Interfacial Nucleation Research Articles

First-principles study on TiC/TiN heterogeneous nucleation interface in high-titanium steel

A systematic study using the first-principles method was conducted to investigate the interface relationship between TiC and TiN in high-titanium steel, where TiC nucleates and grows with TiN as the core. The results showed that the energy of the (111) surface depends on the type of terminal atoms, with the Ti-terminated surface exhibiting lower surface energy than the C(N)-terminated surface. In contrast, the energy of (100) and (110) surfaces was independent of the terminal atom type. The order of surface energy determined to be (111)-Ti<(100)<(110)<(111)-C(N), the work function exhibits the same trend, while the stability is exactly the opposite. Among all interface structures, the interface structure with Ti-C terminal atomic combination was identified as the most stable, which can be attributed to the formation of covalent, ionic, and metallic bonds at the interface. The bonding strength primarily arises from the hybridization between Ti-d orbitals and C(N)-p orbitals. Within the (111) interface structures, metallic bonds were formed in the interface structure with the Ti-Ti terminal atomic combination, leading to the lowest interface energy and making it thermodynamically the most stable. Consequently, TiC is capable of heterogeneously nucleating on TiN, with the preferred nucleation surface of TiN following the order of (111)>(100)>(110).

Silicone‐Assisted Autonomous Growth of Strainless Perovskite Single Crystals for Integrated Low‐Dose X‐Ray Imaging Arrays

AbstractMetal halide perovskite single crystals (SCs) have emerged as promising candidates for high‐performance X‐ray detectors. However, mitigating the adverse effects of thermal and interfacial stress during SC growth remains a significant challenge. In this study, the solution growth of high‐quality perovskite SCs using silicone containers through a constant‐temperature autonomous crystallization process is presented. Unlike conventional hard glass vessels, soft silicone containers significantly reduce the negative impact of thermal and interfacial stress on SC growth. Additionally, the microporous nature of silicone containers permits solvent leakage, facilitating autonomous SC growth at constant temperatures. The hydrophilic surface of the silicone further increases the interfacial nucleation barrier and enhances mass transfer, promoting the rapid growth of larger SCs. This multifaceted approach results in MAPbBr3 SCs with an exceptionally low defect density of 2.15×108 cm−3 and an optimal full‐width‐at‐half‐maximum of X‐ray diffraction rocking curves at 19.04 arcsec, consequently leading to an ultralow X‐ray detection limit of 850 pGyair s−1 for the X‐ray detectors. The superior quality of the SCs, combined with a low‐temperature flip‐chip bonding process, enables the integration of the crystals with pixelated arrays on a printed circuit board for both single‐photon detection and low‐dose X‐ray imaging.

The Inhibition of Interfacial Ice Formation and Stress Accumulation with Zwitterionic Betaine and Trehalose for High-Efficiency Skin Cryopreservation.

Cryopreservation is a promising technique for the long-term storage of skin. However, the formation of ice crystals during cryopreservation unavoidably damages skin structure and functionality. Currently, the lack of thorough and systematic investigation into the internal mechanisms of skin cryoinjury obstructs the advancement of cryopreservation technology. In this study, we identified 3 primary contributors to skin cryoinjury: interfacial ice nucleation, stress accumulation, and thermal stress escalation. We emphasized the paramount role of interfacial ice nucleation in provoking ice growth within the skin during the cooling process. This progress subsequently leads to stress accumulation within the skin. During the rewarming process, the brittleness of skin, previously subjected to freezing, experienced a marked increase in thermal stress due to ice recrystallization. Based on these insights, we developed a novel zwitterionic betaine-based solution formulation designed for cryopreservation skin. This cryoprotective agent formulation exhibited superior capability in lowering ice nucleation temperatures and inhibiting ice formation at interfaces, while also facilitating the growth of smooth and rounded ice crystals compared to sharp-edged and cornered crystals formed in aqueous solutions. As a result, we successfully achieved prolonged cryopreservation of the skin for at least 6 months, while preserving 98.7% of structural integrity and 94.7% of Young's modulus. This work provides valuable insights into the mechanisms of ice crystal damage during organ cryopreservation and profoundly impacts the field of organ transplantation and regenerative medicine.

