Interface and energy band manipulation of Bi2O3-Bi2S3 electrode enabling advanced magnesium-ion storage

Rechargeable magnesium-ion(Mg-ion)batteries have attracted wide attention for energy storage.However,magnesium anode is still limited by the irreversible Mg plating/stripping procedure.Herein,a well-designed binary Bi_(2)O_(3)-Bi_(2)S_(3)(BO-BS)heterostructure is fulfilled by virtue of the cooperative interface and energy band engineering targeted fast Mg-ion storage.The built-in electronic field resulting from the asymmetrical electron distribution at the interface of electron-rich S center at Bi_(2)S_(3) side and electron-poor O center at Bi_(2)O_(3) side effectively accelerates the electrochemical reaction kinetics in the Mg-ion battery system.Moreover,the as-designed heterogenous interface also benefits to maintaining the electrode integrity.With these advantages,the BO-BS electrode displays a remarkable capacity of 150.36 mAh g^(−1) at 0.67 A g^(-1) and a superior cycling stability.This investigation would offer novel insights into the rational design of functional heterogenous electrode materials targeted the fast reaction kinetics for energy storage systems.

Interaction energy of interface dislocation loops in piezoelectric bi-crystals

Interface dislocations may dramatically change the electric properties, such as polarization, of the piezoelectric crystals. In this paper, we study the linear interactions of two interface dislocation loops with arbitrary shape in generally anisotropic piezoelectric bi-crystals. A simple formula for calculating the interaction energy of the interface dislocation loops is derived and given by a double line integral along two closed dislocation curves. Particularly, interactions between two straight segments of the interface dislocations are solved analytically, which can be applied to approximate any curved loop so that an analytical solution can be also achieved. Numerical results show the influence of the bi-crystal interface as well as the material orientation on the interaction of interface dislocation loops.

Mode-I fracture and durability of FRP-concrete bonded interfaces

In this study, a work-of-fracture method using a three-point bend beam （3PBB） specimen, which is commonly used to determine the fracture energy of concrete, was adapted to evaluate the mode-I fracture and durability of fiber-reinforced polymer （FRP） composite-concrete bonded interfaces. Interface fracture properties were evaluated with established data reduction procedures. The proposed test method is primarily for use in evaluating the effects of freeze-thaw （F-T） and wet-dry （W-D） cycles that are the accelerated aging protocols on the mode-I fracture of carbon FRP-concrete bonded interfaces. The results of the mode-I fracture tests of F-T and W-D cycle-conditioned specimens show that both the critical load and fracture energy decrease as the number of cycles increases, and their degradation pattern has a nearly linear relationship with the number of cycles. However, compared with the effect of the F-T cycles, the critical load and fracture energy degrade at a slower rate with W-D cycles, which suggests that F-T cyclic conditioning causes more deterioration of carbon fiber-reinforced polymer （CFRP）-concrete bonded interface. After 50 and 100 conditioning cycles, scaling of concrete was observed in all the specimens subjected to F-T cycles, but not in those subjected to W-D cycles. The examination of interface fracture surfaces along the bonded interfaces with varying numbers of F-T and W-D conditioning cycles shows that （1） cohesive failure of CFRP composites is not observed in all fractured surfaces; （2） for the control specimens that have not been exposed to any conditioning cycles, the majority of interface failure is a result of cohesive fracture of concrete （peeling of concrete from the concrete substrate）, which means that the cracks mostly propagate within the concrete; and （3） as the number of F-T or W-D conditioning cycles increases, adhesive failure along the interface begins to emerge and gradually increases. It is thus concluded that the fracture properties （i.e., the critical load and fracture energy） of the bonded interface are controlled primarily by the concrete cohesive fracture before conditioning and by the adhesive interface fracture after many cycles of F-T or W-D conditioning. As demonstrated in this study, a test method using 3PBB specimens combined with a fictitious crack model and experimental conditioning protocols for durability can be used as an effective qualification method to test new hybrid material interface bonds and to evaluate durability-related effects on the interfaces.

