Diffuse Interface Research Articles

Interfacial and mass transport phenomena in the tri-ethylene glycol-methane system at process conditions of natural gas dehydration

AbstractUnderstanding the phase and interphase behavior at equilibrium and during the mass transfer between two adjacent fluid phases is relevant for optimizing and designing efficient separation processes. This study experimentally investigates the interfacial and transport behavior of systems comprising tri-ethylene glycol (TEG) and methane (CH4) under conditions relevant to the gas dehydration process. A comprehensive review of the interfacial tension (IFT) and diffusivity of systems involving non-polar and polar compounds at elevated pressures was studied. However, a research gap exists, particularly concerning the interfacial tension of systems involving TEG, TEG + water, and different types of gases as well as the diffusivity of CH4 in TEG. To address this gap, this study presents new data on mixture densities, interfacial tension, and drop volumes of TEG and TEG + water in CH4 and CH4 + CO2 mixtures at temperatures ranging from 20 to 50 °C and pressures up to 250 bar using the oscillating U-tube and pendant drop methods, respectively. Additionally, time-dependent fluid mixture densities and TEG droplet volumetric expansion, coupled with an analytical approach for the binary diffusion were applied to determine the CH4 solubility and diffusivity in TEG. The results show that IFT and drop volume of TEG and TEG + water in CH4 and CH4 + CO2 mixtures decrease with increasing pressure. The presence of water increases the IFT of TEG-CH4 up to $$\sim$$ ∼ 5mN/m, while CO2 reduces it by $$\sim$$ ∼ 2mN/m. Interestingly, the IFT and drop volume of TEG-CH4 show no significant change at elevated pressures when temperatures rise from 20 to 50 °C. IFT remains relatively constant over time at moderate pressures but decreases by $$\sim$$ ∼ 3mN/m at an elevated pressure of 150 bar, suggesting methane solubilization into TEG to have a significant influence which is confirmed by TEG drop volume expansion. The diffusivity of CH4 in TEG at 150 bar and 50 °C is determined to be in the range of 10–10 m2/s, which is in agreement with the diffusivity of CH4 in liquids of similar viscosity, i.e. according correlations may be applied as good engineering practice. To the best of our knowledge, there is no such comprehensive work on the properties of fluid mixtures relevant in gas dehydration processes published up to date.

Interface kinetic manipulation enabling efficient and reliable Mg3Sb2 thermoelectrics

Development of efficient and reliable thermoelectric generators is vital for the sustainable utilization of energy, yet interfacial losses and failures between the thermoelectric materials and the electrodes pose a significant obstacle. Existing approaches typically rely on thermodynamic equilibrium to obtain effective interfacial barrier layers, which underestimates the critical factors of interfacial reaction and diffusion kinetics. Here, we develop a desirable barrier layer by leveraging the distinct chemical reaction activities and diffusion behaviors during sintering and operation. Titanium foil is identified as a suitable barrier layer for Mg3Sb2-based thermoelectric materials due to the creation of a highly reactive ternary MgTiSb metastable phase during sintering, which then transforms to stable binary Ti-Sb alloys during operation. Additionally, titanium foil is advantageous due to its dense structure, affordability, and ease of manufacturing. The interfacial contact resistivity reaches below 5 μΩ·cm2, resulting in a Mg3Sb2-based module efficiency of up to 11% at a temperature difference of 440 K, which exceeds that of most state-of-the-art medium-temperature thermoelectric modules. Furthermore, the robust Ti foil/Mg3(Sb,Bi)2 joints endow Mg3Sb2-based single-legs as well as modules with negligible degradation over long-term thermal cycles, thereby paving the way for efficient and sustainable waste heat recovery applications.