In-situ construction of high-performance artificial solid electrolyte interface layer on anode surfaces for anode-free lithium metal batteries

The electrochemical performance of lithium metal batteries (LMBs) was hampered by the uncontrolled growth of lithium (Li) dendrites. To address this issue, the extensive application of artificial solid electrolyte interphase (SEI) coatings on anode surfaces emerged as an effective solution. Electrospinning, as an innovative technique for fabricating artificial SEI layers on the surface of copper (Cu) foil, effectively mitigated Li volume strain during cycling. In this study, an electrospun organic–inorganic composite nanofiber membrane was in-situ fabricated on Cu foil, serving as an artificial SEI layer (CuWs) for anode-free LMBs (AF-LMBs) to enhance battery performance. Lithiophilic polyvinylpyrrolidone was used as the polymer matrix, and Cu nitrate served as the inorganic functional particles capable of in-situ redox reactions. The CuWs with their three-dimensional (3D) network structure accommodated electrode volume changes and suppressed Li dendrite growth during Li deposition and stripping. Additionally, CuWs facilitated the in-situ generation of Li nitrate (LiNO3), which helped stabilize SEI layer and enhance Li utilization. The release sites of LiNO3 on the nanofibers enabled the in-situ reduction of metallic Cu, providing nucleation sites for Li deposition and forming the 3D ion–electron hybrid conductive networks. This CuWs layer reduced interfacial resistance and nucleation barriers, promoting uniform Li+ distribution on the anode surface. Li-Cu cells incorporating CuWs exhibited remarkable cycling stability, enduring over 460 cycles at 1.0 mA cm−2 and 1.0 mAh cm−2 with an average Coulombic efficiency of over 98.6 %. In Li-poor cells, the LFP|PE|CuWs achieved stable cycling for more than 30 cycles at 1.0 C, with a capacity retention rate of 92.0 %. These findings demonstrated that the CuWs membrane significantly enhanced the electrochemical performance of Li-poor cells and provided a novel artificial SEI protective strategy for advanced AF-LMBs with high energy density.

Implementing numerical algorithms to optimize the parameters in Kampmann–Wagner Numerical (KWN) precipitation models

The Kampmann–Wagner Numerical (KWN) model of precipitation is a powerful tool to simulate the precipitation of the second phase considering the nucleation, growth, and coarsening. Some quantities such as interfacial energy and nucleation site number density are required to accomplish the simulation. Practically, those quantities are hard to measure in the experiment directly, and the derivation of those quantities through modeling can also be costly. In this work, we hereby adopt the minimization algorithm implemented in the open-source Scipy Python package to derive that important information in terms of very limited experimental data. The convergence and robustness of different algorithms are discussed. Among those algorithms, the Nelder–Mead and Powell algorithms are successfully applied to optimize multiple parameters during KWN modeling. This work will shed light on the design of experiments/processes and facilitate integrated computational materials engineering (ICME).

Highly stable anode-free sodium batteries enabled by mechanically deformable nucleation interface

Anode-free sodium metal batteries (AFNMBs) with zero excess sodium offer superior energy density, lower cell cost, and design practicality for next-generation EVs and other applications. However, reaching consistent high Coulombic efficiency (CE) greater than 99.9 % remains a challenge for this battery architecture. In this study, our findings support that using a soft Li metal interface under a current collector coated with a thin carbon black nucleation layer facilitates extremely stable nucleation and growth of Na metal by locally distributing pressure to mitigate SEI or dead sodium formation. Specifically, our findings demonstrate Na half cells with stable CE of 99.98 % over 500 cycles at 0.5 mA/cm2. Further, zero-excess sodium full cell AFNMBs with Na3V2(PO4)3 cathodes exhibit total first cycle formation loss of only 5.4 % at C/10 rates, which is over two times lower than commercial Li-ion cells, with capacity retention of 97.4 % after 100 cycles at 0.5 mA cm-2 (∼ C/3) and average round-trip charge efficiency of 99.97 %.

