Solid Diffusion Research Articles

Mesoscopic characteristics, microstructure evolution, friction mechanisms, and corrosion behavior of Ni60-SiCp coatings fabricated by laser-based directed energy deposition

The influence of varying SiCp on the mesoscopic characteristics, microstructural evolution, microhardness, frictional mechanisms, and corrosion resistance behavior of laser-based directed energy deposition Ni60-SiCp composite coatings was investigated. Coatings reinforced with varying SiCp, the innovative concept of the ''Temperature-SiCp joint effect'' mechanism was proposed. The microstructure was progressively refined due to the SiCp, while microhardness was affected by the solid solution strengthening and diffusion strengthening effects of high SiCp. Furthermore, based on wear scar morphologies, wear scar EDS analysis, and wear mechanism modeling, the frictional mechanisms were elucidated. Simultaneously, a clear understanding of the relationship between SiCp and corrosion behavior were established. It is evident that the analysis of SiCp reinforcement content in composite holds significant guiding significance.

Shear force effect of the dry process on cathode contact coverage in all-solid-state batteries

The state-of-the-art all-solid-state batteries have emerged as an alternative to the traditional flammable lithium-ion batteries, offering higher energy density and safety. Nevertheless, insufficient intimate contact at electrode-electrolyte surface limits their stability and electrochemical performance, hindering the commercialization of all-solid-state batteries. Herein, we conduct a systematic investigation into the effects of shear force in the dry electrode process by comparing binder-free hand-mixed pellets, wet-processed electrodes, and dry-processed electrodes. Through digitally processed images, we quantify a critical factor, ‘coverage’, the percentage of electrolyte-covered surface area of the active materials. The coverage of dry electrodes was significantly higher (67.2%) than those of pellets (30.6%) and wet electrodes (33.3%), enabling superior rate capability and cyclability. A physics-based electrochemical model highlights the effects of solid diffusion by elucidating the impact of coverage on active material utilization under various current densities. These results underscore the pivotal role of the electrode fabrication process, with the focus on the critical factor of coverage.

Role of passivation ligand in exciton diffusion and emission mechanism of metal halide perovskite nanocrystal solid

Shorter-ligand passivated metal halide perovskite nanocrystal (PNC) solids possess smaller inter-NC edge distance which can potentially activate shorter-range nonradiative routes of energy transfer. However, these PNCs are prone to develop surface defects due to ligand detachment and the photogenerated excitons also have high probability to undergo dissociation. It remains unclear how these factors influence the exciton diffusion and emission mechanism of PNC solids. Herein, we prepare two PNC solids passivated with alkylamine and alkylacid ligands of different chain lengths and investigate the exciton diffusion and emission properties by combining time-resolved photoluminescence (PL) and low temperature PL spectroscopy. Our results show that due to the easy ligand detachment and rich surface defects, no prominent exciton transfer occurs in PNC solid passivated with short ligands, despite of the shorter distance between adjacent PNCs. In comparison, the PNC solid passivated with long ligands shows significant occurrence of exciton diffusion from high energy sites towards low energy sites. Accordingly, the PL spectra of thick PNC solid passivated with different ligands show a strikingly different evolution trend with decreasing temperature: in short ligand passivated PNC solid, an intrinsic emission is observed along with a defect-related emission arising from carrier trapping and subsequent radiative recombination, and both emissions are enhanced at lower temperature; in long ligand passivated PNC solid, high energy emission quenches while low energy emission is strengthened at lower temperature due to enhanced exciton transfer. This work reveals that the exciton diffusion and emission properties of PNC solid is strongly mediated by the passivation ligands, providing important insights for their applications in optoelectronic devices.

