Atomic-level characterization of liquid/solid interface

The detailed understanding of various underlying processes at liquid/solid interfaces requires the development of interface-sensitive and high-resolution experimental techniques with atomic precision.In this perspective,we review the recent advances in studying the liquid/solid interfaces at atomic level by electrochemical scanning tunneling microscope(EC-STM),non-contact atomic force microscopy(NC-AFM),and surface-sensitive vibrational spectroscopies.Different from the ultrahigh vacuum and cryogenic experiments,these techniques are all operated in situ under ambient condition,making the measurements close to the native state of the liquid/solid interface.In the end,we present some perspectives on emerging techniques,which can defeat the limitation of existing imaging and spectroscopic methods in the characterization of liquid/solid interfaces.

Recent Progress in Metallurgical Bonding Mechanisms at the Liquid/Solid Interface of Dissimilar Metals Investigated via in situ X-ray Imaging Technologies

The liquid/solid(L/S)interface of dissimilar metals is critical to the microstructure,mechanical strength,and structural integrity of interconnects in many important applications such as electronics,automotive,aeronautics,and astronautics,and therefore has drawn increasing research interests.To design preferential microstructure and optimize mechanical properties of the interconnects,it is crucial to understand the formation and growth mechanisms of diversified structures at the L/S interface during interconnecting.In situ synchrotron radiation or tube-generated X-ray radiography and tomography technologies make it possible to observe the evolution of the L/S interface directly and therefore have greatly propelled the research in this field.Here,we review the recent progress in understanding the L/S interface behaviors using advanced in situ X-ray imaging techniques with a particular focus on the following two issues:(1)interface behaviors in the solder joints for microelectronic packaging including the intermetallic compounds(IMCs)during refl ow,Sn dendrites,and IMCs during solidification and refl ow porosities and(2)growth characteristics and morphological transition of IMCs in the interconnect of dissimilar metals at high temperature.Furthermore,the main achievements and future research perspectives in terms of metallurgical bonding mechanisms under complex conditions with improved X-ray sources and detectors are remarked and discussed.

Understanding fundamentals of electrochemical reactions with tender X-rays:A new lab-based operando X-ray photoelectron spectroscopy method for probing liquid/solid and gas/solid interfaces across a variety of electrochemical systems

Electrocatalysis is key to improving energy efficiency,reducing carbon emissions,and providing a sustainable way of meeting global energy needs.Therefore,elucidating electrochemical reaction mechanisms at the electrolyte/electrode interfaces is essential for developing advanced renewable energy technologies.However,the direct probing of real-time interfacial changes,i.e.,the surface intermediates,chemical environment,and electronic structure,under operating conditions is challenging and necessitates the use of in situ methods.Herein,we present a new lab-based instrument commissioned to perform in situ chemical analysis at liquid/solid interfaces using ambient pressure X-ray photoelectron spectroscopy(APXPS).This setup takes advantage of a chromium source of tender X-rays and is designed to study liquid/solid interfaces by the“dip and pull”method.Each of the main components was carefully described,and the results of performance tests are presented.Using a three-electrode setup,the system can probe the intermediate species and potential shifts across the liquid electrolyte/solid electrode interface.In addition,we demonstrate how this system allows the study of interfacial changes at gas/solid interfaces using a case study:a sodium–oxygen model battery.However,the use of APXPS in electrochemical studies is still in the early stages,so we summarize the current challenges and some developmental frontiers.Despite the challenges,we expect that joint efforts to improve instruments and the electrochemical setup will enable us to obtain a better understanding of the composition–reactivity relationship at electrochemical interfaces under realistic reaction conditions.

In situ formation of an intimate solid-solid interface by reaction between MgH_(2) and Ti to stabilize metal hydride anode with high active material content

MgH_(2) and TiH_(2) have been extensively studied as potential anode materials due to their high theoretical specific capacities of 2036 and 1024 mAh/g,respectively.However,the large volume changes that these compounds undergo during cycling affects their performance and limits practical applications.The present work demonstrates a novel approach to limiting the volume changes of active materials.This effect is based on mechanical support from an intimate interface generated in situ via the reaction between MgH_(2) and Ti within the electrode prior to lithiation to form Mg and TiH_(2).The resulting Mg can be transformed back to MgH_(2) by reaction with LiH during delithiation.In addition,the TiH_(2) improves the reaction kinetics of MgH_(2) and enhances electrochemical performance.The intimate interface produced in this manner is found to improve the electrochemical properties of a MgH_(2)-Ti-LiH electrode.An exceptional reversible capacity of 800 mAh/g is observed even after 200 cycles with a high current density of 1 mA/cm^(2) and a high proportion of active material(90 wt.%)at an operation temperature of 120℃.This study therefore showcases a new means of improving the performance of electrodes by limiting the volume changes of active materials.