In situ formed LiF-Li_(3)N interface layer enables ultra-stable sulfide electrolyte-based all-solid-state lithium batteries

Sulfide solid electrolytes are promising for high energy density and safety in all-solid-state batteries due to their high ionic conductivity and good mechanical properties.However,the application of sulfide solid electrolytes in all-solid-state batteries with lithium anode is restricted by the side reactions at lithium/electrolytes interfaces and the growth of lithium dendrite caused by nonuniform lithium deposition.Herein,a homogeneous LiF-Li_(3)N composite protective layer is in situ formed via a manipulated reaction of pentafluorobenzamide with Li metal.The LiF-Li_(3)N layer with both high interfacial energy and interfacial adhesion energy can synergistically suppress side reactions and inhibit the growth of lithium dendrite,achieving uniform deposition of lithium.The critical current densities of Li_(10)GeP_(2)S_(12)and Li_(6)PS_(5)Cl are increased to 3.25 and 1.25 mA cm^(-2)with Li@LiF-Li_(3)N layer,which are almost triple and twice as those of Li-symmetric cells in the absence of protection layer,respectively.Moreover,the Li@LiF-Li_(3)N/Li10GeP2S12/Li@LiF-Li_(3)N cell can stably cycle for 9000 h at 0.1 mA cm^(-2)under 0.1 mA h cm^(-2),and Li@LiF-Li_(3)N/Li_(6)PS_(5)Cl/Li@LiF-Li_(3)N cell achieves stable Li plating/stripping for 8000 h at 0.1 mA cm^(-2)under10 m A h cm^(-2).The improved dynamic stability of lithium plating/stripping in Li@LiF-Li_(3)N/Li_(10)GeP_(2)S_(12)or Li_(6)PS_(5)Cl interfaces is proved by three-electrode cells.As a result,LiCoO_(2)/electrolytes/Li@LiF-Li_(3)N batteries with Li_(10)GeP_(2)S_(12)and Li_(6)PS_(5)Cl exhibit remarkable cycling stability of 500 cycles with capacity retentions of 93.5%and 89.2%at 1 C,respectively.

Dendritic tip selection during solidification of alloys:Insights from phase-field simulations

The effect of undercooling DT and the interface energy anisotropy parameter e4 on the shape of the equiaxed dendritic tip has been investigated by using a quantitative phase-field model for solidification of binary alloys.It was found that the tip radius r increases and the tip shape amplitude coefficient A4 decreases with the increase of the fitting range for all cases.The dendrite tip shape selection parameter sdecreases and then stabilizes with the increase of the fitting range,and sincreases with the increase of e4.The relationship between sand e4 follows a power-law function sµea 4,and a is independent of DT but dependent on the fitting range.Numerical results demonstrate that the predicted sis consistent with the curve of microscopic solvability theory(MST)for e4<0.02,and sobtained from our phase-field simulations is sensitive to the undercooling when e4 is fixed.

Effects of external stress aging on morphology and precipitation behavior of θ'' phase in Al-Cu alloy

The exposure of Al-5Cu alloy to an external stress with normal aging was carried out. The effects of external stress-aging on the morphology and precipitation behavior of θ＂ phase were investigated by transmission electron microscopy （TEM）, differential scanning calorimetry （DSC） and first principle calculation. The size of the θ＂ phase precipitated plates in stress-aging （453 K, 6 h, 50 MPa） is 19.83 nm, which is smaller than that of those present （28.79 nm） in stress-flee aging （453 K, 6 h）. The precipitation process of θ＂ phase is accelerated by loading external stress aging according to the analysis of DSC results. The apparent activation energy for the external stress-aging is 10% lower than the stress-free one. The first principle calculation results show that the external stress makes a decrease of 6% in the interface energy. The effects of the stress on aging process of the alloy are discussed on the basis of the classical theory. The external stress changes the morphology and precipitation behavior of θ＂ phase because the critical nucleation energy is decreased by 19% under stress aging.

Stress/strain aging mechanisms in Al alloys from first principles

First-principles based calculations were carried out to explore the possible mechanisms of stress/strain aging in Al alloys. Potential effects of temperature and external stress/strain were evaluated on the solvus boundary of Al3Se in Al-Sc alloy, and the interface energy of Al/θ＂ in Al-Cu alloys. Results show that applying tensile strain/stress during conventional aging can significantly decrease the solubility entropy, by red-shifting the phonon DOS at high states. The resulted solvus boundary would shift up on the phase diagram, suggesting a reduced solubility limit and an increased maximum possible precipitation volume of AlaSc in Al-Sc alloy. Moreover, the applied strain/stress has different impacts on the formation energies of different orientated Al/θ＂ interfaces in Al-Cu alloys, which can be further exaggerated by the Poisson effect, and eventually affect the preferential precipitation orientation in Al-Cu alloy. Both mechanisms are expected to play important roles during stress/strain aging.