Modeling of pulse and relaxation of high-rate Li/CFx-SVO batteries in implantable medical devices

We present a Hybrid Multiphase Porous Electrode Theory (Hybrid-MPET) model that accurately predicts the performance of Medtronic’s implantable medical device battery lithium/carbon monofluoride (CFx) - silver vanadium oxide (SVO) under both low-rate background monitoring and high-rate pulsing currents. The distinct properties of multiple active materials are reflected by parameterizing their thermodynamics, kinetics, and mass transport properties separately. Diffusion limitations of Li+ in SVO are used to explain cell voltage transient behavior during pulse and post-pulse relaxation. We also introduce change in cathode electronic conductivity, Li metal anode surface morphology, and film resistance buildup to capture evolution of cell internal resistance throughout multi-year electrical tests. We share our insights on how the Li+ redistribution process between active materials can restore pulse capability of the hybrid electrode, allow CFx to indirectly contribute to capacity release during pulsing, and affect the operation protocols and design principles of batteries with other hybrid electrodes. We also discuss additional complexities in porous electrode model parameterization and electrochemical characterization techniques due to parallel reactions and solid diffusion pathways across active materials. We hope our models can complement future experimental research and accelerate development of multi-active material electrodes with targeted performance.

Molecular Autonomous Pathfinder Using Deep Reinforcement Learning.

Diffusion in solids is a slow process that dictates rate-limiting processes in key chemical reactions. Unlike crystalline solids that offer well-defined diffusion pathways, the lack of similar structural motifs in amorphous or glassy materials poses great challenges in bridging the slow diffusion process and material failures. To tackle this problem, we propose an AI-guided long-term atomistic simulation approach: molecular autonomous pathfinder (MAP) framework based on deep reinforcement learning (DRL), where the RL agent is trained to uncover energy efficient diffusion pathways. We employ a Deep Q-Network architecture with distributed prioritized replay buffer, enabling fully online agent training with accelerated experience sampling by an ensemble of asynchronous agents. After training, the agents provide atomistic configurations of diffusion pathways with their energy profile. We use a piecewise nudged elastic band to refine the energy profile of the obtained pathway and the corresponding diffusion time on the basis of transition-state theory. With the MAP framework, we demonstrate atomistic diffusion mechanisms in amorphous silica with time scales comparable to experiments.

Assessment of antimicrobial and anti-biofilm activities of lemongrass and bay leaf extracts on microorganisms from fermented cereal-based porridges in northern Benin

Lemongrass (Cymbopogon citratus) and bay leaf (Laurus nobilis) are condiments in food processing. This study aimed to assess the antimicrobial and anti-biofilm activities of lemongrass and bay leaf extract on the microorganisms isolated from cereal-based fermented porridges produced in northern Benin. The phytochemical components of lemongrass and bay leaf extracts were analyzed qualitatively using two solvents: water and alcohol. The antimicrobial activity of the extracts was tested using the solid media diffusion method, and the minimum concentration was determined using the microdilution method. The extracts were also evaluated for their ability to inhibit biofilm formation using qualitative assays. The two plants have different phytochemical profiles. Tannins, flavonoids, mucilage, and alkaloids were detected in both plants. Cyanogenic derivatives, O-heterosides, and genin-reduced O-heterosides were absent. L. nobilis contained anthocyanins, quinone derivatives, saponosides, reducing compounds, and free anthracenes, absent in C. citratus. The inhibition diameters ranged from 4.4 to 26.3, depending on the strains and extracts, and varied significantly. The MICs for Escherichia coli ranged from 4.5 mg/ml to 7 mg/ml, staphylococci from 3.75 mg/ml to 10 mg/ml, and lactic bacteria from 2.5 mg/ml to 4.44 mg/ml. The CMB varied between 8.125 mg/ml and 14 mg/ml for E. coli, 7.5 mg/ml to 20 mg/ml for staphylococci, and 6 mg/ml to 10 mg/ml for lactic bacteria. It is worth noting that staphylococci are the most biofilm-producing strains (80%), followed by E. coli (60%), and lactic bacteria produce less biofilm (30%). The findings of this research confirm the presence of a wide range of biological activities, including antibacterial and anti-biofilm, in the aqueous and ethanolic extracts of these two aromatic plants. Further research is required to identify and isolate the active components responsible for their medicinal properties and ascertain their operation mode.