Toughening Mechanism of CaAl12O19 in Red Mud–Al2O3 Composite Ceramics

The utilization of red mud in the production of ceramic products represents an efficient approach for harnessing red mud resources. Composite ceramics were prepared from Al2O3, red mud, and Cr2O3 by atmospheric pressure sintering, and the phase composition and microscopic morphology of the composite ceramics were investigated by XRD, SEM, and EDS. The flexural strength and fracture toughness of composite ceramics were measured by three-point bending and SENB methods. The results showed that the composite ceramics sintered at 1500 °C with the addition of 1.5 wt.% Cr2O3 had a flexural strength of 297.03 MPa, a hardness of 17.44 GPa, and a densification of 97.75% and fracture toughness of 6.57 MPa·m1/2. The addition of Cr2O3 helps to improve the low strength of red mud composite ceramic samples. The CaAl12O19 phase can form a similar “endo-crystalline” structure with Al2O3 grains, which changes the fracture mode of the ceramics and thus significantly improves the fracture toughness. The wettability tests conducted on Cu and RM–Al2O3 composite ceramic materials revealed that the composites exhibited non-wetting behavior towards Cu at elevated temperatures, while no interfacial reactions or elemental diffusion were observed. Composites have higher surface energy than Al2O3 ceramic at high temperatures. The present study provides a crucial foundation for enhancing the comprehensive utilization value of red mud and the application of red mud ceramics in the field of electronic packaging.

Coupling Manipulation of Interfacial Chemistry and Coordination Structure in Vanadium Oxides Enables Rapid Magnesium Ion Diffusion Kinetics

AbstractRechargeable magnesium batteries (RMBs) are a highly promising energy storage system due to their high volumetric capacity and intrinsic safety. However, the practical development of RMBs is hindered by the sluggish Mg2+ diffusion kinetics, including at the cathode‐electrolyte interface (CEI) and within the cathode bulk. Herein, we propose an efficient strategy to manipulate the interfacial chemistry and coordination structure in oligolayered V2O5 (L−V2O5) for achieving rapid Mg2+ diffusion kinetics. In terms of the interfacial chemistry, the specific exposed crystal planes in L−V2O5 possess strong electron donating ability, which helps to promote the degradation dynamics of C−F/C−S bonds in the electrolyte, thereby establishing the inorganic‐organic interlocking CEI layer for rapid Mg2+ diffusion. In terms of the coordination structure, the straightened V−O structure in L−V2O5 provides efficient ions diffusion path for accelerating Mg2+ diffusion in the cathode. As a result, the L−V2O5 delivers a high reversible capacity (355.3 mA h g−1 at 0.1 A g−1) and an excellent rate capability (161 mAh g−1 at 1 A g−1). Impressively, the interdigital micro‐RMBs is firstly assembled, exhibiting excellent flexibility and practicability. This work gives deeper insights into the interface and interior ions diffusion for developing high‐kinetics RMBs.

Electrocatalytic Applications in Hydrogen Evolution of Two Nitrogen Heterocyclic Cu(I) Coordination Polymer Modified Electrodes

ABSTRACTThe development of low‐cost, high‐efficiency, stable, and structurally adjustable electrocatalysts for hydrogen evolution reaction (HER) is of great significance for energy conversion. In this study, two new Cu(I) coordination polymers (CPs), formulated as {[Cu(L1)](PF6)·CH2Cl2}n (1) and {[Cu2(L2)1.5(PPh3)](PF6)2}n (2) (L1 = 1,3‐bis[1‐(pyridin‐3‐ylmethyl) ‐1H‐benzimidazol‐2‐yl]propane, L2 = 1,4‐bis[1‐(3‐pyridylmethyl)‐1H‐benzimidazol‐2‐yl]butane), were synthesized by interfacial diffusion method and characterized by single‐crystal x‐ray diffraction and IR and UV–Vis spectra. Structural analysis shows that the CP‐1 is a one‐dimensional chain structure, whereas the CP‐2 is a two‐dimensional layered structure, which is due to the different coordination modes of ligands L1 (bridging chelation) and L2 (bridging). The electrocatalytic activity for HER of Cu(I) CPs was studied by preparing modified glassy carbon electrodes (CP‐1/GCE and CP‐2/GCE). Electrochemical HER studies manifest that in 0.5 M H2SO4, the overpotential (η10298K) and Tafel slope (b 298K) are −769 mV and 173 mV dec−1 for CP‐1/GCE, −933 mV and 301 mV dec−1 for CP‐2/GCE, and −930 mV and 298 mV dec−1 for bare/GCE, respectively. The η10298K and b298K of CP‐1/GCE were significantly positive shifted and decreased compared with the bare/GCE, indicating that CP‐1/GCE has significant electrocatalytic activity and electrocatalytic HER activity order is CP‐1/GCE > CP‐2/GCE ≈ bare/GCE. This work provides an important reference for the application of non‐noble metal CPs in the field of electrocatalysis.