Fluorinated ester additive to regulate nucleation behavior and interfacial chemistry of room temperature sodium-sulfur batteries

Room temperature sodium-sulfur (RT Na-S) batteries are considered as advanced energy storage technology due to their low cost and high theoretical energy density. However, challenges such as the growth of sodium dendrite and dissolution of sodium polysulfides significantly hinder the electrochemical performance. Herein, we developed a propylene carbonate (PC)-based electrolyte with Methyl 2-Fluoroisobutyrate (MFB) as an additive. The ester group in the MFB additive is capable of participating in and reconfiguring the coordination of their Na+ solvated structures, thereby lowering the desolvation barrier and regulating the Na anode’s interfacial reaction and nucleation behavior. The polar C−F bond at the other end helps to reduce the lowest unoccupied molecular orbital (LUMO) energy of the MFB additive, enabling the preferential decomposition of MFB to form the F-rich inorganic phase strong polar solid electrolyte interphase (SEI), contributing to the inhibition of Na dendrite growth, the accumulation of dead Na. In addition, NaF-riched cathode electrolyte interphase (CEI) was also observed on sulfur-based cathode, which can effectively inhibited the shuttle effect. Consequently, the developed RT Na-S battery exhibit excellent electrochemical performance.

The mechanical coupling effect of α and β phases in Ti6Al4V alloy undergoing laser shock peening: A molecular dynamics study

In the dual- or multi-phase metallic materials, the influence of different microstructural constituents on the plastic strain/stress distribution is still an area of great controversy. Herein, the heterogeneous deformation behavior of α and β phases in Ti6Al4V duplex titanium alloy undergoing laser shock peening (LSP) has been investigated by molecular dynamics simulations, and the corresponding typical microstructural features are characterized at varied strains. Also, the relationship between the theoretical microstructural morphologies and the micro stress is revealed. It evidently indicates that, the grain refinement process can be summarized as: (i) dislocation motions1 interacting with deformation twins in α phases, (ii) a combination of dislocation propagations and the deformation-induced phase transition from β phase to α phase. In addition, unlike the α single-phase titanium alloy, the representative stress – strain curve of α + β titanium alloy presents a gentle fluctuation trend with smaller amplitude value, suggesting an occurrence of the coupling deformation behavior between α and β phases. The initial interfacial dislocation nucleation prefers to site in the α/α interface rather than the α/β interface, then emitting to the interior of α grains. Features of dislocation slip, twin growth, stacking fault, and phase transformation dominate the release of LSP-generated micro stress, while grain and interphase boundaries, as well as dislocation locks, contribute to the increment of the LSP-generated micro stress.

Solid-liquid interfacial nanobubble nucleation dynamics influenced by surface hydrophobicity and gas oversaturation

Over the past two decades, extensive research efforts have been devoted to exploring the existence, stability, and applications of interfacial nanobubbles (INBs). However, investigations into the microscopic nucleation process of INBs have been relatively limited. In this study, we utilized molecular dynamics simulations to elucidate the nucleation dynamics of INBs, with a particular focus on examining the influence of surface hydrophobicity and gas oversaturation. Our findings revealed a distinct preference for INBs to form on hydrophobic surfaces compared to hydrophilic ones, which agrees well with the experimental results. Temporal evolution analysis of the interfacial density of gas and liquid near the solid–liquid interface indicated a gradual enrichment of gas molecules at the hydrophobic surface, accompanied by a gradual disruption of the hydration layer, phenomena not observed on hydrophilic surfaces. The affinity of gas molecules towards the hydrophobic surface was further confirmed by potential of mean force (PMF) analysis, which demonstrated a decrease in the energy barrier and an increase in the potential well with increasing surface hydrophobicity. Moreover, increasing bulk gas supersaturation and surface hydrophobicity both contribute to shortening the INB nucleation time, primarily due to the enhanced gas enrichment rate. Further studies indicated that the gas enrichment rate had a directly proportional linear relationship with the bulk gas concentration. However, as the surface hydrophobicity increased, the gas enrichment rate initially rose rapidly and then entered a plateau phase. This may be because, when surface hydrophobicity is strong, the gas enrichment rate becomes limited by the diffusion of gas molecules in the liquid. These findings offer valuable insights into the nucleation mechanism of INBs on hydrophobic surfaces under gas oversaturation, contributing to a deeper understanding of their behavior and potential applications.