Theoretical modeling of defect diffusion in wide bandgap semiconductors

Since the 1940s, it has been known that diffusion in crystalline solids occurs due to lattice defects. The diffusion of defects can have a great impact on the processing and heat treatment of materials as the microstructural changes caused by diffusion can influence the material qualities and properties. It is, therefore, vital to be able to control the diffusion. This implies that we need a deep understanding of the interactions between impurities, matrix atoms, and intrinsic defects. The role of density functional theory (DFT) calculations in solid-state diffusion studies has become considerable. The main parameters to obtain in defect diffusion studies with DFT are formation energies, binding energies, and migration barriers. In particular, the utilization of the nudged elastic band and the dimer methods has improved the accuracy of these parameters. In systematic diffusion studies, the combination of experimentally obtained results and theoretical predictions can reveal information about the atomic diffusion processes. The combination of the theoretical predictions and the experimental results gives a unique opportunity to compare parameters found from the different methods and gain knowledge about atomic migration. In this Perspective paper, we present case studies on defect diffusion in wide bandgap semiconductors. The case studies cover examples from the three diffusion models: free diffusion, trap-limited diffusion, and reaction diffusion. We focus on the role of DFT in these studies combined with results obtained with the experimental techniques secondary ion mass spectrometry and deep-level transient spectroscopy combined with diffusion simulations.

Enhanced Nanotwinned Copper Bonding through Epoxy-Induced Copper Surface Modification.

For decades, Moore's Law has neared its limits, posing significant challenges to further scaling it down. A promising avenue for extending Moore's Law lies in three-dimensional integrated circuits (3D ICs), wherein multiple interconnected device layers are vertically bonded using Cu-Cu bonding. The primary bonding mechanism involves Cu solid diffusion bonding. However, the atomic diffusion rate is notably low at temperatures below 300 °C, maintaining a clear and distinct weak bonding interface, which, in turn, gives rise to reliability issues. In this study, a new method of surface modification using epoxy resin to form fine grains on a nanotwinned Cu film was proposed. When bonded at 250 °C, the interfacial grains grew significantly into both sides of the Cu film. When bonded at 300 °C, the interfacial grains extended extensively, eventually eliminating the original bonding interface.

Can large lattice volume always facilitate ion diffusion in solids?

Large lattice volume is usually expected to expand the bottleneck size and enlarge free volume for fast Li ion transport in solids. But the universality of lattice expansion decreasing activation energy barrier for Li ion migration is still debatable. Herein, our molecular dynamics simulations and density functional theory calculations detect the unconventional phenomenon of lattice expansion increasing activation energy barrier for Li ion migration in β-Li3PS4, Li4SnS4 and Li4GeS4 sulfides with the hcp-type anion sublattice, and discover the underlying mechanism. On one hand, lattice expansion enlarges the relative energies between the octahedral and tetrahedral Li sites, and correspondingly increase activation energy barrier for tetrahedral Li ions migration along the Tet-Oct-Tet migration paths in β-Li3PS4, Li4SnS4 and Li4GeS4. On the other hand, the lattice dynamics calculations show Li energy landscapes of β-Li3PS4, Li4SnS4 and Li4GeS4 are anharmonic and enlarging lattice volume make the local minimum of Li potential energy surface flatter, simultaneously reduce the relative energy of Li occupation site, eventually resulting in the higher activation energy barrier for Li ion migration. Thus, understanding the effect of lattice volume on ion migration in solids should not only consider the factor of bottleneck size and free volume, but also combine the aspects of Li ion occupation type, Li ion migration path and anion sublattice type. These new understandings of the lattice expansion increasing activation energy barrier for ion migration would further promote the further optimization and rational design of superionic conductors by element doping or strain engineering.