An analytical solution for the elastic fields near spheroidal nano-inclusions

When the size of an inclusion shrinks to nanometers, interface energy plays an important role in the deformation around it. In the present paper, we consider the effect of interface energy on the elastic fields near a spheroidal nanoinclusion embedded in an elastic medium on the basis of surface elasticity theory. Using Boussinesq-Sadowsky potential function method, we obtain the deformation field near the inclusion subjected to a uniformly uniaxial loading at infinity. The results show that the elastic fields near the nano-inclusion depend strongly on the interface properties, the size and shape of inclusion. These new characteristics may be helpful to understand various relevant mechanical performances of nanosized inhomogeneities.

First Principle Calculation of NbC Precipitation Competition between TiC Particle and Ferrite Matrix

The electronic structure, cohesive energy and interfacial energy of ferrite（100）/NbC（100） and TiC（100）/NbC（100） interfaces have been investigated by the first-principles calculation. Moreover, the heterogeneous nuclei mechanism of NbC particle was also analyzed. The results showed that the stacking sequences have a great influence on the cohesive energy and equilibrium interfacial separation of the abovementioned interfaces. Compared with C-terminated interfaces, the cohesive energy of Nb-terminated ones is lower while the equilibrium interface distance is larger. Among the two C-terminated interface structures, the interfacial energy between the NbC and ferrite is 4.54 J/m^2, which is larger than that of NbC/TiC interface（1.80 J/m^2）. Therefore, NbC particles prefer heterogeneous nucleation on TiC particles surface rather than the ferrite matrix, which agrees well with the experimental result.

Surface Characterization and in Vitro Blood Compatibility of Poly (Ethylene Terephthalate) Immobilized with Hirudin

Poly （ethylene terephthalate）（dacron, PET） films were exposed under argon plasma glow discharge with different glows and induced polymerization of acrylic acid（AA） in order to in- troduce carboxylic acid group onto PET （PET-AA） assisted by ultraviolet radiation（UV）. Hirudin- immobilized PET （PET-HRD） films were prepared by the grafting of PET-AA, followed by chem- ical reaction with hirudin. The surface structure of the treated PET was determined by X-ray photoelectron spectroscopy （XPS）. The wettability, surface free energy, and interface free energy of the films were investigated by contact angle measurement. The blood compatibility of the films was assessed by platelet-adhesion test and fibrinogen conformational change measurements to eval- uate the viability of the materials in biomedical engineering. Measurement by scanning electron microscopy （SEM） revealed that the amounts of adhered, aggregated and morphologically changed platelets were reduced on the hirudin-immobilized PET films. Enzyme-linked-immunoassay mea- surements that disclosed fibrinogen conformational changes showed results consistent with the platelets＇ behavior.

Effects of a high magnetic field on single-phase interface evolution,additional interfacial energy and nucleation undercooling in Al-based alloy

The effects of a high magnetic field on the evolution of the single-phase interface and the liquid-solid interface energy in Al-Cu alloy were investigated experimentally.It is found that the application of the magnetic field has a significant promotion effect on the migration of liquid droplets,accelerating the formation of the single-phase interface.This should be attributed to the thermoelectric(TE)magnetic convection in the droplets which has enhanced the diffusion and increased the migration speed of liquid droplets.Further,the effect of the high magnetic field on the solid-liquid interface energy is analyzed by an improved grain boundary groove(GBG)method.The average solid-liquid interface energy of theα-Al/Al-Cu and Al2Cu/Al-Cu systems increases and decreases with the increase of the magnetic field,respectively.The above experiment results are well explained based on the formation and interaction of the magnetic dipole at the solid-liquid interface.Moreover,experimental results reveal that the magnetic-field-induced interface energy increases and decreases the nucleation undercooling of the Al-30wt.%Cu alloy and Al-35wt.%Cu alloy,respectively.By studying the effect of the magnetic-field-induced interface energy on the nucleation undercooling,the understanding of the interface energy-induced nucleation undercooling deepens.

A novel interfacial thermodynamic model for predicting solubility of nanoparticles coated by stabilizers

To improve the stability of nanoparticles in aqueous solution,polymer or surfactant,etc.are often added in solutions during the preparation process of nanoparticles,which can induce new interfaces that influence the solubility of nanoparticles.In this work,a novel interfacial thermodynamic model for describing the Gibbs energy of the nanoparticles coated by stabilizers was proposed to predict the solubility of nanoparticles.Within the developed model,the activity coefficient of nano metal system was determined by Davies model and that of nano drug system by Perturbed-Chain Statistical Associating Fluid Theory(PC-SAFT).The Gibbs energy of the interface was established as a function of molecular parameters via the application for nano metal system.Furthermore,the model was further used to predict the solubility of nano drugs itraconazole,fenofibrate,and griseofulvin.It was found that the Gibbs energy of the interface plays an important role especially when the radius of nano metal is less than 40 nm,and the developed model can predict the solubility of nano drug with high accuracy in comparison with the experimental data as well as predict the changing trend of solubility of nano drugs that increases as the particle size decreases.Meanwhile,the stabilization mechanism of stabilizers on nano drugs was studied which provided theoretical guidance for the selection of polymer or surfactant stabilizer.These findings showed that the developed model can provide a reliable prediction of the solubility of nanoparticles and help to comprehend the stabilization mechanism of the stabilizers on nano drugs with different particle sizes,which is expected to provide important information for the design of nano drugs formulations.

