Role of Kirkendall effect in diffusion processes in solids

In the 1940s, KIRKENDALL showed that diffusion in binary solid solutions cannot be described by only one diffusion coefficient. Rather, one has to consider the diffusivity of both species. His findings changed the treatment of diffusion data and the theory of diffusion itself. A diffusion-based framework was successfully employed to explain the behaviour of the Kirkendall plane. Nonetheless, the complexity of a multiphase diffusion zone and the morphological evolution during interdiffusion requires a physico-chemical approach. The interactions in binary and more complex systems are key issues from both the fundamental and technological points of view. This paper reviews the Kirkendall effect from the circumstances of its discovery to recent developments in its understanding, with broad applicability in materials science and engineering.

Fabrication and Optical Property of Cu_7S_4 Hollow Nanoparticles Formed Through Kirkendall Effect

1 Introduction In recent years, there has been increasing interest in the controlled synthesis of hollow nanoparticles because of their widespread potential applications. The hollow nanoparticles can be used as catalysts, adsorbents, drug-delivery carriers, chemical reactors, and so on^[1-6]. Some nano and micro spheres are em- ployed as hard or soft templates to produce hollow structures＆[7-10].

The Kirkendall effect on erosion resistance of chrome-coated 25Cr3Mo2WNiV and 30SiMn2MoV gun barrel steels

This study aimed to investigate the erosion behavior and mechanism of a newly developed 25Cr3Mo2WNiV steel with a chrome coating using promoted ignition combustion tests.The erosion threshold pressure and temperature of the chrome-coated 25Cr3Mo2WNiV steel were determined to be 0.2 MPa and 254.3 K higher than those of traditional chrome-coated 30SiMn2MoV steel.Furthermore,Kirkendall voids and inter-diffusion between the Cr coating and matrix were first observed before ero-sion.The improved erosion resistance of the chrome-coated 25Cr3Mo2WNiV steel was attributed to the suppression of the Kirkendall effect,which minimized heat generation at the Cr/matrix interface by pre-venting oxygen diffusion and reducing oxygen affinity.

Controllable synthesis of one-dimensional silicon nanostructures based on the dual effects of electro-deoxidation and the Kirkendall effect

In this study,we successfully synthesized silicon nanotubes(Si-NTs)and silicon nanowires(Si-NWs)in a controllable manner using a catalyst-and template-free method through the direct electrolysis of SiO_(2)in a molten CaCl_(2)-CaO system,while also proposing a novel formation mechanism for Si-NTs.Si-NWs are formed through electro-deoxidation when the cell voltage is within the range of CaO decomposition voltage and SiO_(2)decomposition voltage.By subsequently adjusting the voltage to a value between the decomposition potentials of CaCl_(2)and CaO,in-situ electro-deoxidation of CaO takes place on the surface of the synthesized Si-NWs,leading to the formation of a Ca layer.The formation of Ca-Si diffusion couple leads to the creation of vacancies within the Si-NWs,as the outward diffusion rate of Si exceeds the inward diffusion rate of Ca.These differential diffusion rates between Si and Ca in a diffusion couple exhibit an analogy to the Kirkendall effect.These vacancies gradually accumulate and merge,forming large voids,which ultimately result in the formation of hollow SiCa-NTs.Through a subsequent dealloying process,the removal of the embedded calcium leads to the formation of Si-NTs.Following the application of a carbon coating,the Si-NTs@C composite showcases a high initial discharge capacity of 3211 mAh·g^(-1)at 1.5 A·g^(-1)and exhibits exceptional long-term cycling stability,maintaining a capacity of 977 mAh·g^(-1)after 2000 cycles at 3.0 A·g^(-1).

Microfluidic synthesis of hollow CsPbBr_(3) perovskite nanocrystals through the nanoscale Kirkendall effect

All inorganic metal halide perovskite nanocrystals(NCs)have attracted much attention for their outstanding optoelectronic properties,which can be tuned by the composition,surface,size and morphology in nanoscale.Herein,we report the microfluidic synthesis of hollow CsPbBr_(3)perovskite NCs through the nanoscale Kirkendall effect.The formation mechanism of the hollow structure(Kirkendall void)controlled by the temperature,flow rate,ratios of precursors and ligands was investigated.Compared with the solid CsPbBr_(3)NCs of the same size,the hollow CsPbBr_(3)NCs exhibit blue shifts in ultraviolet-visible(UV-vis)absorption and photoluminescence(PL)spectra,and remarkably longer PL average lifetime(~98.2 ns).Quantum confinement effect,inner surface induced additional trap states and lattice strain of the hollow CsPbBr_(3)NCs were discussed in understanding their unique optoelectronic properties.The hollow CsPbBr_(3)NC based photodetector exhibits an outstanding negative photoconductivity(NPC)detectivity of 8.9×10^(12)Jones.They also show potentials in perovskite NC based photovoltaic and light emitting diodes(LEDs).