Measuring the in-plane thermal diffusivity of anisotropic solids by lock-in infrared thermography: Laser-spot vs laser-line heating

A method is proposed to measure the in-plane thermal diffusivity of anisotropic solids along an arbitrary direction using laser-line lock-in thermography. In this method, the sample is heated by an intensity-modulated laser beam, which impinges on the sample surface with the shape of a narrow strip. The resulting temperature oscillations are recorded by a thermographic camera and a phase thermogram is obtained by lock-in processing the image sequence. The thermal diffusivity along the direction perpendicular to the laser line can be determined from the linear dependence of phase lag with the distance to the heating line using the slope method. Unlike laser-spot lock-in thermography, in which the slope method only provides the thermal diffusivity along the principal directions, in this configuration, the thermal diffusivity can be measured experimentally along any direction, just selecting the relative orientation of the sample with respect to the laser line. Moreover, this configuration allows averaging several parallel phase profiles leading to more reliable thermal diffusivity values. The experimental results are presented for a highly anisotropic material, namely, a unidirectional carbon fiber-reinforced polymer plate.

Inhibition of the second phase precipitation and improvement of intergranular corrosion resistance by boron segregation at the grain boundary of S31254 superaustenitic stainless steel

The inhibition of Mo segregation and phase precipitation is vital for improving the hot workability and corrosion resistance of superaustentic stainless steels (SASS). The boron non-equilibrium segregation of S31254 SASS was implemented through solid solution, air cooling, and diffusion at low-temperature treatment (SADT). The precipitation process and intergranular corrosion (IGC) of S31254 SASS with various boron distributions were researched at a sensitive temperature. The second phases were observed and identified by SEM and TEM. IGC susceptibility was evaluated by double-loop potentiodynamic reactivation (DL-EPR) measurements. The SADT treatment promoted more segregation of B at the grain boundary, leading to lower amounts of grain boundary precipitation before aging for 6 h. The decrease of σ phases in B-regulated samples enhances the IGC resistance, compared with the samples without B addition specimens.

Quenching extinction of solid sphere diffusion flames induced by a sudden removal of gravity

The response of a diffusion flame around a PMMA solid sphere to a sudden transition to zero-gravity is investigated both experimentally and numerically. The initial flame is established in normal gravity with a low speed forced flow in a 17% oxygen by volume atmosphere. An abrupt (step change) normal-to-zero gravity transition occurs when the test package is released in the drop tower. The dynamic flame response is recorded by video and modeled numerically. By the end of the 5.18-s drop, the flame tip retreats, and the flame base may either remain stabilized near the forward stagnation region or extinguish depending on several parameters. The two parameters investigated are: forced flow velocity and the degree of preheating in the surface layer of the solid sample. The amount of preheating or equivalently the conductive flame heat loss rate to the solid interior is varied by controlling the duration of the normal gravity burning before releasing to microgravity. The heat loss is quantified by using embedded thermocouples to measure the solid subsurface temperature gradient near the stagnation point. The detailed numerical model reveals details of the flow field and flame structure including oscillatory extinction and quantifies the various transient gas-solid surface energy balance terms.

A competitive trivalent-europium-activated phosphor: Achieving highly efficient red light emission in a sodium-rich garnet host

The reaction temperature is key factor for light-emitting phosphors synthesized by solid state method because it directly determines the crystallinity and further affects the luminescence property of the phosphors. While high temperature certainly benefits to the solid diffusion in reaction, it would waste enormous energy during long time heating. Herein, a novel Eu3+-activated and highly efficient red phosphor, NaGd2Ga3Ge2O12:Eu3+, is reported. By the reconstruction of the traditional Y3Al5O12 garnet host into the sodium-rich NaGd2Ga3Ge2O12 one, huge decrease of the synthesis temperature is successfully achieved. More importantly, such decrease of the synthesis temperature does not dissatisfy the luminescence property of the NaGd2Ga3Ge2O12:Eu3+ phosphors. Instead, the Eu3+ in the NaGd2Ga3Ge2O12 exhibits extremely high quantum yield up to 96.78% upon 394 nm excitation, showing great competitiveness among other iso-structral garnet hosts. This work indicates that the introduction of sodium in the eight-coordinated rare earth site of the garnet host can not only reduce the energy consumption during the stage of phosphor synthesis but also avoid the loss of excitation energy during the light converting stage of the Eu3+ to a large extent. By fabricating the as-synthesized red phosphor into a near-UV chip together with commercial green and blue phosphors, quality white light-emitting diodes with satisfactory color rendering index (as high as 90) and correlated color temperature (as low as 3986 K) can be easily obtained.