Evolution of bonding interface in solid-liquid cast-rolling bonding of Cu/Al clad strip

Cu/Al clad strips are prepared using solid?liquid cast-rolling bonding(SLCRB)technique with a d160mm×150mm twin-roll experimental caster.The extent of interfacial reactions,composition of the reaction products,and their micro-morphology evolution in the SLCRB process are investigated with scanning electron microscope(SEM),energy dispersive spectrometer(EDS),and X-ray diffraction(XRD).In the casting pool,initial aluminized coating is first generated on the copper strip surface,with the diffusion layer mainly consisting ofα(Al)+CuAl2and growing at high temperatures,with the maximum thickness of10μm.After sequent rolling below the kiss point,the diffusion layer is broken by severe elongation,which leads to an additional crack bond process with a fresh interface of virgin base metal.The average thickness is reduced from10to5μm.The reaction products,CuAl2,CuAl,and Cu9Al4,are dispersed along the rolling direction.Peeling and bending test results indicate that the fracture occurs in the aluminum substrate,and the morphology is a dimple pattern.No crack or separation is found at the bonding interface after90°-180°bending.The presented method provides an economical way to fabricate Cu/Al clad strip directly.

An APXPS endstation for gas–solid and liquid–solid interface studies at SSRF

In the past few decades, various surface analysis techniques find wide applications in studies of interfacial phenomena ranging from fundamental surface science,catalysis, environmental science and energy materials.With the help of bright synchrotron sources, many of these techniques have been further advanced into novel in-situ/operando tools at synchrotron user facilities, providing molecular level understanding of chemical/electrochemical processes in-situ at gas–solid and liquid–solid interfaces.Designing a proper endstation for a dedicated beamline is one of the challenges in utilizing these techniques efficiently for a variety of user's requests. Many factors,including pressure differential, geometry and energy of the photon source, sample and analyzer, need to be optimized for the system of interest. In this paper, we discuss the design and performance of a new endstation at beamline02 B at the Shanghai Synchrotron Radiation Facility for ambient pressure X-ray photoelectron spectroscopy studies.This system, equipped with the newly developed hightransmission HiPP-3 analyzer, is demonstrated to be capable of efficiently collecting photoelectrons up to 1500 eV from ultrahigh vacuum to ambient pressure of 20 mbar.The spectromicroscopy mode of HiPP-3 analyzer also enables detection of photoelectron spatial distribution with resolution of 2.8 ± 0.3 lm in one dimension. In addition,the designing strategies of systems that allow investigations in phenomena at gas–solid interface and liquid–solid interface will be highlighted through our discussion.

Interface issues and challenges for NASICON-based solid-state sodium-metal batteries

All-solid-state sodium(Na)-metal batteries(ASSSMBs)are considered promising candidates for large-scale energy storage systems due to their abundant sodium resources,unparalleled safety performance,and impressive energy density.Na superionic conductors(NASICONs)are among the best enablers of ASSSMBs in view of their high ionic conductivity,ease of synthesis,and excellent thermal stability and good electrochemical/chemical compatibility with common electrodes.However,challenges surrounding the NASICON/electrode interface,such as high interfacial resistance and dendrite formation,have hindered the development of practical ASSSMBs based on NASICONs.This review starts with an explicit summary of the interface problems between the metallic Na anode and NASICON arising from mechanical,chemical,and electrochemical aspects(i.e.,poor interface contact,insulating side-reaction products,and irregular dendrite growth).Subsequently,we systematically analyze and logically categorize modification strategies for addressing anode interface problems and provide a comprehensive discussion on the underlying enhancement mechanisms.As such,we identify underlying and universal interface enhancement mechanisms by comparatively studying various modification strategies.Furthermore,we briefly summarize the challenges in the cathode/electrolyte interface and early-stage research efforts in constructing stable cathode/electrolyte interface and fabricating high-performance composite cathodes.Finally,key suggestions and future prospectives for the advancement of NASICON-based ASSSMBs are outlined.