Facile synthesis of yolk-shell Ni@void@SnO2（Ni3Sn2） ternary composites via galvanic replacement/Kirkendall effect and their enhanced microwave absorption properties

Yolk-shell ternary composites composed of a Ni sphere core and a SnO2（Ni3Sn2） shell were successfully prepared by a facile two-step method. The size, morphology, microstructure, and phase purity of the resulting composites were characterized by scanning electron microscopy, energy dispersive X-ray spectroscopy, transmission electron microscopy （TEM）, high-resolution TEM, selected-area electron diffraction, and powder X-ray diffraction. The core sizes, interstitial void volumes, and constituents of the yolk-shell structures varied by varying the reaction time. A mechanism based on the time-dependent experiments was proposed for the formation of the yolk-shell structures. The yolk-shell structures were formed by a synergistic combination of an etching reaction, a galvanic replacement reaction, and the Kirkendall effect. The yolk-shell ternary SnO2 （Ni3Sn2）@Ni composites synthesized at a reaction time of 15 h showed excellent microwave absorption properties. The reflection loss was found to be as low as -43 dB at 6.1 GHz. The enhanced microwave absorption properties may be attributed to the good impedance match, multiple reflections, the scattering owing to the voids between the core and the shell, and the effective complementarities between the dielectric loss and the magnetic loss. Thus, the yolk-shell ternary composites are expected to be promising candidates for microwave absorption applications, lithium ion batteries, and photocatalysis.

Engineered porous Ni2P-nanoparticle/Ni2P-nanosheet arrays via the Kirkendall effect and Ostwald ripening towards efficient overall water splitting

Transitional metal phosphides with array-like structure grown on conductive support materials are promising bifunctional catalysts for the oxygen evolution reaction(OER)and hydrogen evolution reaction(HER).In this study,a method was developed to synthesize directly porous Ni2P nanosheet arrays and Ni2P nanoparticles onto nickel foam via a hydrothermal reaction followed by a phosphorization process.Mechanistic studies revealed that the allomorphs of Ni2P nanosheets and Ni2P nanoparticles in the array-like structure were formed via the Kirkendall effect and Ostwald ripening.A fully functional water electrolyzer containing Ni2P as electrodes for the OER and HER exhibited promising activity and stability.At 10 mA·cm^−2,a Ni2P cell voltage of 1.63 V was obtained,which was only 0.05 V smaller than that found for Pt/C/NF||RuO2/NF cell.The enhanced electrocatalytic performance resulted from the favorable porosity of the Ni2P arrays and the synergistic effect between Ni2P nanosheets and Ni2P nanoparticles.

Unexpected Kirkendall effect in twinned icosahedral nanocrystals driven by strain gradient

Nanoscale Kirkendall effect has been widely used for rationally fabricating high-quality hollow nanocrystals, but often requires the intrinsic diffusion coefficient of out-diffusion materials higher than that of in-diffusion components. Here we demonstrate an unexpected Kirkendall effect that occurs in diffusing intrinsically faster Cu atoms into Pd icosahedra, leading to the formation of PdCu alloyed hollow nanocrystals. The control experiment with Pd octahedra replacing icosahedra indicates the critical role of twin boundaries in facilitating such unexpected Kirkendall effect. In addition, geometric phase analysis and density functional theory calculation show that out-diffusion of Pd atoms in the icosahedra is faster than in-diffusion of Cu atoms, particularly through the twin boundaries, upon the strain gradient with an inward distribution from tensile to compressive strains. The unexpected Kirkendall effect is also found in the interdiffusion of Ag and Pd atoms in Pd icosahedra. Our finds break the limitation of the intrinsic diffusion coefficient for the synthesis of hollow nanocrystals through Kirkendall effect and are expected to enormously enrich the family of hollow nanocrystals which have shown great potential in broad areas, such as fine chemical production, energy storage and conversion, and environmental protection. This work also provides a deep understanding in the diffusion behavior of atoms upon the strain gradient.