Integrative models for environmental forecasting of phthalate migration from microplastics in aquaculture environments

The pervasive utilization of plastic tools in aquaculture introduces significant volumes of microplastic fibers, presenting a consequential risk through the leaching of additives such as phthalates. This study scrutinizes the leaching dynamics of six prevalent phthalate esters (PAEs) from thirteen plastic aquaculture tools comprising polyethylene terephthalate (PET), polypropylene (PP), and polyethylene (PE), with ΣPAEs ranging from 0.24 to 4.26 mg g−1. Di(2-ethylhexyl) phthalate (DEHP) and dibutyl phthalate (DBP) emerged as predominant, marking significant environmental concern. Over a 30-day period, leaching quantities of Σ6PAEs from PET, PP, and PE fibers reached 36.65 μg g−1, 21.87 μg g−1 and 19.11 μg g−1, respectively, influenced by factors such as time, temperature, turbulence, and salinity. Notably, turbulence exerted the most pronounced effect, followed by temperature, with negligible influence from salinity. The kinetic models aligning with interface diffusion control was developed, predicting PAEs' leaching behavior with activation energies (Ea) indicative of the process's thermodynamic nature. The application of this model to real-world aquaculture waters forecasted significant risks, corroborating with empirical data and underscoring the pressing need for regulatory and mitigation strategies against PAEs contamination from aquaculture practices.

Microstructure of interfacial diffusion layer of cross-layered silver–copper composite strip and its effect on resistivity

Microstructure of interfacial diffusion layer of cross-layered silver–copper composite strip and its effect on resistivity

Structure, orientation, and dynamics of per- and polyfluoroalkyl substance (PFAS) surfactants at the air-water interface: Molecular-level insights

HypothesisUnderstanding the intricate molecular-level details of toxic per- and polyfluoroalkyl substances (PFAS) partitioning to the air–water interface holds paramount importance in evaluating their fate and transport, as well as for finding safer alternatives for various applications, including aqueous film forming foams. The behavior of these substances at interfaces strongly depends on molecular architecture, chemistry, and concentration, which define molecular packing, self-assembly, interfacial diffusion, and the surface tension. SimulationsModeling of three PFAS surfactants, namely, longer-tail (perfluorooctanoate (PFOA)) and shorter-tail (perfluorobutanoate (PFBA) and 2,3,3,3-tetrafluoro-2-(heptafluoropropoxy) propanoate (GenX)) has been conducted using atomistic molecular dynamics simulations. A systematic comparison between these representative PFAS of different sizes and structure reveals factors influencing their association behavior, mechanism of surface tension reduction, and interfacial mobility as a function of surface coverage. FindingsShorter-chain PFAS surfactants (GenX or PFBA) require lower surface coverage compared to longer chain (PFOA) PFAS to achieve the same decrease in surface tension. However, a higher concentration of GenX and PFBA is necessary in the bulk aqueous solution to achieve the same surface coverage as PFOA, due to their higher solubility in water. The PFAS molecular orientation and mobility at the interface are found to be vastly influenced by the length and architecture of the hydrophobic fluorocarbon tail. A significant ordering of the water dipole moment near the anionic headgroup is apparent at high surface concentration. A direct correlation is established between the PFAS interfacial properties and PFAS-PFAS, PFAS-counterion, and PFAS-water interactions.

Incorporation of TC4 (Ti-6Al-4V) to construct strong interfacial bonding with Mg matrix to achieve improved hydrogen storage kinetics