Microstructure and Solid/Liquid Interface Evolutions of Directionally Solidified Fe-Al-Ta Eutectic Alloy

A modified Bridgman directional solidification technique was used to prepare Fe-Al-Ta eutectic in situ composites at different growth rates ranging from 6 to 80 μm/s. The directionally solidified FeAl-Ta eutectic composites are composed of two phases: Fe（Al,Ta） matrix phase, and Fe2 Ta（Al） Laves phase. Solidification microstructure is affected by solidification rate. Microstructure of the Fe-Al-Ta eutectic alloy grown at 6.0 μm/s is broken-lamellar eutectic. Eutectic colonies are formed with the increase of the solidification rate. Microstructures are mainly composed of the lamellar or fibrous eutectic at the center of the colony and coarse lamellar eutectic zone at the boundary. Meanwhile, the inter-lamellar spacing（or the inter-rod spacing） is decreased. The spacing adjustments are also observed in Fe-Al-Ta eutectic alloy. The solid/liquid interface evolves from planar interface to shallow cellular interface, then to deep cellular, and finally to shallow cellular planar with the increase of the solidification rate.

Treatment of discontinuous interface in liquid-solid forming with extended finite element method

Extended finite element method(XFEM) is proposed to simulate the discontinuous interface in the liquid-solid forming process.The discontinuous interface is an important phenomenon happening in the liquid-solid forming processes and it is difficult to be simulated accurately with conventional finite element method(CFEM) because it involves solid phase and liquid phase simultaneously.XFEM is becoming more and more popular with the need of solving the discontinuous problem happening in engineering field.The implementation method of XFEM is proposed on Abaqus code by using UEL(user element) with the flowchart.The key is to modify the element stiffness in the proposed method by using UEL on the platform of Abaqus code.In contrast to XFEM used in the simulation of solidification,the geometrical and physical properties of elements were modified at the same time in our method that is beneficial to getting smooth interface transition and precise analysis results.The analysis is simplified significantly with XFEM.

First‐mode of negative streamers:Inception at liquid/solid interfaces

An experimental study of the inception of the first‐mode negative streamer at liquid/solid interfaces is presented in this article.The study is performed with a point‐plane configuration under square high voltage pulses.The electrode configuration is immersed in mineral oil and the liquid/solid interface is assembled in contact with the point electrode or in its vicinity.Four polymers and two impregnated papers have been tested as solids of the liquid/solid interface.Thus,it is possible to compare the influence of different parameter of the solid and the interface on the streamer inception.For example:Permittivity,solid surface roughness,chemical composition,etc.It has been observed that streamer inception voltages at interfaces with solids of higher permittivity to that of the mineral oil are statistically similar.Additionally,streamer inception voltages of streamer initiated free in the oil(no liquid/solid interface)are similar to that of the inception voltage of cases with solids with high permittivity.In contrast,the inception voltage of streamers initiated at permittivity matched interfaces are shown to be highest of the cases.The streamer inception voltage is also studied for different distances be-tween the liquid/solid interface and the point electrode with a permittivity matched interface.The results show a dependency of the inception voltage and the distance be-tween the point electrode and the interface.Finally,an analysis of the observation is performed to show that the Townsend‐Meek criterion cannot predict the obtained results.

Mathematical Modelling of Particle Movement Ahead of the Solid-liquid Interface in Continuous Casting

Whether the particle will be trapped by the solid-liquid interface or not is dependent on its moving behavior ahead of the interface, so a mathematical model has been developed to investigate the movement of the particle ahead of the solid-liquid interface. Based on the theory for the boundary layer, the fluid velocity field near the solid-liquid interface was obtained, and the trajectories of particles were calculated by the equations of motion for particles. In this model, the drag force, the added mass force, the buoyance force, the gravitational force, the Saffman force and the Basset history force are considered. The results show that the behavior of the particle ahead of the solid-liquid interface is affected by the physical property of the particle and fluid flow. And in the continuous casting process, if it moves in the stream directed upward or downward near vertical solid-liquid interface or in the horizontal flow under the solid-liquid interface, the particle with the diameter from 5 um to 60um can reach the solid-liquid interface. But if it moves in horizontal flow above the solid-liquid interface, only the particle with the diameter from 5 um to 10 um can reach the solid-liquid interface.