The accelerating nanoscale Kirkendall effect in Co films–native oxide Si(100)system induced by high magnetic fields

The morphology evolution and magnetic properties of Co films–native oxide Si(100)were investigated at 873,973,and 1073 K in a high magnetic field of 11.5 T.Formation of Kirkendall voids in the Co films was found to cause morphology evolution due to the difference in diffusion flux of Co and Si atoms through the native oxide layer.The high magnetic fields had considerable effect on the morphology evolution by accelerating nanoscale Kirkendall effect.The diffusion mechanism in the presence of high magnetic fields was given to explain the increase of diffusion coefficient.The morphology evolution of Co films on native oxide Si(100)under high magnetic fields during annealing resulted in the magnetic properties variation.

Facile synthesis of hollow Ti_(3)AlC_(2)microrods in molten salts via Kirkendall effect

The microstructure and morphology of Ti_(3)AlC_(2)powders not only affect the preparation of Ti_(3)C_(2) MXene but also have a great influence on their potential applications,such as microwave absorbers,alloy additives,or catalytic supports.However,the synthesis of Ti_(3)AlC_(2)powders with desired microstructure and morphology remains a challenge.Herein,hollow Ti_(3)AlC_(2)microrods were prepared for the first time in NaCl/KCl molten salts by using titanium,aluminum,and short carbon fibers as starting materials.It was found that the short carbon fibers not only performed as carbon source but also acted as sacrificial template.Furthermore,it was revealed that TiC and Ti2AlC were initially formed on the surface of carbon fibers.The subsequent reactions between the outer Ti,Al and the inner carbon were dominated by the Kirkendall effect which gave rise to the formation of a hollow structure.Based on this mechanism,hollow Ti_(3)AlC_(2)microspheres and a series of hollow TiC,Ti_(2)AlC,and V_(2)AlC powders were also successfully fabricated.This work provides a facile route to synthesize hollow MAX phases and may give enlightenment on preparing other hollow carbide powders via the Kirkendall effect in the molten salts.

Influence of Electric Current on Kirkendall Diffusion of Zn/Cu Couples

The influence of electric current on Kirkendall diffusion in Zn/Cu couples was investigated. Under the action of different electric currents, the Zn/Cu diffusion couples were annealed at 785℃ for different holding time. The experimental results show that the displacement of the Kirkendall plane increases with increasing holding time. However, the displacement of the Kirkendall plane with electric current is larger than that without electric current. The relationship between the displacement of the Kirkendall plane and the holding time is changed under the action of electric current. The likely reason for the electric current enhancing effect is the energy transfer from electron to jumping atom, increasing the integrated diffusion coefficient, which leads to the increase in the velocity of Kirkendall plane.

Porous FeS nanofibers with numerous nanovoids obtained by Kirkendall diffusion effect for use as anode materials for sodium-ion batteries

Porous FeS nanofibers with numerous nanovoids for use as anode materials for sodium-ion batteries were prepared by electrospinning and subsequent sulfidation. The post-treatment of the as-spun Fe（acac）3-polyacrylonitrile composite nanofibers in an air atmosphere yielded hollow Fe2O3 nanofibers due to Ostwald ripening. The ultrafine Fe2O3 nanocrystals formed at the center of the fiber diffused toward the outside of the fiber via Ostwald ripening. On sulfidation, the Fe2O3 hollow nanofibers were transformed into porous FeS nanofibers, which contained numerous nanovoids. The formation of porosity in the FeS nanofibers was driven by nanoscale Kirkendall diffusion. The porous FeS nanofibers were very structurally stable and had superior sodium-ion storage properties compared with the hollow Fe2O3 nanofibers. The discharge capacities of the porous FeS nanofibers for the Ist and 150th cycles at a current density of 500 mA.g-1 were 561 and 592 mA.h-g-1, respectively. The FeS nanofibers had final discharge capacities of 456, 437, 413, 394, 380, and 353 mA-h.g-1 at current densities of 0.2, 0.5, 1.0, 2.0, 3.0, and 5.0 A.g-1, respectively.

