Chemical Potential Difference Research Articles

Sodium ion conduction in perovskite-type sodium lanthanum niobate ceramics

The electrical conductivity of NaxLa(1−x)/3NbO3 ceramics has been studied over a composition range of 0.15 ≤ x ≤ 0.45 to identify optimal conductivity conditions and to elucidate the structural and chemical factors affecting the Na+ ion conductivity. The composition with x = 0.25 achieves the highest total conductivity of 7.0 × 10−4 S cm−1 at 350 °C, with Na+ ion transference number of unity. The random distribution of Na, La and vacancy in the two crystallographically independent A sites in perovskite structures significantly impacts the conductivity. In addition, NaxLa(1−x)/3NbO3 perovskite ceramics exhibit high dielectric constants (εr = 220−470) and suppressed electronic conductivity, making them potentially beneficial as an interfacial material to mitigate chemical potential differences between electrolytes and electrode active materials.

Using the total chemical potential to generalize the capillary pressure concept and therefrom derive a governing equation for two-phase flow in porous media

This work presents a governing equation (GE) for two-phase flow in porous media connecting capillary pressure to frictional pressure loss and external chemical potential supplied to a system in either stationary or diffusive equilibrium. It is based on the difference between non-wetting and wetting phase chemical potential (physically, pressure or energy density), which leads to a generalization of the capillary pressure concept. The difference in phase internal chemical potentials is characterized by changes in both interfacial areas and entropy densities due to variation in fluid saturations and is balanced by the system external chemical potential supplied. A definition of the capillary pressure concept is formulated based on the diffusive equilibrium criterion. The GE can explain the origin of the dynamic capillary pressure term, hysteresis, and connect the shift in the capillary pressure curve upon injecting water phases with varying salinities to all the other chemical potentials acting. It can connect, constrain, and potentially quantify all effects which can be formulated in terms of chemical potentials since it is based on a balance equation all two-phase flow systems must obey when either in stationary or diffusive equilibrium.

Generalized Einstein relations between absorption and emission spectra at thermodynamic equilibrium

We present Einstein coefficient spectra and a detailed-balance derivation of generalized Einstein relations between them that is based on the connection between spontaneous and stimulated emission. If two broadened levels or bands overlap in energy, transitions between them need not be purely absorptive or emissive. Consequently, spontaneous emission can occur in both transition directions, and four Einstein coefficient spectra replace the three Einstein coefficients for a line. At equilibrium, the four different spectra obey five pairwise relationships and one lineshape generates all four. These relationships are independent of molecular quantum statistics and predict the Stokes' shift between forward and reverse transitions required by equilibrium with blackbody radiation. For Boltzmann statistics, the relative strengths of forward and reverse transitions depend on the formal chemical potential difference between the initial and final bands, which becomes the standard chemical potential difference for ideal solutes. The formal chemical potential of a band replaces both the energy and degeneracy of a quantum level. Like the energies of quantum levels, the formal chemical potentials of bands obey the Rydberg-Ritz combination principle. Each stimulated Einstein coefficient spectrum gives a frequency-dependent transition cross-section. Transition cross-sections obey causality and a detailed-balance condition with spontaneous emission, but do not directly obey generalized Einstein relations. Even with an energetic width much less than the photon energy, a predominantly absorptive forward transition with an energetic width much greater than the thermal energy can have such an extreme Stokes' shift that its reverse transition cross-section becomes predominantly absorptive rather than emissive.