Effective contact between the catalyst and the Mg/MgH2 matrix is the key to efficiently enhancing the hydrogen storage kinetics. In this work, a Mg-10 wt% TC4 (Ti-6Al-4V) composite with strong interfacial bonding was prepared by vacuum hot pressing sintering, and the reinforcement mechanism of TC4 was investigated. The results indicated that TC4 has a significant improvement effect on the activation efficiency and hydrogen absorption/desorption kinetics. The hydrogen absorption and desorption activation energies of AZ91-TC4 (53.0/111.3 kJ/mol) are 19.6 and 37.2 kJ/mol lower than that of AZ91 without TC4, respectively. Moreover, TC4 can cause AZ91 to start dehydrogenation at 449 K, and the reduction is about 110 K. Except for the increase of grain boundaries and microcracks caused by TC4, the transition diffusion interface formed by TC4 and Mg matrix with a lower diffusion barrier can be used as a special fast diffusion channel to accelerate the hydrogenation process controlled by H atom diffusion. Meanwhile, the kinetic calculations indicate that the dehydrogenation process of AZ91 is controlled by the nucleation and growth step of Mg, and its nucleation activation energy is ca. 4 times the growth activation energy. TC4 and its induced precipitation of TiAl and Al8Mn5 can dramatically accelerate the nucleation process of Mg, resulting in the rate-determining step changing to the surface penetration of H atoms, and the desorption rate is significantly improved. These positive findings provide new tactics for designing excellent hydrogen storage catalysts.

Uniqueness of the blow‐down limit for a triple junction problem

AbstractWe prove the uniqueness of blow‐down limit at infinity for an entire minimizing solution of a planar Allen–Cahn system with a triple‐well potential. Consequently, can be approximated by a triple junction map at infinity. The proof exploits a careful analysis of energy upper and lower bounds, ensuring that the diffuse interface remains within a small neighborhood of the approximated triple junction at all scales.

Diffusion Interface Evolution of Low-Alloy Steel Q235 and Ti by Electro-Assisted Hot-Pressing Bond

Diffusion Interface Evolution of Low-Alloy Steel Q235 and Ti by Electro-Assisted Hot-Pressing Bond

A coated hypotrochoidal compressible liquid inclusion neutral to a hydrostatic stress field after relaxation by interface slip and diffusion

We study the steady-state response of a three-phase composite composed of an internal hypotrochoidal compressible liquid inclusion, an intermediate isotropic elastic coating and an outer isotropic elastic matrix with simultaneous interface slip and diffusion occurring on the solid–solid interface when the matrix is subjected to a uniform hydrostatic stress field. We design a neutral coated hypotrochoidal liquid inclusion that does not disturb the prescribed uniform hydrostatic stress field in the surrounding matrix. The neutrality is achieved when the plane-strain bulk modulus or the compressibility of the elastic matrix is determined by solving a system of simultaneous linear algebraic equations for given geometric and material parameters of the coated liquid inclusion.

High-performance polyurea nanofiltration membrane for waste lithium-ion batteries recycling: Leveraging synergistic control of bulk and interfacial monomer diffusion

The development of high-performance nanofiltration (NF) membranes with extreme chemical stability is urgently needed for the recovery of spent lithium. In this study, a series of polyurea membranes with high lithium recovery efficiency and pH stability were fabricated by zone-regulated interfacial polymerization (IP). The reaction inhibitor Cu2+ in the bulk aqueous phase reduces IP intensity by reversibly binding to the amino groups of polyethyleneimine monomers through chelate bonds. Meanwhile, surfactant promote the uniform diffusion of macromolecular aqueous monomers at the phase interface. The milder polymerization reaction and the more stable phase interface endow the polyurea membrane (NF10k PEI-SDS-Cu2+) with higher water permeance (2.1 L m-2 h-1 bar-1), desirable MgCl2 rejection (94.7%), and excellent fabrication repeatability. Moreover, the membrane demonstrates stable separation selectivity for Co2+/Li+ and SO42-/Li+ under conditions of 0.05 mol L-1 H2SO4 and 2 mol L-1 LiOH, respectively. Our study provides a facile method for constructing NF membranes with extreme pH stability and confirms the feasibility of membrane-based lithium recovery.