Microstructure characterization of NiFe_2O_4-NiO solid-solid diffusion couple

The solid state interdiffusion between NiFe204 and NiO in nitrogen atmosphere was studied by means of diffusion couple technique. NiFe204/NiO diffusion couple with plane interfaces was made by clamping method and sintering at 1 300℃ for 10 h. Scanning electronic microscopy （SEM） and energy-dispersive X-ray spectrometry （EDS） were used to analyze the microstructure and phase composition of the diffusion couples. The results indicate that a porous layer of uniform thickness forms along the NiFe2O4/NiO bonding interface and exhibits a deep penetration in the NiFe2O4 due to the Kirkendall effect. Furthermore, SEM observations reveal that the needle-like nickel ferrite precipitates form in NiO near the interface and the formation mechanism of them are inferred to be diffusion type solid-state phase changes.

Analysis of Corrosion Mechanisms of Low-cement or No-cement Al_(2)O_(3)-MgO Gunning Mix with Special Calcined Alumina in Rotary Slag Test

Al_(2)O_(3)-MgO and Al_(2)O_(3)-spinel low cement castables(LCC-AM and LCC-AS)have been extensively used in steel ladles as working linings.Nevertheless,the use of alumina-magnesia gunning mixes has been mainly kept for maintaining these castable linings,because of high rebound loss,poor green strength,high porosity and short life-span.Thanks to a high BET alumina(MC-G),it is now possible to develop a series of high-performance no-cement or low-cement Al_(2)O_(3)-MgO gunning mixes(NCG-AM or LCG-AM).The paper focuses on the BOF slag resistance of NCG-AM,LCG-AM,LCC-AM and LCC-AS.The corrosion mechanisms of rotary slag samples were studied by scanning electron microscopy(SEM/EDS).The results reveal different microstructures around MgO particles,depending on the four used compositions.Continuous and thicker spinel phases were formed in NCG-AM,which was proved to have the best corrosion resistance after the dynamic slag test.MC-G can provide a high diffusion flux of Al^(3+)in terms of kinetics and hence inhibits Kirkendall porosity around MgO particles.In addition,a continuous spinel phase acts like a pinning nail to reinforce the matrix and thus decreases erosion by slag.In contrast to NCG-AM,the porous spinel phase was found around unreacted MgO particles and some particles were carried away near the interface of LCC-AM and slag.The NCG-AM containing MC-G had been tested in two steel plants,and it extended the service life of the ladles up to 50%.In addition,this study suggests the potential application of NCG-AM as steel ladle linings.

Nanostage Alloying of Metals in Liquid Phase

Alloying of metals is known from antiquity. Alloy making i.e., homogenizing metals started in a “hit-or-miss” way. The 1st alloy from copper (Cu) and tin (Sn) was produced around 2500 BC and from then Bronze Age began. Subsequently iron (Fe) age started after the Bronze Age. Aluminium (Al) alloying was discovered much later because pure Al could not be recovered easily even though Al is the most abundant metal in the earth’s crust. Refining of Al is a very difficult job because of its strong affinity towards oxygen. To ease alloying, melting points (mp) of the individual constituents and reactivity of metal towards oxygen were the hurdles. Now understanding the thermodynamics of metal mixing has paved alloying. Periodic properties of elements concerning size, electronegativity, crystal structure, valency, lattice spacing, etc. are considered for alloying. In this feature article, more emphasis is given to Hume-Rothery rules in which the necessary parameters for alloying have been illustrated. Importantly standard electrode potential (E0) values, eutectic, phase diagram, size-related strain in metals, etc. have been looked into in the present discussion. One elegant example is Sn-Pb alloy, known as soft solder. Soft solder was in use for many years to connect metals and in electric circuitry. Low melting, flowability, and conductivity of soft solder had placed Sn-Pb alloy a unique position in industries, laboratories and even in cottage industries. However, toxic Pb volatilizes during soldering and hence soft solder is banned almost in all countries. We felt the need for a viable alternative to obtain soldering material and then silver (Ag) based highly conducting, an eco-friendly alloy of Sn resulted in from a high boiling liquid. The discovery engenders not only a new conducting soldering alloy but also a new concept of melting metals together. Furthermore, new ideas of alloying have been generalized at their nanostages from a suitable high boiling solvent.