Suppressing interfacial nucleation competition through supersaturation regulation for enhanced perovskite film quality and scalability.

The growing interest in cost-effective and high-performing perovskite solar cells (PSCs) has driven extensive research. However, the challenge lies in upscaling PSCs while maintaining high performance. This study focuses on achieving uniform and compact perovskite films without pinholes and interfacial voids during upscaling from small PSCs to large-area modules. Competition in nucleation at concavities with various angles on rough-textured substrates during the gas-pumping drying process, coupled with different drying rates across the expansive film, aggravates these issues. Consequently, substrate roughness notably influences the deposition window of compact large-area perovskite films. We propose a supersaturation regulation approach aimed at achieving compact deposition of high-quality perovskite films over large areas. This involves introducing a rapid drying strategy to induce a high-supersaturation state, thereby equalizing nucleation across diverse concavities. This breakthrough enables the production of perovskite photovoltaics with high efficiencies of 25.58, 21.86, and 20.62% with aperture areas of 0.06, 29, and 1160 square centimeters, respectively.

Optimized EBSD-TEM method for the investigation of Al/Al2O3 interfacial orientation mismatch

The combined electron backscattered diffraction (EBSD) and transmission electron microscopy (TEM) method has been commonly applied to investigate material interfaces, from the perspectives of orientation and atomic structure. However, the loose combination is inadequate to capture some slight deviation from the ideal mismatch of interface, which limits an in-depth understanding of the interface. In this study, the combined EBSD-TEM method was systematically optimized and applied to investigate Al-Al2O3 heterogeneous nucleation interface. In this optimized EBSD-TEM method, the cylindrical equidistant projection was employed to illustrate the orientation mismatch relationship instead of the widely used pole figure. Lattice planes and directions from two phases are systematically presented in one figure, which provides a thorough perspective to identify all the potential matching features within the interface, meanwhile ensures a precise guidance for TEM sampling and observation. Such guidance is crucial for interface investigations, thereby this optimized EBSD-TEM method has great potential to be widely applied. Complex interface configurations of Al-Al2O3 interfaces were revealed, including the tilting of Al phase low-indexed planes relative to the interface and the deviations of matched lattice direction pairs between two phases. The complex interface configurations urge further development in the theory of nucleation interface mismatch.

First-Principles Calculations on Electronic Structure, Adhesion Strength, and Interfacial Stability of Mg(0001)/AlB2(0001) Nucleation Interface

First-Principles Calculations on Electronic Structure, Adhesion Strength, and Interfacial Stability of Mg(0001)/AlB2(0001) Nucleation Interface

A novel UV-curable amphiphobic coating with dynamic air-layer copolymer brush offering stable dual-functional anti-scaling and anti-corrosion properties

Scale deposition and metal corrosion, especially in the petroleum industry, have always been serious issues that seriously affect economic efficiency and safety. However, conventional anti-scaling strategies including mechanical descaling and chemical detergents are energy-consuming and environmentally damaging, which can't achieve efficient and long-term protection. Based on mechanical descaling and chemical detergents, and anti-corrosion strategies based on filler are inadequate to realize efficient protection. Herein, this work reports a novel UV-curable polymer coating with long-term anti-scaling and anti-corrosion properties. The excellent anti-scaling capability was achieved by inhibiting interfacial nucleation and reducing interfacial adhesion work of scaling products. Significantly, the anti-scaling capability of the designed coating mainly originates from two aspects: inhibiting interfacial nucleation and reducing interfacial adhesion work of scaling. Compared with pure polyurethane acrylic coating (0 % FGSS), the 20 % FGSS coating shows significantly improved scaling repellence even after a 240 h dynamic scaling test while maintaining a fairly low theoretical adhesion work (≈0.1 mN/m). This outstanding anti-corrosion capability of the FGSS coating mainly originates from two aspects: the physical barrier effect of the air layer and low surface energy resistance barriers with dynamic FGSS brushes. The physical barrier effect of the air layer and the low surface energy resistance barriers also lead to outstanding anti-corrosion property (with the |Z|0.01 Hz value maintained at 108 Ω·cm2). This study presents a simple and effective design and fabricated strategy, paving a new pathway for developing UV-cured coatings with unique anti-corrosion and anti-scaling properties. This facile and effective UV-curable polymer coating shows great potential in metal protection and paves a new pathway for the development of long-term functional protection coatings.