A diffuse interface model for electro-chemo-mechanical systems

Electro-chemo-mechanics plays a critical role in the performance and longevity of energy storage systems, such as lithium-ion batteries and hydrogen energy storage. These systems involve multi-material composites comprising both liquid and solid phases, with their behavior influenced by processes in the bulk phases and at their interfaces.Traditional multi-phase theoretical and numerical models often adopt a discrete representation of material interfaces, introducing discontinuities in the problem’s fields. The numerical implementation is carried out using special interface elements, a methodology that requires conformal meshes and is not always supported by open-source computing platforms.This paper introduces a novel modeling framework that employs a diffuse representation of material interfaces, inspired by the phase-field method. From a modeling perspective, this approach allows for the consistent coupling of bulk and interface electro-chemo-mechanical processes, adhering to thermodynamic principles. Numerically, the proposed model is particularly suited for simulating real material microstructures using regular meshes, facilitating advanced numerical implementations.The methodology is detailed for a generic multi-material electro-chemo-mechanical system and applied specifically to Li-ion batteries. Numerical examples demonstrate the model’s effectiveness in simulating coupled interface processes without resorting to interface elements. This work provides a significant advancement in the simulation of electro-chemo-mechanical systems, offering a robust tool for studying the complex interplay of bulk and interface processes.

Investigation of the sintering behavior of nanoparticulate SiC by molecular dynamics simulation

Sintering is a valuable processing technique utilized to create bulk materials from powder compacts. In recent years, sintering has a garnered significant attention in the research community due to its versatility and applicability in various fields, including additive manufacturing. Herein, we investigate the sintering kinetics and mechanism of SiC nanoparticulate using molecular dynamics simulations. The surface morphology, microstructure, radial distribution function, mean square displacement, atomic displacement distribution, structural transformation, and diffusion coefficient are analyzed in detail. The free surface surrounding the neck undergoes a reconstruction to eventually reach an equilibrium dihedral angle. The neck rapidly grows and aligns with the surface, causing the SiC particle to transform from an original spherical shape into a twists shape. The concentration of shear stress results in a change of the local lattice structure from the face-centered cubic phase to amorphous phase in the surface. With an increasing sintering time, the dominant diffusion mechanism gradually shifts from surface diffusion to interface diffusion. This trend leads to a rise in the atomic migration, the consumption of interface energy, and the degree of particle fusion. Ultimately, the sintered SiC particles have the spherical shape, low surface energy, and stable structure. Additionally, the high mobility of melted atom causes a gradual dissolution of SiC particle into the large particle from the surface towards the interior. This process leads to high-altitude concentration structures that facilitate atomic migration. These results shed light on an atomic sintering mechanism in SiC nanoparticulate for applications in the preparation of nanostructured materials, and additive manufacturing.

Pt thin-film resistance thermo detectors with stable interfaces for potential integration in SiC high-temperature pressure sensors

Due to the excellent mechanical, chemical, and electrical properties of third-generation semiconductor silicon carbide (SiC), pressure sensors utilizing this material might be able to operate in extreme environments with temperatures exceeding 300 °C. However, the significant output drift at elevated temperatures challenges the precision and stability of measurements. Real-time in situ temperature monitoring of the pressure sensor chip is highly important for the accurate compensation of the pressure sensor. In this study, we fabricate platinum (Pt) thin-film resistance temperature detectors (RTDs) on a SiC substrate by incorporating aluminum oxide (Al2O3) as the transition layer and utilizing aluminum nitride (AlN) grooves for alignment through microfabrication techniques. The composite layers strongly adhere to the substrate at temperatures reaching 950 °C, and the interface of the Al2O3/Pt bilayer remains stable at elevated temperatures of approximately 950 °C. This stability contributes to the excellent high-temperature electrical performance of the Pt RTD, enabling it to endure temperatures exceeding 850 °C with good linearity. These characteristics establish a basis for the future integration of Pt RTD in SiC pressure sensors. Furthermore, tests and analyses are conducted on the interfacial diffusion, surface morphological, microstructural, and electrical properties of the Pt films at various annealing temperatures. It can be inferred that the tensile stress and self-diffusion of Pt films lead to the formation of hillocks, ultimately reducing the electrical performance of the Pt thin-film RTD. To increase the upper temperature threshold, steps should be taken to prevent the agglomeration of Pt films.

TexSe1-x Shortwave Infrared Photodiode Arrays with Monolithic Integration.