Manufacturing high-strength and corrosion-resistant 6063Al joints by an ultrasonic-assisted liquid and solid phase diffusion technology

High corrosion-resistance aluminum alloy joint obtained by filler metal containing Sn at relatively low temperatures is a longstanding goal for electronic products. In this research, 6063Al alloys was joined by a novel ultrasonic-assisted diffusion bonding via liquid phase and solid phase synergistic diffusion. It was performed via a hypereutectic interlayer of Zn-30Sn at 360 ℃ to joining 6063Al, obtaining a Zn-Al eutectoid structures joint. By the ultrasonic vibrating, the breaking of oxide film, the diffusing of liquid and solid state had been occurring in sequence during the joining process. It resulted in a series of diffusing phase transitions from “η-Zn phases + Sn-Zn eutectic structures” to “Zn-Al eutectoid structures + η-Zn phases”, and finally to “full Zn-Al eutectoid structures”, which were driven by the grain boundary penetration and chemical potential, respectively. The joints possessed a higher strength than the base metal. The joints with Zn-Al eutectoids have a better corrosion resistance that the tensile strength reduced 37.3% after a corroding of 72 h in 3.5 wt% NaCl solution in comparison with the soldered joints. Finally, the mechanism of ultrasonic accelerated diffusion, joint formation process and mechanism of improving corrosion resistance were discussed in detail.

Persistent enhancement of exciton diffusivity in CsPbBr3 nanocrystal solids.

In semiconductors, exciton or charge carrier diffusivity is typically described as an inherent material property. Here, we show that the transport of excitons among CsPbBr3 perovskite nanocrystals (NCs) depends markedly on how recently those NCs were occupied by a previous exciton. Using transient photoluminescence microscopy, we observe a striking dependence of the apparent exciton diffusivity on excitation laser power that does not arise from nonlinear exciton-exciton interactions or thermal heating. We interpret our observations with a model in which excitons cause NCs to transition to a long-lived metastable configuration that markedly increases exciton transport. The exciton diffusivity observed here (>0.15 square centimeters per second) is considerably higher than that observed in other NC systems, revealing unusually strong excitonic coupling between NCs. The finding of a persistent enhancement in excitonic coupling may help explain other photophysical behaviors observed in CsPbBr3 NCs, such as superfluorescence, and inform the design of optoelectronic devices.

Kinetics of sphalerite dissolution for potential zinc recovery via oxidative leaching

ABSTRACT In this study, the leaching of zinc from sphalerite in nitric acid (HNO3)/hydrogen peroxide (H2O2) binary solution was examined via kinetic study. The result showed that the amount of zinc leached increased as the temperature and leachant concentration increased, from 53.8 to 91% for H2O2 concentrations of 2 and 10 M; 53 to 93.2% for temperature of 30 and 90°C, respectively, and decreased as the solid/liquid ratio and particle diameter increased from 92.3 to 55.9% for S/L ratios of 20 and 50 g/L; 93.4 to 51.1% for particle diameters of <75 µm and <425 µm, respectively. The solid film diffusion model provided the finest description of the experimental data while chemical reaction was established as the rate-limiting step, with activation energy of 26.52 kJ/mol. Hence, a binary solution of HNO3 and H2O2 was established as a viable route towards recovering zinc from sphalerite.

Transferability of atomic energies from alchemical decomposition

We study alchemical atomic energy partitioning as a method to estimate atomization energies from atomic contributions, which are defined in physically rigorous and general ways through the use of the uniform electron gas as a joint reference. We analyze quantitatively the relation between atomic energies and their local environment using a dataset of 1325 organic molecules. The atomic energies are transferable across various molecules, enabling the prediction of atomization energies with a mean absolute error of 23 kcal/mol, comparable to simple statistical estimates but potentially more robust given their grounding in the physics-based decomposition scheme. A comparative analysis with other decomposition methods highlights its sensitivity to electrostatic variations, underlining its potential as a representation of the environment as well as in studying processes like diffusion in solids characterized by significant electrostatic shifts.