Thermodynamics-based unsaturated hydro-mechanical-chemical coupling model for wellbore stability analysis in chemically active gas formations

A thermodynamics-based unsaturated hydro-mechanical-chemical (HMC) coupling model is developed to analyze the coupled response and stability of boreholes in chemically active gas formations. The newly coupled constitutive relations are formulated by incorporating the chemical effect into the solid-gas-liquid unsaturated framework to account for the interactions between rock deformation, gas-liquid two-phase flow, and chemical potential difference. Compared with previous models, the present model shows significant prediction differences in field variables and wellbore stability evolution. The maximum absolute difference of pore pressure, effective radial stress, effective tangential stress, and collapse pressure can reach 8.98 MPa, 7.64 MPa, 7.29 MPa, 7.65 MPa, respectively. It is more conservative to select a long-term wellbore collapse pressure rather than a short-term one to guide drilling operations. The two-phase flow behavior, jointly controlled by wellbore pressure, capillary pressure, and chemical osmosis effect, provides a more realistic observation of the mud intrusion process. Compared with low salinity muds, high salinity muds can effectively impede the mud intrusion into the formation, which is more conducive to preventing wellbore collapse, but at the same time increases the risk of wellbore fracture. Sensitivity analysis shows that solute diffusion and reflection coefficients affect early wellbore stability through pore pressure and solute transport, while the chemical swelling coefficient has a long-term effect through chemically induced deformation. The results can provide theoretical guidance for quantitative optimization of mud parameters and prevention of wellbore instability when drilling in chemically active gas formations.

Bridging classical nucleation theory and molecular dynamics simulation for homogeneous ice nucleation.

Water freezing, initiated by ice nucleation, occurs widely in nature, ranging from cellular to global phenomena. Ice nucleation has been experimentally proven to require the formation of a critical ice nucleus, consistent with classical nucleation theory (CNT). However, the accuracy of CNT quantitative predictions of critical cluster sizes and nucleation rates has never been verified experimentally. In this study, we circumvent this difficulty by using molecular dynamics (MD) simulation. The physical properties of water/ice for CNT predictions, including density, chemical potential difference, and diffusion coefficient, are independently obtained using MD simulation, whereas the calculation of interfacial free energy is based on thermodynamic assumptions of CNT, including capillarity approximation among others. The CNT predictions are compared to the MD evaluations of brute-force simulations and forward flux sampling methods. We find that the CNT and MD predicted critical cluster sizes are consistent, and the CNT predicted nucleation rates are higher than the MD predicted values within three orders of magnitude. We also find that the ice crystallized from supercooled water is stacking-disordered ice with a stacking of cubic and hexagonal ices in four representative types of stacking. The prediction discrepancies in nucleation rate mainly arise from the stacking-disordered ice structure, the asphericity of ice cluster, the uncertainty of ice-water interfacial free energy, and the kinetic attachment rate. Our study establishes a relation between CNT and MD to predict homogeneous ice nucleation.

Development of Bromine Adsorbing Carbon Felt Electrode by Coating of Nitrogen-Doped Mesoporous Carbon Layer for Highly Stable Flowless Zinc-Bromine Battery

Renewable energy is well known for the extreme volatility of power production, and secondary battery-based energy storage systems (BESS) are the key to the novel and safe energy industry to expand the supply of renewable energy. Currently, lithium-ion battery-based ESS is commonly used, but the frequent ignition accidents from these ESSs rather become an obstacle to the growth of the renewable energy field. Among the redox batteries, the flowless zinc-bromine battery (FLZBB) is studied as the alternative since it uses a non-flammable and cost-effective aqueous Zn- Br2 electrolyte. However, its main challenges are that bromine (Br2) and polybromide anions (), formed at the positive electrode during the charging process, cross over to the negative electrode due to the difference in chemical potential between the electrodes. The diffused Br2 oxidizes the zinc metal, electrodeposited on the negative electrode, and causes a self-discharge reaction that consumes the charging active material and Br2 the battery performance and life. Herein, we present a nitrogen-doped mesoporous carbon coated on the pristine graphite felt fibers (NMC/GF). By uniformly forming a nitrogen-doped porous carbon material on the GF fibers through the evaporation-induced self-assembly (EISA) method, it is a simple and cost-effective method to develop the structural and properties of the GF positive electrode to increase the ability of adsorption and storing the active materials, Br2 and polybromide anions (,, and ) generated during the charging process. In addition, it also improved the bromine redox reaction kinetics by having a strong affinity with the aqueous Zn-Br2 electrolyte. This facilitates long-term charge/discharge cycles, enabling high performance and improved durability for Coulombic efficiency over 95% for 5000 cycles in the FLZBB single-cell platform at a current density of 20 mA cm-2 and a high-rate areal capacity of 2 mAh cm-2.

