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.

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.

Effect of Si content on interfacial reaction and properties between solid steel and liquid aluminum

The effect of Si content on the microstructures and growth kinetics of intermetallic compounds(IMCs)formed during the initial interfacial reaction(<10 s)between solid steel and liquid aluminum was investigated by a thermophysical simulation method.The influence of Si addition on interfacial mechanical properties was revealed by a high-frequency induction brazing.The results showed that IMCs layers mainly consisted ofη-Fe_(2)Al_(5)andθ-Fe_(4)Al_(13).The addition of Si reduced the thickness of the IMCs layer.The growth of theηphase was governed by the diffusion process when adding 2 wt.%Si to the aluminum melt.When 5 wt.%or 8 wt.%Si was added to aluminum,the growth was governed by both the diffusion process and interfacial reaction,and ternary phaseτ1/τ9-(Al,Si)_(5)Fe_(3)was formed in theηphase.The apparent activation energies of theηphase decreased gradually with increasing Si content.The joint with pure aluminum metal had the highest tensile strength and impact energy.

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.

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.

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.

Interfacial Reaction Between Solid Nickel and Liquid Zinc

Interfacial reactions between solid nickel and liquid zinc at 450-650 ℃ for 30-600 s were studied. The morphology and growth behavior of intermetallic compound layers at the interface between solid nickel and liquid zinc were observed and analyzed by SEM and EDS. The results show that γ and 8 phases are formed at 450 ℃ at the Ni/Zn interface, and at 550 ℃ and 650 ℃ only ）,phase is formed at the interthce and some δ phase particles will be participated during solidification on the surface of γphase layer. The β1 phase is absent under experimental conditions. Many cracks occur in the layers due to the difference in thermal expansion coefficients of these phases. It is found that the kinetics of the intermetallic compounds growth follows a parabolic law of time, as controlled by the diffusion mechanism. The apparent activation energies are 113.9 kJ/mol for the growth of γphase and 125.87 kJ/mol for γ1 phase, respectively.

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.

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.

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.

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.

Process intensification in gas/liquid/solid reaction in trickle bed reactors: A review

As an important form of reactors for gas/liquid/solid catalytic reaction,trickle bed reactors (TBRs) are widely applied in petroleum industry,biochemical,fine chemical and pharmaceutical industries because of their flexibility,simplicity of operation and high throughput.However,TBRs also show inefficient production and hot pots caused by non-uniform fluid distribution and incomplete wetting of the catalyst,which limit their further application in chemical industry.Also,process intensification in TBRs is necessary as the decrease in quality of processed crude oil,caused by increased exploitation depths,and more restrictive environmental regulations and emission standards for industry,caused by increased environment protection consciousness.In recent years,lots of strategies for process intensification in TBRs have been proposed to improve reaction performance to meet the current and future demands of chemical industry from the environmental and economic perspective.This article summarizes the recent progress in techniques for intensifying gas/liquid/solid reaction in TBRs and application of intensified TBRs in petroleum industry.

FINE STRUCTURES OF BOTH INTERFACES AND INTERFACIAL REACTION PRODUCTS

The characteristic of interface depending on the atomic structure exerts an inportant,and sometime controlling,influence on performance of the interacial materials. The present paper reviews the main studies on fine structure of both the materials inter- faces and interfacial reaction products in semiconductor uperlattice,metal multilayer ceram- ics and composite materials by mean of selected area electron doffraction patterns and high resolution electron microscopy. The following features of interfaces are reviewed:the orientation relationships;the char- acteristic of steps,facets and ronghness of interfaces;atomic bonding across the interface;the degree of coherency,the structure of misfit dislocations and elastic relaxations at the inter- faces:the presence of defects at the onterfaces:the structure of the interfacial reaction prod- ucts as well as the reaction kinetics and reaetion mechanism.