Theoretical analysis of droplet transition from Cassie to Wenzel state

Whether droplets transit from the Cassie to the Wenzel state （C-W） on a textured surface is the touchstone that the superhydrophobicity of the surface is still maintained. However, the C-W transition mechanism, especially the spontaneous transition of small droplets, is still not very clear to date. The interface free energy gradient of a small droplet is firstly proposed and derived as the driving force for its C-W evolution in this study based on the energy and gradient analysis. Then the physical and mathematical model of the C-W transition is found after the C-W driving force or transition pressure, the resistance, and the parameters of the meniscus beneath the droplet are formulated. The results show that the micro/nano structural parameters significantly affect the C-W driving force and resistance, The smaller the pillar diameter and pitch, the minor the C-W transition pressure, and the larger the resistance. Consequently, the C-W transition is difficult to be completed for the droplets on nano-textured surfaces. Meanwhile if the posts are too short, the front of the curved liquid-air interface below the droplet will touch the structural substrate easily even though the three phase contact line （TPCL） has not depinned. When the posts are high enough, the TPCL beneath the drop must move firstly before the meniscus can reach the substrate. As a result, the droplet on a textured surface with short pillars is easy to complete its C-W evolution. On the other hand, the smaller the droplet, the easier the C-W shift, since the transition pressure becomes larger, which well explains why an evaporating drop will collapse spontaneously from composite to Wenzel state. Besides, both intrinsic and advancing contact angles affect the C-W transition as well. The greater the two angles, the harder the C-W transition. In the end, the C-W transition parameters and the critical conditions measured in literatures are calculated and compared, and the calculations accord well with the experimental results.

Analysis of meniscus beneath metastable droplets and wetting transition on micro/nano textured surfaces

Tile expressions of interface flee energy （IFE） of composite droplets with meniscal liquid-air interlhce in metastable state on nlicro/nano textured snrfaces were formulated. Then tile parameters to describe the meniscus were determined based on the principle of minimtun 1FE. Furthermore, the IFE barriers and the necessary and sufficient conditions of drop wetting transition fl＇om Cassie to Wenzel were analyzed and the corresponding criteria were lk^rmulated. The results show that the liquid-air interface below a composite droplet is fiat when the post pitches are relatively small, but in a shape of curved meniscus when the piteches are comparatively large and the curvature depends on structural parameters. The angle between meniscus and pillar wall is just equal to the supplementary angle of intrinsic contact angle of post material. The calculations also illustrate that Cassie droplets will transform to Wenzel state when post pitch is large enough or when drop volume is sufficiently small. The opposite transition from Wenzel to Cassie state, however, is unable to take place spontaneously because the energy barrier is always positive. Finally, the calculation results of this model are well consistent with tile experimental obserwttions in literatures for the wetting transition of droplets from Cassie to Wenzel state.

Interface associativity and energy absorption capability of anti-vibration porous Al-MM alloy core with iron alloy skin structures

The interface associativity and energy absorption capability of composite structure with anti-vibration porous Al-MM（cerium-rich mischmetal）alloy core and iron alloy skin were investigated.Porous aluminum core/iron alloy skin structures were fabricated considering an iron alloy tube as its shell and closed-cell porous Al-MM alloy as its core.A peeling experiment was carried out to calculate the capacity of interfacial bonding and a compression test was carried out to determine the energy absorption capability.The results showed that the addition of MM significantly enhanced both the interfacial bonding and the energy absorption capacity.

Accurate Determination for the Energy & Temperature Dependence of Electron Capture CrossSection of Si-SiO_2 Interface States Using a New Method

A new technique for accurate determination of the electron and hole capture cross-sections of interface states at the insulator-semiconductor interface has been developed through measuring the initial time variation in the carrier filling capacitance transient, and full consideration is given to the charge-potential feedback effect on carrier capture process. A simplified calculation of the effect is also given. The interface states have been investigated with this technique at the Si-SiO_2 interface in an n-type Si MOS diode. The results show that the electron capture cross-section strongly depends on both temperature and energy.