Hydrogen Evolution Reaction: Log j0 Versus Work Function Φ As Viewed from Transition State Theory As an Eyring Plot

In 1972, Trasatti correlated the log of the exchange current density (j0) for the hydrogen evolution reaction (HER) with the work functions of 31 metal electrodes to yield two parallel regression lines. [1] The lines are separated by Δ log j0 = 3. Thermodynamically, work function 𝚽 is the energy to remove an electron from a metal to infinity. Perhaps counterintuitively, platinum group metals (PGMs) with the highest 𝚽 sustain the highest j0 values.The elementary, interfacial electron transfer occurs between the electrode and adsorbed hydrogen cation and adsorbed hydrogen atom.H+ ads + e ⇌ H● ads A materials dependent rate expression is developed as follows. [2]The properties of the metal are introduced explicitly into reaction mechanism, characterized by M(e) and M(0), the metal electrode with and without the electron.M(e) + H+ ads ⇄ M(0) + H● ads Classical transition state theory (TST) characterizes the free energy of activation ΔG‡ as the energy difference between the transition state (TS) and the minimum energy of the reactants. The TS forms at equilibrium, where adsorbed hydrogen and metal electrode share the electron.M(e) + H+ ads ⇌ [M ●●● e ●●● Hads]‡ ⇌ M(0) + H● ads Electrochemical potentials set the energy difference in the products and reactant, which sets ΔG‡. Chemical potential (𝞵) difference for the metal without and with the electron define 𝚽. F𝚽 = 𝞵M(0) - 𝞵M(e) F𝚽 is further defined as a chemical free energy that that lowers ΔG‡. F𝚽 is a material specific property that is atypically specified in the rate equation. Because log j0 ∝ - ΔG‡, and chemical free energy F𝚽 lowers ΔG‡, log j0 ∝ F𝚽. Thus, j0 increases exponentially with F𝚽, so PGMs with highest 𝚽 sustain highest j0. Further, the rate expression embeds material specific property 𝚽.The classical Eyring perspective for generic rate constant k’ is k’ = A’ exp[-ΔG‡/RT]. Rate constant is typically determined by varying temperature in a plot of ln k’ versus T-1, where ln k’ = ln A’ - ΔG‡/RT. For isothermal measurements, log j0 is linear with 𝚽 because F𝚽 is a term ΔG‡ chem that is a component in the total ΔG‡. For metals, where 𝚽 > 0, F𝚽 always lowers ΔG‡ for HER; the total activation energy is lowered in proportion to F𝚽. The slopes of log j0 versus 𝚽 is proportional to 𝝰𝚽F𝚽/2.303, where partition coefficient 𝝰𝚽 characterizes ∂ΔG‡/∂𝚽. For the parallel lines in Trasatti’s plot, 𝝰𝚽 = 0.38. The intercepts are independent of 𝚽.The material specific rate expressions derived from classical TST and electrochemical potentials may provide guidance on design of electrocatalysts and provide a path to integration of classical and contemporary modeling of important reaction processes such as HER.

