always lower than those of nanowires with the same cross-sectional radius. The present formulation is accurate and convenient, which not only shows deeper insight into the physical origins of a melting thermodynamic property response to perturbations but also provides guidance for the design and optimization of electronic nanodevices. [ABSTRACT FROM AUTHOR]

The distributed flow calorimeter is employed to measure reaction enthalpy, mixing enthalpy, and other thermodynamic parameters of hydrocarbon fuels. This information serves as a foundation for selecting and developing hydrocarbon fuels for hypersonic flight. The fluid temperature in the tube is a key factor in characterizing its thermodynamic behavior. Given the challenges of monitoring fluid temperature within a tube using current flow calorimetry, a distributed method for calculating fluid temperature in tubes under high-temperature conditions is proposed. This method realizes the interpolation of the enthalpy function of the experimental fluid through several sets of experiments with varying power levels. The fluid temperature in the tube is calculated by considering the microelement as the research object. First, the methodology for calculating fluid temperature in narrow pipes across a wide temperature range is presented. Second, the simulation model of the flow calorimeter is established, and the methodology is verified through numerical simulation. Finally, a flow calorimetric experimental device is setup. N-decane was used as the fluid in the experiment, and the temperature was calculated, and the calculated results were compared with the NIST data. In the temperature range of 295.50–609.38 K, the relative error range of the calculation of n-decane temperature is −0.61% to 1.24%. The experimental results show that the method can effectively estimate the fluid temperature of the distributed flow calorimeter. [ABSTRACT FROM AUTHOR]

With advances in research on hypersonic vehicles, the precise simulation of the effects of thermochemical non-equilibrium has become increasingly important in their design. In light of this, this study explores the influence of high-temperature thermochemical non-equilibrium on the characteristics of the flow field around the hypersonic wings of an aircraft. We initially conducted a numerical simulation by using the model of flow through a cylinder to validate the accuracy and reliability of an 11-species gas model in representing high-enthalpy flow fields. Subsequently, a systematic analysis was conducted on the impact of thermochemical nonequilibrium effects on the temperature, pressure, and enthalpy distribution in the flow field around a symmetric diamond wing under different Mach numbers and angles of attack. The research results indicated that the deeper reason behind the differing thermochemical nonequilibrium effects in the flow field at various Mach numbers lies in the distinct distribution of enthalpy of the air components at different locations, which provided a new perspective for understanding flow field variations from the standpoint of enthalpy. It is disclosed that the thermochemical non-equilibrium significantly altered the characteristics of the flow field, particularly at high Mach numbers and angles of attack, with a significant impact on the aerodynamic parameters of both the windward and the leeward sides of the wing. Through explaining the mechanisms of thermochemical non-equilibrium under flow fields with different structures, this study provides a theoretical foundations for and a fresh perspective on the design of hypersonic vehicles. [ABSTRACT FROM AUTHOR]

Although extensive experimental and numerical investigations have been performed for a jet in crossflow (JICF), the formation mechanism and vorticity source of its wake vortex are still not well understood. In the present study, large eddy simulations were conducted to analyze the wake vortex structures for a JICF with a jet-to-crossflow velocity ratio of 3.3 and a Reynolds number of 2100. The proper orthogonal decomposition analysis and the numerical smoke experiment reveal that jet sheds a significant amount of vorticity into the wake vortex. Also, the vorticity generated near the bottom wall of crossflow is pulled into the wake vortex due to the higher wall-normal velocity. Therefore, the wake vortex of JICF originates from both the jet and the bottom wall of crossflow (not just either of them). Furthermore, the role of the wake vortex in turbulent heat transport was examined. The wake vortex with a large vorticity ( | ω z + | ≥ 1.3) contributes to 49% of the total heat flux in the vertical direction, although its occurrence ratio is only 26%. Hence, the wake vortex with a large vorticity plays an important role in the turbulent heat transport in the vertical direction. [ABSTRACT FROM AUTHOR]