TexSe1-x shortwave infrared (SWIR) photodetectors show promise for monolithic integration with readout integrated circuits (ROIC), making it a potential alternative to conventional expensive SWIR photodetectors. However, challenges such as a high dark current density and insufficient detection performance hinder their application in large-scale monolithic integration. Herein, we develop a ZnO/TexSe1-x heterojunction photodiode and synergistically address the interfacial elemental diffusion and dangling bonds via inserting a well-selected 0.3 nm amorphous TeO2 interfacial layer. The optimized device achieves a reduced dark current density of -3.5 × 10-5 A cm-2 at -10 mV, a broad response from 300 to 1700 nm, a room-temperature detectivity exceeding 2.03 × 1011 Jones, and a 3 dB bandwidth of 173 kHz. Furthermore, for the first time, we monolithically integrate the TexSe1-x photodiodes on ROIC (64 × 64 pixels) with the largest-scale array among all TexSe1-x-based detectors. Finally, we demonstrate its applications in transmission imaging and substance identification.

Investigating Material Interface Diffusion Phenomena through Graph Neural Networks in Applied Materials.

Understanding and predicting interface diffusion phenomena in materials is crucial for various industrial applications, including semiconductor manufacturing, battery technology, and catalysis. In this study, we propose a novel approach utilizing Graph Neural Networks (GNNs) to investigate and model material interface diffusion. We begin by collecting experimental and simulated data on diffusion coefficients, concentration gradients, and other relevant parameters from diverse material systems. The data are preprocessed, and key features influencing interface diffusion are extracted. Subsequently, we construct a GNN model tailored to the diffusion problem, with a graph representation capturing the atomic structure of materials. The model architecture includes multiple graph convolutional layers for feature aggregation and update, as well as optional graph attention layers to capture complex relationships between atoms. We train and validate the GNN model using the preprocessed data, achieving accurate predictions of diffusion coefficients, diffusion rates, concentration profiles, and potential diffusion pathways. Our approach offers insights into the underlying mechanisms of interface diffusion and provides a valuable tool for optimizing material design and engineering. Additionally, our method offers possible strategies to solve the longstanding problems related to materials interface diffusion.

A self-organized sandwich structure of chromium nitride for ultra-long lifetime in liquid sodium.

The development of fast neutron reactors with improved efficiency and sustainability, being a tangible solution to the large-scale utilization of nuclear energy, serves as a critical step prior to the commercialization of fusion energy. These reactors use liquid metal coolants, which can weaken the durability of metallic components. Conventional design of protective coatings counts upon thermodynamics, which often overlooks the kinetic factors such as structural evolutions, resulting in deteriorated coating properties. Herein, we present a novel interface-engineering strategy involving the control of the phase transformation direction and interface diffusion reaction. Through iterations of self-organization, desired surfaces and interfaces can be achieved for materials used in harsh environments. Specifically, a CrN-coated steel sample with an interfacial Cr layer was designed and fabricated. After ultra-long (up to 6000 h) immersion in liquid sodium, the CrN/Cr coating structure was converted into a sandwich Cr2N/CrN/Cr2N structure dynamically. As a consequence, the coating system exhibited enhanced properties, namely increased surface hardness (by ∼36%), reduced coefficient of friction (by ∼13%), and enhanced interfacial adhesion (by ∼37%). Thus, the proposed strategy can guide the future design of robust coatings with ultra-long service life in harsh environments.

Electrochemical-mechanical coupled interfacial degradation model of Ternary polymer composite cathodes in all-solid-state batteries

Despite significant attention focused on the composite cathode composed of active particles, which is considered to increase the interfacial areas and satisfy high areal load, suffers from interfacial issues. In this article, we formulate an electrochemical-mechanical model of LiNixMnyCozO2 (NMC) composite cathode coupling the relations between interfacial degradation, charge transformation, diffusion transport, and mechanical deformation under cyclic loads. Based on the transition state theory, we regard the interfacial degradation as an energy barrier dependent on the interfacial debonding state. Physical mismatch due to chemical expansion results in interfacial current distinction, anisotropic Li diffusion and excessive local stress. Compared to single-crystal NMC particles, the effect of interfacial separation and internal cracks triggers an extremely nonuniformity of Li distribution within random orientation polycrystalline-type particles. The external pressure in the range of operation can cause mechanical deformation to fill in the interface vacancies, which effectively alleviates the rapid growth of damage and provides a better cyclic performance. Moreover, soft polymer-based solid electrolytes take advantage of their flexible property to deal with solid-solid contact, providing considerable maintenance of interface stability. This present framework reveals the failure mechanism with electrochemical-mechanical coupled relations for composite cathode materials and broadens the design guidance toward improving interfacial integrity.