Effects of non-equilibrium phase behavior in nanopores on multi-component transport during CO2 injection into shale oil reservoir

Injecting CO2 into shale oil reservoirs is one of the most effective methods for enhancing oil recovery (EOR) while simultaneously facilitating CO2 capture, utilization, and storage (CCUS). However, it is not always that gas dissolution or condensate evaporation reaches equilibrium instantaneously during the CO2 injection process. In cases where equilibrium is not attained instantaneously, conventional vapor-liquid equilibrium models will have certain limitations in characterizing phase transition hysteresis. These limitations will affect the accuracy of simulating multi-component transport in porous media. In this paper, a robust and generic vapor-liquid non-equilibrium thermodynamic model considering nano-confinement effects (NC) was established by introducing component mass transfer rates proportional to the chemical potential difference. The established model was then used to modify the fully-compositional, projection-based embedded discrete fracture model (pEDFM). Furthermore, C++ hybrid programming and the Graphics Processing Unit (GPU) parallel method were both used to accelerate both the nonlinear and linear solvers. By comparing with results from MATLAB Reservoir Simulation Tools (MRST), Eclipse, and tNavigator, the accuracy and advantages of our solver were demonstrated. The results show that if the underground fluid undergoes a phase transition from a vapor-liquid two-phase state to a single-phase state, non-equilibrium thermodynamic effects need to be considered, and the simulation results show a larger two-phase zone, higher bottom hole pressure, and lower cumulative liquid production. But the nano-confinement effects will weaken the non-equilibrium thermodynamic effects.

Interdiffusion behavior and compositional tailoring of AlCoCrFeNiY high-entropy alloy coating on a Hastelloy-X superalloy

This study investigated the microstructural evolution and interdiffusion behavior of an AlCoCrFeNiY coating deposited on a Hastelloy-X superalloy substrate at 1050 °C, 1100 °C and 1150 °C, and compared it with a conventional NiCoCrAlY coating. Element interdiffusion behavior indicates that Al and Co diffuse inward from the coating to the substrate, while Ni and Cr diffuses outward from the substrate to the coating. However, the interdiffusion behavior of Fe is different in two types of coating/substrate systems, which results from the big difference in Fe concentration. The AlCoCrFeNiY coating undergoes extensive β to γ phase transformation than the NiCoCrAlY coating, and thermodynamic calculations suggest that Fe can dramatically extend the γ/σ two-phase region. This causes formation of a thicker β-depleted zone near the coating/substrate interface and more Cr-rich σ phase precipitates in the AlCoCrFeNiY/Hastelloy-X system. Based on thermodynamic calculations of the effect of Fe content on Y solubility and phase composition, as well as the chemical potential difference in Fe, a novel Ni23Co17Cr12Al10FeY coating is proposed to reduce element interdiffusion without sacrificing oxidation resistance.

Enhanced sludge dewatering using a novel synergistic iron/peroxymonosulfate-polyacrylamide method

In the sludge dewatering process, a formidable challenge arises due to the robust interactions between extracellular polymeric substances (EPS) and bound water. This study introduces a novel, synergistic conditioning method that combines iron (Fe2+)/peroxymonosulfate (PMS) and polyacrylamide (PAM) to significantly enhance sludge dewatering efficiency. The application of the Fe2+/PMS-PAM conditioning method led to a substantial reduction in specific filtration resistance (SFR) by 82.75% and capillary suction time (CST) by 80.44%, marking a considerable improvement in dewatering performance. Comprehensive analyses revealed that pre-oxidation with Fe2+/PMS in the Fe2+/PMS-PAM process effectively degraded EPS, facilitating the release of bound water. Subsequently, PAM enhanced the flocculation of fine sludge particles resulting from the advanced oxidation processes (AOPs). Furthermore, analysis based on the Extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) theory demonstrated shifts in interaction energies, highlighting the breakdown of energy barriers within the sludge and a transition in surface characteristics from hydrophilic (3.79 mJ m−2) to hydrophobic (−61.86 mJ m−2). This shift promoted the spontaneous aggregation of sludge particles. The innovative use of the Flory-Huggins theory provided insights into the sludge filtration mechanism from a chemical potential perspective, linking these changes to SFR. The introduction of Fe2+/PMS-PAM conditioning disrupted the uniformity of the EPS-formed gel layer, significantly reducing the chemical potential difference between the permeate and the water in the gel layer, leading to a lower SFR and enhanced dewatering performance. This thermodynamic approach significantly enhances our understanding of sludge dewatering and conditioning. These findings represent a paradigm shift, offering innovative strategies for sludge treatment and expanding our comprehension of dewatering and conditioning techniques.