Acidic leaching kinetics study on vanadium from magnesiation-roasted vanadium slag

In order to promote the industrial application of the magnesiation roasting–acid leaching method, the acidic leaching kinetics of vanadium from magnesiation-roasted vanadium slag was investigated. By combination of XRD, XPS, and SEM, it was revealed that MgSiO3 and most vanadates consumed acid sharply to produce SiO2 and V(V)-containing vanadyl in the initial 10 min. The variation of vanadium extraction efficiency with leaching time was studied to establish the kinetic models for leaching. Results indicated two distinct stages in the leaching process and the kinetics of both stages followed the shrinking core model. The leaching rate in 0−10 min was controlled by both solid product layer diffusion and chemical reactions, while the leaching rate in 10−30 min was controlled only by chemical reactions. Therefore, it is essential to accelerate the mass transfer in initial 10 min and accurately control the temperature in the following 20 min during leaching.

Low-Temperature and High-Performance Vanadium-Based Aqueous Zinc-Ion Batteries.

Aqueous zinc-ion batteries have attracted attention due to their low cost and high safety. Unfortunately, dendrite growth, hydrogen evolution reactions, cathodic dissolution, and other problems are more serious; not only that, but also the cathodic and anodic materials' lattices contract when the temperature drops, and charge transfer and solid phase diffusion become slow, seriously aggravating dendrite growth. At present, there are few studies on the low-temperature system, and studies on retaining high specific capacity are even more rare. Herein, ethylene glycol (EG) and manganese sulfate (MSO) are selected as additives, and the manganese vanadate (MVO) cathode is used to find a high-performance solution at low temperature. MVO can provide higher specific capacity and better structural stability than MnO2 to adapt to a low-temperature environment. At the same time, Mn2+ in MSO can produce a cationic shield covering the initial zinc tip at an appropriate concentration to avoid the tip effect and inhibit the dissolution of MVO. EG can not only reduce the freezing point of the electrolyte but also promote the desolvation of [Zn(H2O)6]2+. The synergistic effect of the three elements prevents the dissolution equilibrium of Mn2+ in MVO from fluctuating greatly due to the change of temperature. Therefore, when we use EG@0.2 M MnSO4 + 2 M ZnSO4 (EG + 0.2Mn/2ZSO) electrolyte at -30 °C, the Zn||Zn batteries which used this type of electrolyte can remain 350 h at 1 mA cm-2 without failure. The Zn||Cu batteries can retain 100% Coulombic efficiency after more than 2000 cycles at 0.2 mA cm-2. The Zn||MVO battery can reach 231.13 mA h g-1 at its first cycle, and the capacity retention rate is still above 85% after 1000 cycles, which is higher than that of the existing low-temperature research system.

Nanoscale Kirkendall shift in thin films studied using x-ray waveguide structures

Kirkendall effect has played an important role in developing the understanding of atomic diffusion and mass transport in solids. In thin films and multilayers, in which the microstructure may be far from thermal equilibrium, behavior of a system can be very different from that of the bulk. Therefore, there is a great need to understand the peculiarities of Kirkendall shift occurring at nanometer or sub-nanometer length scale in such systems. In the present work, Kirkendall shift in thin films has been measured with sub-nanometer accuracy, by making use of x-ray planar waveguide structures. Using this technique, we report an apparently counterintuitive result of Kirkendall shift associated with self-diffusion in nanocrystalline iron. The cavity of the waveguide consists of two layers of iron having different microstructures, separated by a thin marker layer of Ag. Thermal annealing results in shift of the Ag marker towards the Fe layer having a coarser grain structure. The effect is established unambiguously by studying two samples with the order of the two Fe layers reversed, and a third sample with the two Fe layers having the same microstructure. The result can be understood in terms of the difference in the microstructure of the two Fe layers; difference in the grain size and hence different concentration of the grain boundaries in the two layers results in a net mass transfer from one region to the other.