Effect of current density on distribution coefficient of solute at solid-liquid interface

When current passes through the solid-liquid interface, the growth rate of crystal, solid-liquid interface energy and radius of curvature at dendritic tip will change. Based on this fact, the theoretical relation between the distribution of solute at solid-liquid interface and current density was established, and the effect of current on the distribution coefficient of solute through effecting the rate of crystal growth, the solid-liquid interface energy and the radius of curvature at the dendritic tip was discussed. The results show that as the current density increases, the distribution coefficient of solute tends to rise in a whole, and when the former is larger than about 400 A/cm 2, the latter varies significantly.

Fractal Description of the Solid/Liquid Interface of a Directionally Solidified Superalloy with Different Phosphorus Content

The solid/liquid interface of a directionally solidified Ni-base superalloy with different phosphorus contents was quantitatively described by means of fractat method.When the solidification rate was fixed,the relationship between the fractal dimensionality of the solid/liquid interface and the phos- phorus content of the test alloy was given.Combined the thermodynamics and fractal theory,the ef- fect mechanism of phosphorus content on fractal dimensionality of the solid/liquid interface was discussed.

Thermal rectification induced by Wenzel–Cassie wetting state transition on nano-structured solid–liquid interfaces

Thermal rectification refers to the phenomenon by which the magnitude of the heat flux in one direction is much larger than that in the opposite direction.In this study,we propose to implement the thermal rectification phenomenon in an asymmetric solid–liquid–solid sandwiched system with a nano-structured interface.By using the non-equilibrium molecular dynamics simulations,the thermal transport through the solid–liquid–solid system is examined,and the thermal rectification phenomenon can be observed.It is revealed that the thermal rectification effect can be attributed to the significant difference in the interfacial thermal resistance between Cassie and Wenzel states when reversing the temperature bias.In addition,effects of the liquid density,solid–liquid bonding strength and nanostructure size on the thermal rectification are examined.The findings may provide a new way for designs of certain thermal devices.

Apparent Active Adsorption Force at a Solid-Liquid Interface with Active Adsorption

The paper presents a new relationship between the three surface tensions on the solid-liquid-vapor interface, γ_(sl)-γ_(sv)+γ_(lv)cosθ=βin order to understand the wetting on the liquid-solid interface in the case of active adsorption.The authors suggest a new force“apparent active adsorption force”βto take part in the balance at the three interface lines of contact in the solid-liquid-vapor phases,its dimen- sion isβ=Σα_iRT(Γ_i^(sl)-Γ_i^(sv)+Γ_i^(lv)cosθ),and its direction is dependent on the sign of β,whenβis a positive, the direction is agree with surface tension of the sol- id-vapor interface γ and vice versa.

Phase difference and interference between reflected cylindrical wave and head wave at a liquid/solid interface

The reflected field of pulsed cylindrical waves from a liquid-solid interface is studied by the numerical method and the experimental method. The reflected field is calculated and shown in gray pictures. The calculated incident angles θn (n=1, 2, 3, ...) of a series of minimums (or nulls) on the reflected wavefront are presented. The measured angle of the minimum from Schlieren photograph is consistent with that by calculation. The appearance of minimums is explained by the interference between the reflected wave and the head wave, and by the radiated dissipation of the head wave. The leading phase angle of the head wave to the reflected wave is proved to be about 3π/4 by the numerical calculation.

From Liquid to Solid‑State Lithium Metal Batteries:Fundamental Issues and Recent Developments

The widespread adoption of lithium-ion batteries has been driven by the proliferation of portable electronic devices and electric vehicles,which have increasingly stringent energy density requirements.Lithium metal batteries(LMBs),with their ultralow reduction potential and high theoretical capacity,are widely regarded as the most promising technical pathway for achieving high energy density batteries.In this review,we provide a comprehensive overview of fundamental issues related to high reactivity and migrated interfaces in LMBs.Furthermore,we propose improved strategies involving interface engineering,3D current collector design,electrolyte optimization,separator modification,application of alloyed anodes,and external field regulation to address these challenges.The utilization of solid-state electrolytes can significantly enhance the safety of LMBs and represents the only viable approach for advancing them.This review also encompasses the variation in fundamental issues and design strategies for the transition from liquid to solid electrolytes.Particularly noteworthy is that the introduction of SSEs will exacerbate differences in electrochemical and mechanical properties at the interface,leading to increased interface inhomogeneity—a critical factor contributing to failure in all-solidstate lithium metal batteries.Based on recent research works,this perspective highlights the current status of research on developing high-performance LMBs.