Thermodynamic of solid-state sintering: Contributions of grain boundary energy

This study aimed to highlight the importance of solid-solid interfaces or grain boundaries in the thermodynamics of interfaces during the sintering of materials. Among the three chemical potentials identified in this study, the difference in chemical potential between the grain boundary and the surface emerges as the most critical factor for pore elimination. However, once equilibrium is achieved between the grain boundary and the surface, a second chemical potential associated with the difference in grain size becomes predominant, promoting a new microstructural configuration that reactivates grain boundary formation and perpetuates sintering. A third potential was identified because of the edges, contributing to the rounding of the neck region between grains. The change in interfacial energy resulting from the adsorption or segregation processes plays a pivotal role in pore elimination during sintering. Models attempting to simultaneously predict the stability of grain boundary formation and pore elimination with grain growth were revisited.

Finite Temperature String with Order Parameter as Collective Variables for Molecular Crystal: A Case of Polymorphic Transformation of TNT under External Electric Field.

An external electric field is an effective tool to induce the polymorphic transformation of molecular crystals, which is important practically in the chemical, material, and energy storage industries. However, the understanding of this mechanism is poor at the molecular level. In this work, two types of order parameters (OPs) were constructed for the molecular crystal based on the intermolecular distance, bond orientation, and molecular orientation. Using the K-means clustering algorithm for the sampling of OPs based on the Euclidean distance and density weight, the polymorphic transformation of TNT was investigated using a finite temperature string (FTS) under external electric fields. The potential of mean force (PMF) was obtained, and the essence of the polymorphic transformation between o-TNT and m-TNT was revealed, which verified the effectiveness of the FTS method based on K-means clustering to OPs. The differences in PMFs between the o-TNT and transition state were decreased under external electric fields in comparison with those in no field. The fields parallel to the c-axis obviously affected the difference in PMF, and the relationship between the changes in PMFs and field strengths was found. Although the external electric field did not promote the convergence, the time of the polymorphic transformation was reduced under the external electric field in comparison to its absence. Moreover, under the external electric field, the polymorphic transformation from o-TNT to m-TNT occurred while that from m-TNT to o-TNT was prevented, which was explained by the dipole moment of molecule, relative permittivity, chemical potential difference, nucleation work and nucleation rate. This confirmed that the polymorphic transformation orientation of the molecular crystal could be controlled by the external electric field. This work provides an effective way to explore the polymorphic transformation of the molecular crystals at a molecular level, and it is useful to control the production process and improve the performance of energetic materials by using the external electric fields.

Spontaneous Structuration of Biohydrogels by Membrane‐Free Osmosis

AbstractMany bio‐hydrogels are prepared thanks to the addition of divalent ions. These gels usually exhibit partial ionic selectivity, a feature is leveraged to instigate an osmotic flow during the gelation process across a range of bio‐hydrogels. A simple experimental setup consisting a glass capillary filled by the reactant solution is taken as an advantage, brought into contact with a reservoir of calcium chloride. Direct observation allows to characterize the gelation kinetics, the permeability and the selectivity of several gels, including some made of protein aggregates, pectin, and alginate. It is shown that these intrinsic properties, coupled with appropriate gelation kinetics, intricately govern the osmotic flow induced by the chemical potential difference of the calcium chloride ions imposed during gel formation, consistent with the Kedem–Kashalsky equation. The forming gel acts as a semi‐permeable membrane for calcium chloride ions. The consequences of this osmotic flow are of potentially great interest since it triggers an increase of the gel concentration close to its boundary, opening the road to their spontaneous structuration. The formation of this dense shell is well accounted for the combination of a mass balance and a kinetic model.