The total internal partition sum, Qint(T), and the translational partition sum, Qtrans(T), were computed for six isotopologues of NO: 14N16O, 15N16O, 14N18O, 14N17O, 15N18O, 15N17O. These were used to determine the total partition sum, Q(T), and its first and second moments, Q ̃ ′ T and Q ̃ ″ T . The total internal partition sum was computed using term values determined by Qu et al. [Mon. Not. R. Astron. Soc. 504, 5768–5777 (2021)] for 14N16O and those of Wong et al. [Mon. Not. R. Astron. Soc. 470, 882–897, (2017)] for the other isotopologues. These term values are the best available and hence provide the most accurate total internal partition sums and its first and second moments. The uncertainties in Qint(T), its moments, and the resulting thermodynamic functions were determined from the uncertainty in the term values and the uncertainty due to the convergence of the partition sum and its moments. From these quantities, the isobaric heat capacity, Helmholtz energy, entropy, enthalpy, Gibbs function, and the JANAF functions hef and gef, and their uncertainties, were computed on a 1 K grid from 1 to 9000 K. The data are compared with the literature values. The resulting thermodynamic quantities are the most accurate determined from direct summation of Q(T), Q ̃ ′ T , and Q ̃ ″ T . [ABSTRACT FROM AUTHOR]

A common belief is that any closed, counterclockwise cycle on a pV diagram represents a refrigerator or heat pump. It has been established that this is not the case, but previous papers on this topic have made unnecessary assumptions about the temperatures of the energy reservoirs and about how the system exchanges energy with the reservoirs. Relaxing these assumptions leads to a wide array of unexpected behaviors. In some cases, the same pV cycle can be a heat pump, a cold pump, or a Joule pump simply by changing how the system is connected to the reservoirs. This paper explores the strange world of counterclockwise cycles. Editor's note: In this paper, author Randall Knight explores the rich behavior of counterclockwise thermodynamic cycles. A counterclockwise cycle can function as a heat pump or refrigerator, but this is not the only possibility. The choice of thermal reservoirs and the choice of which reservoir heat is absorbed from and exhausted to during the cycle affect the coefficient of performance and even the basic function of the device. The author illustrates these possibilities through an analysis of counterclockwise Carnot, Kelvin, Brayton, and Stirling cycles. The analysis includes interesting possibilities, such as a cycle that operates with a single reservoir, as well as practical applications like the role of heat exchangers. The surprising results of this analysis will likely be of interest to anyone who has studied thermodynamics, and the material can easily be incorporated into any course that includes thermodynamics, from introductory physics to graduate study. [ABSTRACT FROM AUTHOR]

Interplay of Coulomb interaction energy, free ion entropy, and conformational elasticity is a fascinating aspect in polyelectrolytes (PEs). We develop a theory for complexation of two oppositely charged PEs, a process known to be the precursor to the formation of complex coacervates in PE solutions, to explore the underlying thermodynamics of complex formation, at low salts. The theory considers general degrees of solvent polarity and dielectricity within an implicit solvent model, incorporating a varying Coulomb strength. Explicit calculation of the free energy of complexation and its components indicates that the entropy of free counterions and salt ions and the Coulomb enthalpy of bound ion-pairs dictate the equilibrium of PE complexation. This helps decouple the self-consistent dependency of charge and size of the uncomplexed parts of the polyions, derive an analytical expression for charge, and evaluate the free energy components as functions of chain overlap. Complexation is observed to be driven by enthalpy gain at low Coulomb strengths, driven by entropy gain of released counterions but opposed by enthalpy loss due to reduction of ion-pairs at moderate Coulomb strengths, and progressively less favorable due to enthalpy loss at even higher Coulomb strengths. The total free energy of the system is found to decrease linearly with an overlap of chains. Thermodynamic predictions from our model are in good quantitative agreement with simulations in literature. [ABSTRACT FROM AUTHOR]