Multistate transition and coupled solid-liquid modeling of motion process of long-runout landslide

The recognition,repetition and prediction of the post-failure motion process of long-runout landslides are key scientific problems in the prevention and mitigation of geological disasters.In this study,a new numerical method involving LPF3D based on a multialgorithm and multiconstitutive model was proposed to simulate long-runout landslides with high precision and efficiency.The following results were obtained:(a)The motion process of landslides showed a steric effect with mobility,including gradual disintegration and spreading.The sliding mass can be divided into three states(dense,dilute and ultradilute)in the motion process,which can be solved by three dynamic regimes(friction,collision,and inertial);(b)Coupling simulation between the solid grain and liquid phases was achieved,focusing on drag force influences;(c)Different algorithms and constitutive models were employed in phase-state simulations.The volume fraction is an important indicator to distinguish different state types and solid‒liquid ratios.The flume experimental results were favorably validated against long-runout landslide case data;and(d)In this method,matched dynamic numerical modeling was developed to better capture the realistic motion process of long-runout landslides,and the advantages of continuum media and discrete media were combined to improve the computational accuracy and efficiency.This new method can reflect the realistic physical and mechanical processes in long-runout landslide motion and provide a suitable method for risk assessment and pre-failure prediction.

Construction of Dynamic Alloy Interfaces for Uniform Li Deposition in Li-Metal Batteries

It is well accepted that a lithiophilic interface can effectively regulate Li deposition behaviors,but the influence of the lithiophilic interface is gradually diminished upon continuous Li deposition that completely isolates Li from the lithiophilic metals.Herein,we perform in-depth studies on the creation of dynamic alloy interfaces upon Li deposition,arising from the exceptionally high diffusion coefficient of Hg in the amalgam solid solution.As a comparison,other metals such as Au,Ag,and Zn have typical diffusion coefficients of 10-20 orders of magnitude lower than that of Hg in the similar solid solution phases.This difference induces compact Li deposition pattern with an amalgam substrate even with a high areal capacity of 55 mAh cm^(-2).This finding provides new insight into the rational design of Li anode substrate for the stable cycling of Li metal batteries.

Influence of Ni interlayer on interfacial microstructure and mechanical properties of Ti-6Al-4V/AZ91D bimetals fabricated by a solid–liquid compound casting process

The solid–liquid compound casting of Mg-AZ91D and Ti-TC4 alloys was developed by using pure Ni electro-deposited coating.The pouring temperatures of 660℃,690℃,720℃and 750℃were chosen to investigated the effects of casting temperatures on microstructural evolution,properties,and fracture behaviors of Ni-coated TC4/AZ91D bimetals by the solid–liquid compound casting(SLCC).The scanning electron microscopy(SEM)and the energy dispersive spectroscopy(EDS)results showed that the interfacial zone mainly composed of nickel,Mg_(2)Ni and Mg-Al-Ni in the bimetals cast at 660℃.As the pouring temperature was increased to 750℃,the width of the interface zone,which mainly composed ofδ(Mg),Mg_(2)Ni,Mg-Al-Ni,Mg_(3)TiNi_(2) and Al_(3)Ni,gradually increased.The microhardness tests showed that the micro-hardness of the interface zone was smaller than that of TC4 substrate but larger than that of the cast AZ91D matrix.At the pouring temperature of 720℃,the Ni-coated TC4/AZ91D bimetals had the most typical homogeneous interface,which had granular Mg-Al-Ni ternary phase but no ribbon-like Al3Ni binary phase,and achieved the highest shear strength of 97.35MPa.Meanwhile,further fracture behavior analysis showed that most fracture failure of Ni-coated TC4/AZ91D bimetals occurred at the Mg_(2)Ni+δ(Mg)eutectic structure and Al_(3)Ni hard intermetallic.