Magnon spin capacitor

In this work, we show that a magnon spin capacitor can be realized at a junction between two exchange coupled ferromagnets. In this junction, the buildup of magnon spin over the junction is coupled to the difference in magnon chemical potential, realizing the magnon spin analogue of an electrical capacitor. The relation between magnon spin and magnon chemical potential difference directly follows from considering the magnon density–density interaction between the two ferromagnets. We analyze the junction in detail by considering spin injection and detection from normal metal leads, the tunneling current across the junction, and magnon decay within the ferromagnet, showing that such a structure realizes a magnon spin capacitor in series with a spin resistor. Choosing yttrium iron garnet as the ferromagnet, we numerically calculate the magnon spin capacitance which ranges from picofarad to microfarad, depending on the area of the junction. We therefore conclude that the magnon spin capacitor could directly be of use in applications.

Real-time imaging reveal anisotropic dissolution behaviors of silver nanorods

The morphology and size control of anisotropic nanocrystals are critical for tuning shape-dependent physicochemical properties. Although the anisotropic dissolution process is considered to be an effective means to precisely control the size and morphology of nanocrystals, the anisotropic dissolution mechanism remains poorly understood. Here, using in situ liquid cell transmission electron microscopy, we investigate the anisotropic etching dissolution behaviors of polyvinylpyrrolidone (PVP)-stabilized Ag nanorods in NaCl solution. Results show that etching dissolution occurs only in the longitudinal direction of the nanorod at low chloride concentration (0.2 mM), whereas at high chloride concentration (1 M), the lateral and longitudinal directions of the nanorods are dissolved. First-principles calculations demonstrate that PVP is selectively adsorbed on the {100} crystal plane of silver nanorods, making the tips of nanorods the only reaction sites in the anisotropic etching process. When the chemical potential difference of the Cl− concentration is higher than the diffusion barrier (0.196 eV) of Cl− in the PVP molecule, Cl− penetrates the PVP molecular layer of {100} facets on the side of the Ag nanorods. These findings provide an in-depth insight into the anisotropic etching mechanisms and lay foundations for the controlled preparation and rational design of nanostructures.

Energy harvesting from acid mine drainage using a highly proton/ion-selective thin polyamide film

A huge chemical potential difference exists between the acid mine drainage (AMD) and the alkaline neutralization solution, which is wasted in the traditional AMD neutralization process. This study reports, for the first time, the harvest of this chemical potential energy through a controlled neutralization of AMD using H+-conductive films. Polyamide films with controllable thickness achieved much higher H+ conductance than a commercially available cation exchange membrane (CEM). Meanwhile, the optimal polyamide film had an excellent H+/Ca2+ selectivity of 63.7, over two orders of magnitude higher than that of the CEM (0.3). The combined advantages of fast proton transport and high proton/ion selectivity greatly enhanced the power generation of the AMD battery. The power density was 3.1 W m–2, which is over one order of magnitude higher than that of the commercial CEM (0.2 W m–2). Our study provides a new sustainable solution to address the environmental issues of AMD while simultaneously enabling clean energy production.

Ostwald ripening of gas bubbles in porous media: Impact of pore geometry and spatial bubble distribution

We study pore-scale gas bubble ripening in porous media by combining a mass transfer method based on chemical potential differences with a level-set method for updating the gas/liquid configurations. We examine the impact of pore geometry and initial gas bubble distribution on the evolution, as well as the effect of mesh refinement and numerical parameters controlling the adaptive time steps in the model. Our results show that the pore geometry has a significant impact as it determines the rate of bubble pressure change with volume, while the area for mass transfer influences the time scale of the evolution. Simulations with different spatial patterns of bubbles with high and low pressures yield different ripening behaviors, classified as local and global ripening regimes. Simulations on sandstone with volumetrically similar bubble distributions display different ripening paths depending on the initial bubble locations, emphasizing the importance of capturing displacement history before ripening investigations.