We performed calorimetric measurements on 30 bulk metallic glasses, each differing in their mixing entropies Δ S mix . On this basis, the excess entropies Δ S and excess enthalpies Δ H of glasses with respect to their maternal crystalline states are calculated. It is found that the excess entropy Δ S on the average decreases with increasing mixing entropy Δ S mix . This means that the so-called "high-entropy metallic glasses" (i.e., the glasses having high Δ S mix ) actually constitute glasses with low excess entropy Δ S. We predict that such glasses should have reduced relaxation ability. We also found that the excess enthalpy Δ H of glass linearly increases with its excess entropy Δ S , in line with a general thermodynamic estimate. [ABSTRACT FROM AUTHOR]

Near-space hypersonic vehicles could encounter significant rarefied nonequilibrium effects during the flight through atmosphere, which largely influence the gas-surface momentum and heat transfer. In this paper, hypersonic boundary layer over a flat plate with velocity slip, temperature jump, and shear nonequilibrium effects is theoretically considered. The slip boundary conditions and nonlinear transport relations are embedded into the boundary-layer equations to describe the flow. Local similar solutions are derived, and key parameters for characterizing slip and shear nonequilibrium effects are determined. The velocity-slip and temperature-jump effects are determined by [ (2 − σ u) / σ u ] M a e / R e x and [ (2 − σ T) / σ T ] M a e / R e x respectively, and the shear nonequilibrium effect is characterized by M a e 2 / R e x . The obtained boundary-layer solutions are compared with the Navier–Stokes solutions for a Mach 4.5 slip flow, and the results of Direct Simulation Monte Carlo for a Mach 10 rarefied flow, good agreements are achieved. The separate and combined effects of velocity slip, temperature jump, and shear nonequilibrium on boundary-layer solutions and momentum/heat transfer are clarified. The results show that both the slip and shear nonequilibrium effects cause the boundary layer to become thinner and decrease the skin friction and Fourier heat conduction. However, with including sliding friction, the total heat flux might even increase as the slip degree increases. These results provide valuable insight into the boundary-layer characteristics of hypersonic near-continuum flows. [ABSTRACT FROM AUTHOR]

Using a validated computational approach, the present study examines the flame structure and emission production by spray combustion in an unconfined, swirl-free lab burner. Some species, such as acetylene, a precursor to the formation of polycyclic aromatic hydrocarbons, are generated within the fuel-rich region. A smaller area of the enclosed region reduces the mass concentration of emissive species. This can be accomplished by modifying the operating conditions, such as the spray characteristics, macro-flow velocity, and nozzle geometry. Increasing the co-flow velocity has a significant effect on transforming the flame structure from a single-reaction regime to a double-structure regime. The fuel-rich area shrinks as the co-flow velocity increases, resulting in a decrease in emissive species but a fall in total heat generation. In terms of air passage design, it appears that altering the air passage area has a noticeable impact on the flame structure, where a reaction zone can be established within the flame core. Depending on the equivalence ratio, the total heat generation and output emissions can be modified through the burner air passage improvement, resulting in a 90 % decrease in the production of emissive species and an 18 % increase in total heat production. [ABSTRACT FROM AUTHOR]

Boron, an element of captivating chemical intricacy, has been surrounded by controversies ever since its discovery in 1808. The complexities of boron stem from its unique position between metals and insulators in the Periodic Table. Recent computational studies have shed light on some of the stable boron allotropes. However, the demand for multifunctionality necessitates the need to go beyond the stable phases into the realm of metastability and explore the potentially vast but elusive metastable phases of boron. Traditional search for stable phases of materials has focused on identifying materials with the lowest enthalpy. Here, we introduce a workflow that uses reinforcement learning coupled with decision trees, such as Monte Carlo tree search, to search for stable and metastable boron phases, with enthalpy as the objective. We discover new boron metastable phases and construct a phase diagram that locates their phase space (T, P) at different levels of metastability (ΔG) from the ground state and provides useful information on the domains of relative stability of the various stable and metastable boron phases. [ABSTRACT FROM AUTHOR]