INTERACTION OF PARTICLES WITH A SOLIDIFIED INTERFACE DURING SOLIDIFICATION OF METAL MATRIX COMPOSITE REINFORCED WITH PARTICLES

The interaction of particles with a solid-liquid interface during solidification of metal matrix composites has been investigated theoretically in this paper.Owing to the presence of particles in the melt,the shape of the solidification front and solute concentration field in front of solidification interface have been disturbed The thermodynamic method was employed,and a mathematical expression of the shape of the solidification interface and solute concentration field were deduced.Meanwhile,a theory is developed for evaluation of critical velocities of particles pushed by the solidification interface.A numerical simulation is done in which the critical velocity is evaluated as a function of particle size,thermal conductivity,diffusion coefficient,temperature gradient at the solidification front,the solid-liquid interfacial energy and the melt viscosity.The critical velocity is shown to be closely linked to the shape of the solidification interface and solute concentration field, and hence all the parameters also affect the shape of the solidification interface and solute concentration field of the front.

The Dynamical Model of Chemical Oscillation in CaF_2-HCl-H_2O Solid-Liquid Reaction System

Based on the physical chemistry principle, this paper proposes that the surface adsorption catalytic mechanism of HF is the key to dissolving the oscillation of the CaF\-2\|HCl\|H\-2O solid\|liquid reaction system. Meanwhile the dynamical model of this system has been established in order to study its non\|linear dynamical genesis. Although this mathematics model is based on CSTR reaction apparatus, it is applicable to the foliate flow reaction apparatus, too.

Preparation for intermetallic powders of Cu-Sn and Cu-Ni-Sn systems via solid-liquid reaction milling technique

The Cu-Sn binary intermetallic powders were obtained via a patented reaction ball milling technique. The Sn melt reacted with the solid-state Cu during the milling process at different temperatures for different intervals. Two kinds of binary intermetallics were obtained. For 12 h,Cu6Sn5 was prepared by milling Sn melt at 573 K while Cu3Sn by milling Sn melt at 773 K. And a mixture of Cu6Sn5 and Cu3Sn was fabricated at 673 K. All these intermetallic powders had mean grain sizes of less than 100 nm. A finer microstructure was obtained by milling Sn melt blended with 20%(mass fraction) Ni powders at 573 K for 12 h. The reaction mechanism and advantages were discussed in comparison with that of high-energy ball milling. The results show the solutionizing of Ni powders in the Cu6Sn5 intermetallic.

Effects of Ca(Y)-Si modifier on interface morphology and solute segregation during directional solidification of an austenite medium Mn steel

The austenite medium Mn steel modified with controlled additions of Ca, Y, Si were directionally solidified using the vertical Bridgman method to study the effects of Ca（Y）-Si modifier on the solid-liquid （S-L） interface morphology and solute segregation. The interface morphology and the C and Mn segregation of the steel directionally solidified at 6.9 μtrn/s were investigated with an image analysis and a scanning electron microscope equipped with energy dispersive X-ray analysis. The 0.5wt% Ca-Si modified steel is solidified with a planar S-L interface. The interface of the 1.0wt% Ca-Si modified steel is similar to that of the 0.5wt% Ca-Si modified steel, but with larger nodes. The 1.5wt% Ca-Si modified steel displays a cellular growth parttern. The S-L interface morphology of the 0.5wt% Ca-Si＋1.0wt% Y-Si modified Mn steel appears as dendritic interface, and primary austenite dendrites reveal developed lateral branching at the quenched liquid. In the meantime, the independent austenite colonies are formed ahead of the S-L interface. A mechanism involving constitutional supercooling explains the S-L interface evolution. It depends mainly on the difference in the contents of Ca, Y, and Si ahead of the S-L interface. The segregation of C and Mn ahead of the S-L interface enhanced by the modifiers is observed.

Thermochemical Heat Storage Performance in the Gas/Liquid-Solid Reactions of SrCl2 with NH3

Thermochemical heat storage is a promising technology for improving energy efficiency through the utilization of low-grade waste heat. The formation of a SrCl2 ammine complex was selected as the reaction system for the purpose of this study. Discharge characteristics were evaluated in a packed bed reactor for both the gas-solid reaction and the liquid-solid reaction. The average power of the gas-solid reaction was influenced by the pressure of the supplied ammonia gas, with greater powers being recorded at higher ammonia pressure. For the liquid-solid reaction, the obtained average power was comparable to that obtained for the gas-solid reaction at 0.2 MPa. Moreover, the lower heat transfer resistance in the reactor was observed, which was likely caused by the presence of liquid ammonia in the system. Finally, the short-term durability of the liquid-solid reaction system was demonstrated over 10 stable charge/discharge cycles.