Intercalation in Li-ion batteries: thermodynamics and its relation to non-ideal solid-state diffusion

Intercalation is the key phenomenon taking place in lithium-ion batteries: while its thermodynamics sets the equilibrium voltage of active materials, solid-state diffusion of intercalated lithium determines the rate at which the battery can operate. This study revisits the thermodynamics of intercalation by treating the active material as a binary mixture of filled and empty sites, thus relating the equilibrium potential to the chemical potential difference of intercalated lithium. By setting a reference to unitary activity at half state-of-lithiation, the non-ideal behaviour of the active material is quantified via a revisited form of the thermodynamic enhancement factor, revealing that common solid-solution cathode materials as LiNi x Mn y Co1-x-y O2, LiNi0.8Co0.15Al0.05O2, and LiCoO2 show strong super-ideal behaviour. The latter is related to the thermodynamic enhancement of the diffusion coefficient of intercalated lithium. A comprehensive overview of the functional forms of Li diffusion flux according to linear irreversible thermodynamics is provided and related to the chemical diffusion coefficient obtained by conventional characterisation techniques. A literature analysis made on solid-solution cathode active materials reveals that while the chemical diffusion coefficient varies significantly with state-of-lithiation, there exists a convenient functional form of diffusion flux according to linear irreversible thermodynamics that enables a fairly stable diffusion coefficient with state-of-lithiation. This has clear benefits from both modelling and experimental viewpoints and potentially sheds light on the mechanistic fundamentals of solid-state diffusion.

Kinetics and Thermodynamics of the Phase Transformation in the Nanocrystalline Substance—Gas Phase System

This study presents a model of the reaction of a nanocrystalline substance within the gas phase, where diffusion of gas reactants in the volume of the nanocrystallites is a rate-limiting step. According to the model calculations carried out, the rate of diffusion across the phase boundary located on the nanocrystallite surface limits the rate of the process. It was stated that in chemical processes with a phase transformation, the critical concentration of absorbate depends on two factors: the specific active surface area of the adsorbent and the difference in chemical potentials between the gas phase and the equilibrium potential at which the phase transformation occurs. When the actual adsorbate potential in the gas phase is much greater than the equilibrium potential of the nanocrystallite with the largest specific active surface, nanocrystallites undergo phase changes in the order according to their specific active surfaces from the largest to the smallest. In a process where the actual adsorbate potential is close to an equilibrium one, nanocrystallites undergo phase transformation in the order of their specific active surface from the smallest to the largest.

Microstructure and corrosion properties of Cr41CoFeNi eutectic high-entropy alloy in sulfuric acid solution

A new eutectic high-entropy alloy (EHEA) of Cr41CoFeNi was prepared by arc melting technique. The microstructure and corrosion resistance of the Cr41CoFeNi EHEA were systematically investigated by EBSD, TEM, EIS and XPS analyses. The results revealed that the Cr41CoFeNi EHEA showed a dual-phase structure consisting of BCC phase and FCC phase, and the morphologies displayed the lamellar eutectic and network-shaped eutectic. Compared with 316 L stainless steel, the Cr41CoFeNi EHEA exhibited a better anti-corrosion property in 0.5 M H2SO4 solution. This was mainly attributed to the formation of a dense and stable Cr-oxide layer on the surface of Cr41CoFeNi EHEA, which retarded further dissolution of the matrix. Moreover, bound water could adsorb metal ions to form a new protective film, which played an important role in improving the corrosion resistance of the Cr41CoFeNi EHEA. However, the elemental segregation and chemical potential difference between phases increased the defects in the passive film and accelerated its pitting corrosion of low potential phase. Moreover, the (Co, Fe, and Ni)-enriched FCC structured phase was preferentially eroded.