Two correlations for the ionization constant of water, log10 Kw, over extended temperature and pressure/density ranges have been proposed in the literature: the Marshall–Franck and Bandura–Lvov formulations. The question remains how well these correlations reproduce the experimental values of ΔrHo, Δ r C p o , and ΔrVo, i.e., the standard changes of the enthalpy, heat capacity, and volume of reaction of water ionization. The answer to this question is the main goal of this communication. First, the analytical expressions for calculating ΔrHo, Δ r C p o , and ΔrVo were derived for the Marshall–Franck and Bandura–Lvov models. Then the calculated values of ΔrHo, Δ r C p o , and ΔrVo were compared with the experimental results from the literature. Although the performance of both correlating models can be termed satisfactory, they do not reproduce existing ΔrHo, Δ r C p o , and ΔrVo data within their expected uncertainties, contrary to the situation with log10 Kw. On the other hand, it appears that the potential for the quantitative reproduction of ΔrHo, Δ r C p o , and ΔrVo exists. It is suggested that the ΔrHo, Δ r C p o , and ΔrVo data should be included in the dataset for the global fit of data when developing formulations for log10 Kw. [ABSTRACT FROM AUTHOR]

This work presents a novel study of radiative heat transfer between closely separated plates based on an extension of Planck's spectrum of thermal radiations to systems with a steady heat flux. This extension together with electromagnetic wave theory is chosen specifically to avoid the commonly used so-called fluctuation dissipation theory, which is also limited to equilibrium systems. The spectrum of thermal radiation with a heat flux is described by the introduction of an analog of a chemical potential, which creates a bias toward the direction of heat transfer. This is the first comprehensive study of radiative heat transfer based on the generalization of Planck's spectrum for systems with a heat flux, which eliminates contradictions arising when a heat flux is described in terms of the laws limited to equilibrium systems. The total heat flux is split into fluxes carried by waves with different frequencies, directions of propagation, and polarizations. This simplifies the analysis because due to the stochastic independence, the energy fluxes of such waves are additive, and this also reveals that the heat carrying capacity of radiation with the parallel polarization is significantly higher than that of the perpendicularly polarized radiation. This suggests that the rate of radiative heat transfer may be noticeably increased by the control of the polarization of thermal radiation. [ABSTRACT FROM AUTHOR]

Gibbs energies for reactions involving aqueous ions are challenging to predict due to the large solvation energies of such ions. A stringent test would be the ab initio reproduction of the aqueous-phase chelate effect, an entropic effect in reactions of very small enthalpy changes. This paper examines what is required to achieve such a reproduction for the paradigmatic reaction M(NH3)42+ + 2 en → M(en)22+ + 4 NH3 (en = 1,2-ethylenediamine), for which ΔrxnG* and ΔrxnH* are −2.3 and +1.6 kcal mol−1, respectively, if M = Zn. Explicit solvation via simulation was avoided in order to allow sufficiently accurate electronic structure models; this required the use of continuum solvation models (CSMs), and a great deal of effort was made in attempting to lower the relative errors of ΔsolvG*[M(NH3)42+] vs ΔsolvG*[M(en)22+] from the CSMs available in Gaussian software. CSMs in ADF and JDFTx software were also tested. A uniform 2.2 kcal mol−1 accuracy in ΔrxnG* for all three metal-atom choices M = {Zn, Cd, Hg} was eventually achieved, but not from any of the known CSMs tested, nor from cavity size reoptimization, nor from semicontinuum modeling: post facto solvation energy corrections [one per solute type, NH3, en, M(NH3)42+, M(en)22+] were needed. It is hoped that this study will aid (and encourage) further CSM development for coordination-complex ions. [ABSTRACT FROM AUTHOR]