2D Tungsten Borides Induced Interfacial Modulation Engineering Toward High-Rate Performance Zinc-Iodine Battery.

Aqueous zinc-iodine batteries are promising candidates for large-scale energy storage due to their high energy density and low cost. However, their development is hindered by several drawbacks, including zinc dendrites, anode corrosion, and the shuttle of polyiodides. Here, the design of 2D-shaped tungsten boride nanosheets with abundant borophene subunits-based active sites is reported to guide the (002) plane-dominated deposition of zinc while suppressing side reactions, which facilitates interfacial nucleation and uniform growth of zinc. Meanwhile, the interfacial d-band orbits of tungsten sites can further enhance the anchoring of polyiodides on the surface, to promote the electrocatalytic redox conversion of iodine. The resulting tungsten boride-based I2 cathodes in zinc-iodine cells exhibit impressive cyclic stability after 5000 cycles at 50 C, which accelerates the practical applications of zinc-iodine batteries.

Heterogeneous nucleation interface between NbN(111) and TiN(111) in high-nitrogen austenitic stainless steels: First-principles calculation

Heterogeneous nucleation of NbN induced by TiN inclusions is important to play the role of precipitation strengthening in high-nitrogen austenitic stainless steels. In this work, the atomic structure, interfacial stability, and interfacial fracture toughness of TiN(111)/NbN(111) are investigated based on first-principles calculation. Furthermore, the interfacial bond structure and energy of TiN(111)/NbN(111) are also analyzed with and without Cr doping on the basis of Thermo-Calc phase diagrams. The results indicate that the lattice mismatch between the crystal face of TiN(111) and NbN(111) is lower than 5 %, which reveals that TiN can act as the heterogeneous nucleus for NbN to grow. Besides, the maximum adhesion work at 4.58 J/m2 and the minimum interfacial energy at 1.28 J/m2 are presented on the stacking site of N-Ti TL, which suggests that (Ti, Nb) N phases can precipitate through this interfacial bonding mode. Moreover, from the view of bonding properties on the interface with and without Cr doping, it can be found Cr doping in two layers of the interface can enhance interface stability except for N-Ti TL (2Cr). This work will give promising guidance and theoretical basis for the controllable preparation of high-nitrogen austenitic stainless steels with in-situ precipitated nitride particles.

Experimental studies on the static sharp notch effects during dynamic crack kinking/nucleation at the material interfaces

Dynamic fracture experiments on four bonded polymers using high-speed photography showed that different static sharp notches formed after the incident dynamic cracks met the material interfaces. In one scenario, an incident dynamic crack induced interfacial crack nucleation, and two convex notches formed after the interfacial crack propagated away. In another scenario, interface-induced crack kinking and a “head-to-tail” crack kinking pattern led to a concave notch with a singular stress field, which merits consideration in fracture mechanics modeling. In contrast, load-induced crack kinking did not cause the above scenarios. In another unique experimental phenomenon, a slightly curved/kinked dynamic crack only had a small local crack kinking angle, but its final crack direction was almost 90° to the initial crack direction over a long crack path.

Role of Interface Strain and Chemo-Mechanical Effects during Electroplating in Sodium Metal Battery Anodes.

In this study, we demonstrate that elastic strain applied to a current collector can influence the overall thermodynamic and kinetic picture of sodium metal electrodeposition and hence the performance of a sodium metal battery. To controllably study the role of strain in electrochemical performance, we utilize NiTi foil as a stable current collector, nucleation interface, and superelastic material. Our findings demonstrate that a locked-in elastic tensile strain near 8% results in 40 mV lower onset potential for sodium electrodeposition, 19% decrease in charge transfer resistance, and 20% lower cumulative sodium loss, among other effects. These performance improvements are correlated primarily to the control of the irreversible behavior in the first few minutes of electroplating. Given the prevalence of strain buildup in commercial battery cell configurations, our work highlights that strained current collector interfaces can result in significant long-term chemo-mechanical performance outcomes broadly relevant to sodium and other metal battery design considerations.