Oxidation behavior and microstructural evolution of FeCoNiTiCu five-element high-entropy alloy nanoparticles

High-entropy alloys(HEAs)have attracted extensive attention ascribed to their unique physical and chemical properties induced by the cocktail effect.However,their oxidation behaviors,in particular at nanoscale,are still lack because of multi-element complexity,which could also be completely differ-ent from the bulk counterparts.In this work,we synthesized FeCoNiTiCu five-element HEA nanopar-ticles(NPs)with uniform elemental distribution by arc-discharging approach,and further investigated their oxidation behaviors at 250 ℃,and 350 ℃.The morphology,structure and element distribution of NPs were analyzed by transmission electron microscopy(TEM),energy dispersive spectroscopy(EDS)and electron energy loss spectroscopy(EELS).The surface oxidation in FeCoNiTiCu NPs during the high-temperature process can induce nanoscale pores at core/shell interfaces by Kirkendall effect,and even the eventual coalescence into a single cavity.Additionally,the oxidation states of NPs with diameters(d)varying from 60 to 350 nm were analyzed in detail,revealing two typical configurations:hollow(d<150 nm)and yolk-shell structures(d>150 nm).The experimental results were complemented by first-principles calculations to investigate the diffusion behaviors of five elements,evidencing that the surface oxidation strongly alters the surface segregation preferences:(1)in the initial stage,Cu and Ni appear to prefer segregating on the surface,while Co,Ti and Fe tend to stay in the bulk;(2)in the oxidation process,Cu prefers to stay in the center,while Ti segregates to the surface ascribed to the reduced po-tential energies.The study gives new insights into oxidation of nanoscale HEA,and also provides a way for fabrication of high-entropy oxides with controllable architectures.

Study on Micron Porous Copper Prepared by Physical Vacuum Dealloying

Porous copper was prepared successfully by physical vacuum dealloying method using the CuZn alloy pre- cursors （Cu30Zn70, Cu40Zn60 and Cu50Zn50 alloys）. The micron porous copper showed a three-dimensional continuous porous structure with 1-5 μm pore size. With the increase of the Zn content in the CuZn alloy, the pore structure of the porous copper was more uniform and ordered. Temperature was the key factor for physical dealloying, and the optimized temperature was 500 ℃ for the CuZn alloy. The pores would fuse and disappear when the temperature was over 500 ℃. Physical vacuum dealloying was an effective preparation method for porous copper, which can be used to prepare other porous metals based on the sublimation and the Kirkendall effect.

Mesoporogen-free synthesis of hierarchical sodalite as a solid base catalyst from sub-molten salt-activated aluminosilicate

A rapid and environmentally friendly approach to synthesize hierarchical sodalite from natural aluminosilicate mineral without the involvement of any mesoporogen or post-synthesis treatment was developed.This strategy involves three important steps:the first is the depolymerization of an aluminosilicate mineral into highly reactive silicon and aluminum species with ideal meso-scale structures through activation of a sub-molten salt.The second step is the hydrolysis and condensation of the activated aluminosilicate mineral into zeolitic precursors that also have a meso-scale structure.The third is the rapid zeolitization of the zeolitic precursors through the reversed crystal growth route at room temperature and ambient pressure to form hierarchical sodalite.The physicochemical properties of the as-synthesized sodalite were systematically characterized,and the formation mechanism of the hierarchical pore structure was discussed.When used as a solid base catalyst for Knoevenagel condensation,the as-synthesized sodalite and its potassium ion-exchanged product with hierarchical micro-meso-macroporous structure both exhibited high catalytic activity and product selectivity.

A novel ball-in-ball hollow oxygen-incorporating cobalt sulfide spheres as high-efficient electrocatalyst for oxygen evolution reaction

Transition-metal chalcogenides with hollow nanostructure,especially cobalt sulfides,are considered as the most pro mising non-precious metal catalysts for oxygen evolution reactio n.However,it is difficult to synthesize oxygen-containing cobalt sulphides with hollow structure due to the different physical/chemical properties between metal sulfides and metal cobalts.Herein,we report a novel oxygencontaining amorphous cobalt sulfide ball-in-ball hollow sphere s(Co-S-O BBHS) synthesized by an anion exchange method.Taking advantage of the ball-in-ball hollow structure,the amorphous Co-S-O BBHS shows supe rior oxygen evolution reaction(OER) electrocatalytic performance with a low overpotentiat of285 mV at 10 mA/cm2,small Tafel slope of 49.67 mV/dec,high Faraday efficiency of 96%,and satisfied durability.Experiments and DFT calculations demonstrate that the introduction of oxygen and sulfur modulates the electronic structure of Co-S-O BBHS,thus enhancing the adsorption of *0(adsorbed 0 species on catalyst surface) intermediate,which greatly boosts the catalytic activity towards OER.This work provides a new strategy for controllable synthe sis of complex hollow structures of transition-metal chalcogenides for OER.