Using a laser-induced local-heating experiment combined with temperature analysis, we observed the composition-dependent sign inversion of the Soret coefficient of SiO2 in binary silicate melts, which was successfully explained by a modified Kempers model used for describing the Soret effect in oxide melts. In particular, the diffusion of SiO2 to the cold side under a temperature gradient, which is an anomaly in silicate melts, was observed in the SiO2-poor compositions. The theoretical model indicates that the thermodynamic mixing properties of oxides, partial molar enthalpy of mixing, and partial molar volume are the dominant factors for determining the migration direction of the SiO2 component under a temperature gradient. [ABSTRACT FROM AUTHOR]

Using first-principles calculations in combination with special quasirandom structure and occupation control matrix methods, we study the magnetic ordering and the effect of pressure on manganese sulfide polymorphs. At ambient conditions, MnS is commonly observed in paramagnetic rock salt structure, but as the temperature decreases at constant pressure, it becomes antiferromagnetic. On the other hand, at room temperature, MnS has shown to undergo structural transformations as pressure increases. Here, we show that our approach involving the ordering/disordering of the local magnetic moments in addition to the explicit control of the localization of the Mn d -electrons produces energy bandgaps and local magnetic moments in excellent agreement with those observed experimentally, particularly for paramagnetic MnS. Finally, we focus on how MnS evolves under pressure, and from its enthalpy landscape, we identify at about 21 GPa, the structural transformation from rock salt to orthorhombic MnP-type. This structural transformation resembles closely experimental results in which a new stable but unidentified MnS phase was previously reported. [ABSTRACT FROM AUTHOR]

Distributions of Eu2+ and Eu3+ do affect the optical properties. However, the substitution of the activator ions hardly perturbed the crystal structure of the host lattice. Without the differences in crystal structure, it is not trivial to develop an effective descriptor to investigate stoichiometry-dependent mechanism to explore the effects of Eu species on valence states. In this study, through x-ray nanodiffraction, x-ray fluorescence, x-ray absorption near edge structure, and x-ray excited optical luminescence, we mapped the valence state distributions of Eu species to calculate the local mixing enthalpy and entropy. The calculated thermodynamics parameters show good agreement with the optical properties. We found that Eu2+ of Eu-doped BaAl2O4 predominantly existed in a divalent state, which results in segregation phenomena of local Eu2+ and Eu3+ ions. [ABSTRACT FROM AUTHOR]

Distributions of Eu2+ and Eu3+ do affect the optical properties. However, the substitution of the activator ions hardly perturbed the crystal structure of the host lattice. Without the differences in crystal structure, it is not trivial to develop an effective descriptor to investigate stoichiometry-dependent mechanism to explore the effects of Eu species on valence states. In this study, through x-ray nanodiffraction, x-ray fluorescence, x-ray absorption near edge structure, and x-ray excited optical luminescence, we mapped the valence state distributions of Eu species to calculate the local mixing enthalpy and entropy. The calculated thermodynamics parameters show good agreement with the optical properties. We found that Eu2+ of Eu-doped BaAl2O4 predominantly existed in a divalent state, which results in segregation phenomena of local Eu2+ and Eu3+ ions. [ABSTRACT FROM AUTHOR]