Atomic insights of grain boundary behaviors in TaWNbMo refractory high entropy alloys

Refractory high entropy alloys (RHEAs), such as TaWNbMo, demonstrate promising potential for high-temperature applications owing to their excellent mechanical properties. Given the pivotal role of grain boundaries (GBs) in determining the mechanical behavior of RHEAs, it is imperative to investigate their characteristics. In this work, the mechanical response of TaWNbMo RHEA and its components (Ta, W, Nb, and Mo) bicrystal samples with Σ3{112‾}<110> and Σ3{111‾}<110> GB under shear were performed using molecular dynamics simulations to investigate the motion characteristics of GBs and their influence on mechanical properties, as well as the variations brought by high entropy GBs. Both types of GBs were observed to migrate coupled with shear deformation, and the migration mechanism was analyzed based on the theory of interface defects. Additionally, twin nucleation and growth were observed in the samples with Σ3{111‾}<110> GB influenced by the high GB energy, and its mechanism was analyzed. Furthermore, a comparison was made between TaWNbMo and its component element metals, and the influence of high entropy GBs was analyzed. The multicomponent complexity invoked the local interfacial disconnection nucleation in HEA for both Σ3{112‾}<110> and Σ3{111‾}<110> GBs, the inhomogeneity of HEA also influenced the twin growth process from Σ3{112‾}<110> GB to proceed and thicken in a localized and non-uniform manner. These results contribute to a deeper understanding of the GB characteristics of TaWNbMo RHEA.

Nucleation-Inhibited Emulsion Interfacial Assembled Polydopamine Microvesicles as Artificial Antigen-Presenting Cells.

Albeit microemulsion systems have emerged as efficient platforms for fabricating tunable nano/microstructures, lack of understanding on the emulsion-interfacial assembly hindered the control of fabrication. Herein, a nucleation-inhibited microemulsion interfacial assembly method is proposed, which deviates from conventional interfacial nucleation approaches, for the synthesis of polydopamine microvesicles (PDA MVs). These PDA MVs exhibit an approximate diameter of 1µm, showcasing a pliable structure reminiscent of cellular morphology. Through modifications of antibodies on the surface of PDA MVs, their capacity as artificial antigen presentation cells is evaluated. In comparison to solid nanoparticles, PDA MVs with cell-like structures show enhanced T-cell activation, resulting in a 1.5-fold increase in CD25 expression after 1 day and a threefold surge in PD-1 positivity after 7 days. In summary, the research elucidates the influence of nucleation and interfacial assembly in microemulsion polymerization systems, providing a direct synthesis method for MVs and substantiating their effectiveness as artificial antigen-presenting cells.

First principles study on heterogeneous interfaces of TiCu alloys through aluminum addition

This paper investigates the heterogeneous nucleation interface resulting from the addition of Al element to TiCu alloy, focusing on the essential phases Ti2Cu and TiCu. Employing first principles calculations, we explore the refinement mechanism of this interface. Initially, the lattice mismatch between Al/Ti2Cu and Al/TiCu interfaces is calculated to assess the potential for heterogeneous nucleation. Four distinct interfacial types are established following a surface convergence test. The adhesive work (Wad) and Interfacial energy (γ) are computed for each interface to ascertain their crystallization potential. Furthermore, the differential charge density (DCD) and projected density of states (PDOS) for the four interfacial types are determined to analyze bonding characteristics. Results indicate a mismatch degree of 4.09 % for Al (110)/Ti2Cu (110) and 5.29 % for Al (110)/TiCu (110). These values suggest a tendency to form a heterogeneous interface with a coherent lattice, primarily characterized by Cu-Al and Ti-Al metallic bonds. The Al-Ti2Cu interface exhibits a larger nucleation work of 2.23 J/m2 and a smaller interface energy of −53.007 J/m2. This study demonstrates that Al effectively serves as a heterogeneous nucleation center within the Ti2Cu/TiCu system, contributing to substrate phase refinement and strengthening the TiCu alloy. The optimization of these findings provides valuable insights into the alloy's microstructural evolution, facilitating the design and enhancement of advanced materials for diverse applications.