Interface structure of Ag(111)/SnO_(2)(200)composite material studied by density functional theory

Electric contact material of Ag/SnO2 was successfully synthesized by in situ process method.The in-terface structure was characterized by high-resolution transmission electron microscopy(HTEM) and simulated at atomic scale on computer.The mean-square displacements of atoms near the interface were calculated,and the results showed that near the interface both Ag side and SnO2 were mis-matched and this effect decays rapidly far from the interface.By inspecting the calculated density of states(DOS),we found that the electric-conductivity of this composite material was decreased because of the localized 4d and 2p electrons of Ag and O near the Fermi surface,respectively.Electron density changed acutely across the interface,so that there was no extra compound precipitated.A mi-cro-electric field also formed in the whole material due to the interface structure,and this may affect the electron conduction and the related electric-conductivity of the composite.It is found that the interface cohesive energy of Ag(111)/SnO2(200) was-3.50 J/m2,which is higher than the experimental results.

Grain-interior planar defects induced by heteroatom monolayer

A new type of grain-interior planar defect in a ceramic phase in TiC doped cemented tungsten carbides was discovered.It is unique in that the monolayers of metal atoms exist stably in ceramic grains.The planar defects were induced by the ordered heteroatoms distributing on certain crystal planes of the matrix,which are distinct from the known planar defects such as phase-,grain-,and twin-boundaries,stacking faults,and complexions.Detailed characterization on the atomic scale was performed for the composition,structure,and crystallography of the planar defects,and their energy state and stability were evaluated by modeling.It was found that the Ti monolayer assists nucleation of the new WC crystal along the normal direction to its basal plane.Due to the disturbance of the heteroatom layer,the deposition of W and C atoms deviates from the regular sites occupied in the perfect crystal lattice,resulting in variations of the W–C arrangement in the grain structure.Experiments confirmed that tailoring the distribution density of the planar defects could give the best comprehensive mechanical performance with simultaneously outstanding strength and fracture toughness in the materials containing the grain-interior planar defects.This study provides a new strategy to greatly enhance the mechanical properties of materials by introducing and tailoring planar defects in the grain interiors.

Predicting the Transition between Upper and Lower Bainite via a Gibbs Energy Balance Approach

The transition temperature between upper bainite and lower bainite is calculated with an extended Gibbs energy balance model, which is able to quantitatively describe the evolution of carbon supersaturation within bainitic ferrite sheaves during the entire thickening process. The nucleation rate of intra-lath cementite precipitation on a dislocation is calculated based on of the degree of carbon supersaturation.Upper bainite and lower bainite are thus distinguished by the effective nucleation density and therefore a numerical criterion can be set to define the transition. The model is applied to Fe-xC-1Mn/2Mn/1 Mo ternary alloys. Results show that the transition temperature increases with bulk carbon content at lower carbon concentration but decreases in the higher carbon region. This prediction agrees very well with the experimental observations in Mn and Mo alloyed systems. Moreover, the highest transition temperature and the carbon content at which it occurs in the Fe-xC-2Mn system are in good agreement with reported experimental data. The inverse ＂V＂ shaped character of the carbon concentration-transition temperature curve indicates two opposite physical mechanisms operating at the same time. An analysis is carried out to provide an explanation.

Insight into the role of ethylene glycol on thermodynamics and nucleation kinetics of dimethyl terephthalate in mixed solvent system

Dissolution and nucleation are two essential processes for industrial crystallization.This paper in-vestigates the effect of ethylene glycol addition on the crystallization behavior of dimethyl terephthalate(DMT)in solution.The DMT solubility in mixed solvent system(methanol-ethylene glycol)was deter-mined by isothermal satiation approach,and the solubility was associated using seven models.The model fitting results were consistent with the experimental values.Based on the results,the metastable zone width(MSZW)of DMT was detected by the polythermal approach;the modified Sangwal's theory was used to investigate the nucleation behavior,which can provide a new way of thought for better analysis of the crystallization behavior.The results demonstrated that MSZW was associated with various elements,such as cooling rate,saturation temperature and mass fraction of ethylene glycol.The addition of ethylene glycol slowed down the nucleation rate as shown by the broadening of MSZW.We derive the solid-liquid interface energy,the nucleation driving force,the critical nucleation size and the critical Gibbs free energy according to the classical nucleation theory.It is demonstrated that the nucleation driving force and the solid-liquid interface energy are dependent and jointly influence the MSZW.