A novel method to characterize a supersonic plasma jet using a double-jacketed enthalpy probe is presented and applied to Ar supersonic plasma jets generated by a plasma torch operated at an input power level of 5.7 kW and a chamber pressure of 2.3 kPa. The basis of this method is to measure total stagnation pressure, total enthalpy, and static pressure at the backside of a shock wave formed in front of the probe with a single insertion of the probe. Once these three variables are known, normal shock relations before and after the shock wave can disclose information on static pressures, Mach numbers, temperatures, and velocities of the supersonic plasma jet under a calorically perfect gas assumption. For example, measurement experiments carried out with the proposed probe revealed that static pressure of Ar supersonic plasma jet oscillated around the chamber pressure of 2.3 kPa in a range of 1–5 kPa along the jet axis, clearly showing an aerodynamic non-equilibrium. Corresponding to the behaviors of static pressures, Mach numbers also oscillated in the range of 1.1–3.5 along the jet axis. In addition, oscillation patterns of static pressures and Mach numbers agreed well with those of compression and expansion wave zones observed in the photograph of an over-expanded Ar supersonic plasma jet. Although relatively large errors were accompanied due to a low input power level, plasma temperatures and velocities were measured to be decreasing and increasing, respectively, in the expansion wave zone while opposite behaviors were observed in the compression wave zone. [ABSTRACT FROM AUTHOR]

This work extends Doak's momentum potential theory to multi-chemical-component and reactive, time-stationary fluctuating flows. Additional mixture-related components are found to be superimposed on the canonical vortical, acoustic, and thermal parts of momentum fluctuations and total fluctuating enthalpy. These extended relations are used to develop a time-averaged model that relates the acoustic power radiated to the far-field with clearly defined vortical, acoustic, thermal, and compositional near-field sources. The resulting model is designed to offer a more general and comprehensive way to describe the noise generated within combustion chambers. [ABSTRACT FROM AUTHOR]

Due to the extensive usage of superhydrophobic surfaces, numerous studies have investigated the dynamics and heat transfer of a droplet impacting on superhydrophobic surfaces. However, previous studies did not consider the actual superhydrophobic surfaces with randomly distributed rough structures, especially so in heat transfer of droplet impacting on superhydrophobic surfaces with random rough structures. To address this issue, a multiple distribution function phase-field lattice Boltzmann model was developed to model the droplet impacting on randomly rough surfaces. After experimental validation, this model was used in the analysis of the impacting dynamics and heat transfer characteristics. The differences between actual randomly rough surface and ideal smooth surface were revealed. Herein, random rough structures significantly influence the wetting state and heat transfer of impacting droplet on solid surface. Moreover, the effects of roughness on droplet bouncing ability and the total transferred heat were evaluated. The results show that the random rough surface with smaller skewness, a kurtosis of 3.0, and a standard deviation of 0.3 μm could simultaneously promote impacting droplet to rebound from the surface and to reduce the total transferred heat. Subsequently, the predictive correlation for total transferred heat was proposed based on the roughness parameters. This work provides novel insights into the design of rough structures on functional superhydrophobic surfaces. [ABSTRACT FROM AUTHOR]

The hypersonic high enthalpy nitrogen flows over spheres are investigated by high-fidelity state-to-state (StS) modeling. The objective of the study is to understand the nonequilibrium behaviors in the shock layer, including the stagnation line features, surface heat transfer rate, and near-wall properties inside the thermal boundary layer. Two cases with the freestream total enthalpies of 16.5 and 15.5 MJ/kg are considered, and the numerical results are compared with the experimental data. The StS model yields an accurate prediction of the shock stand-off distance with the experiment rather than an underestimation by the traditional two-temperature model. Both the StS and two-temperature models provide general agreement of the stagnation point heat flux with the experiment. In comparison, the heat flux obtained by the StS model is lower than the two-temperature model. Note that our work finds distinctive behaviors of near-wall properties. The vibrational energy is not accommodated with the sphere surface and is in thermal nonequilibrium with the translational energy, with evidence showing that the vibrational temperature is much higher than the wall temperature and the translational temperature. The values of vibrational temperature in the immediate vicinity of the stagnation point are 9.3 and 10.0 times the wall temperature for the cases with total enthalpies of 16.5 and 15.5 MJ/kg, respectively. Moreover, the vibration temperature demonstrates a nonmonotonic variation trend with a local minimum, which can be explained by the nonequilibrium distributions of vibrational energy states due to vibrational-translational energy transfer and molecular recombination. [ABSTRACT FROM AUTHOR]