Phase Nucleation Research Articles

Capturing Different Intermediate Phases during Zeolite Synthesis.

Despite extensive efforts over the past several decades, the current mechanistic understanding of zeolite crystallization is still far from satisfactory, thus precluding the synthesis of designer zeolites. Here we show that the nucleation and in situ transformation pathways during the synthesis of medium-pore zeolite TNU-9 can be altered by controlling the extent of cooperative structure direction between Na+ and Cs+ ions in the presence of 1,4-bis(N-methylpyrrolidinium)butane cations as an organic structure-directing agent. The intermediate phase selectivity was found to change from bikitaite to analcime to layered MCM-22 precursor when the gel Na/Cs ratio was adjusted to 7, 15, and 20, respectively. We also show that the transformation of bikitaite into TNU-9 begins at the surface of intermediate crystals, unlike that of analcime and MCM-22 precursor by a dissolution-recrystallization process. The force field simulation results suggest that the nucleation of different intermediate phases is not thermodynamically but kinetically controlled. This study provides a new basis for advancing the fundamental understanding of zeolite crystallization pathways.

Role of intermediate phases on microstructures, wear and corrosion resistance in new-developed (α + β) titanium alloy

A new (α + β) Ti alloy has been designed and prepared in this work, and the results show that three intermediate phases will be transformed including α′′ martensite, O′ and ω. Upon continuous heating, the α′′ martensite decomposes gradually and disappears before α precipitation. The ω and O′ domains are generated continuously upon aging, and such two intermediate phases co-exist when α phase nucleation occurs. It has been proved that the ω and O′ domains play a direct role in promoting α phase formation. Through the ω and O′ domains assisting α nucleation mechanism, a uniform distribution of fine α precipitates can be obtained after aging. Under the treatment of pre-aging at 300 °C plus aging at 600 °C, the α phase having smallest size and largest number density is obtained, resulting in highest wear resistance and corrosion resistance. For this sample, its average friction coefficient and wear ratio are 0.174 and 3.75×10−4 mm3/(N·m), respectively. During friction tests, the mixture of abrasive wear, adhesive wear and oxidation wear should be activated. Due to the formation of passivation films on the alloy surface, this alloy has exhibited better anti-corrosion properties than Ti-6Al-4 V alloy, and its corrosion current density in 3.5 wt% NaCl solution can be reduced to 1.79×10−8 A·cm−2. Compared with the samples under duplex aging treatments, the direct aged sample also presents outstanding anti-corrosion properties.

Frost crystal growth behavior on a hydrophilic surface over a wide range of cold surface temperature

The initial frosting phenomenon is a discontinuous phase nucleation process, the cold surface temperature and properties have a decisive influence on this phenomenon, especially in the initial frosting stage. With the development of aerospace and energy transportation technology, frost formation at low temperatures (-100 °C∼-30 °C) and ultra-low temperatures (-273 °C∼-100 °C) has gradually attracted the attention of researchers. In this paper, the initial frosting phenomena on hydrophilic surfaces with a contact angle of 10° (CA= 10°) and ordinary (CA= 95°) surfaces are studied experimentally in a wide range of cold surface temperatures (-190 °C∼-30 °C). Four modes are confirmed: cold surface condensation frosting, cold surface sublimation frosting, air boundary layer condensation frosting and air boundary layer sublimation frosting. It is also found that the four frosting modes do not appear in turn with the decrease of the cold surface temperature, but two or more frosting modes appear at the same time. And the surface contact angle has an important influence on the frosting mode. The initial frost crystal morphology mainly depends on the cold surface temperature and the corresponding frosting mode. Four different forms of frost crystals are observed: hexagonal prism (feather), branch (pine needle), cluster (shrub) and floc (grape), in which the cluster frost crystal is more sensitive to the surface contact angle and can appear in different temperature ranges due to different contact angles. Based on the statistics of the size, quantity, and distribution of the initial frost crystals, it is found that -70 °C is a major turning point for frost formation from the cold surface sublimation frosting to the air boundary layer sublimation frosting, and an important change has taken place near this point. Furthermore, it affects the shape and size distribution of frost crystals. These findings are of great significance for the study and understanding of frost crystal growth mechanism in the initial stage of frost formation at low and ultra-low temperatures.

Surface Iodide Defects Control the Kinetics of the CsPbI3 Perovskite Phase Transformation.

Halide perovskites are technologically interesting across a wide range of optoelectronic devices, especially photovoltaics, but material stability has proven to be challenging. One degradation mode of note is the meta stability of the perovskite phase of some material compositions. This was studied by tracking the change of CsPbI3 from its optoelectronically relevant perovskite phase to its thermodynamically stable nonperovskite phase, δ-CsPbI3. We explore kinetics as a function of surface chemistry and observe a quantitatively similar, ∼5-fold, reduction in the phase transition rate between neat films and those treated with CsI and CdI2. Using XPS to explore surface chemistry changes across samples, we link the reduction in the phase transition rate to the surface iodide concentration. When informed by previous theoretical studies, these experiments point to surface iodide vacancies as the nucleation sites for δ-CsPbI3 growth and show that phase nucleation is the rate limiting step in δ-CsPbI3 formation for CsPbI3 perovskite thin films.

Stick-to-slip transition characterized by nucleation and emission of dislocations and the implications in earthquake nucleation

Stick-slip friction exists widely in our life especially the occurrence of large earthquakes, but people cannot predict and control by a limited understanding of the mechanisms involved. In the present work, the whole process of stick-to-slip transition has been investigated through digital image correlation and acoustic emission. Two phases, namely, the nucleation and abrupt rupture phases have been discovered during the transition that are characterized well by nucleation and transient emission of dislocations, which may support the combination of pre-slip and cascade-up models. Based on the findings simple yet analytical expressions then have been obtained to predict the earthquake cycles consistent with available simulations and practical observations.

In situ Synchrotron X-ray Metrology Boosted by Automated Data Analysis for Real-time Monitoring of Cathode Calcination.

Synchrotron X-ray-based in situ metrology is advantageous for monitoring the synthesis of battery materials, offering high throughput, high spatial and temporal resolution, and chemical sensitivity. However, the rapid generation of massive data poses a challenge to on-site, on-the-fly analysis needed for real-time process monitoring. Here, a weighted lagged cross-correlation (WLCC) similarity approach is presented for automated data analysis, which merges with in situ synchrotron X-ray diffraction metrology to monitor the calcination process of the archetypal nickel-based cathode, LiNiO2. The WLCC approach, incorporating variables that account for peak shifts and width changes associated with structural transformations, enables rapid extraction of phase progression within 10 seconds from tens of diffraction patterns. Details are captured, from initial precursors to intermediates and the final layered LiNiO2, providing information for agile on-site adjustments during experiments and complementing post hoc diffraction analysis by offering insights into early-stage phase nucleation and growth. Expanding this data-powered platform paves the way for real time calcination process monitoring and control, which is pivotal to quality control in battery cathode manufacturing.

Assessment of Thermodynamic variables affecting phase nucleation

Complete understanding of any natural phenomenon can only be achieved by explicitly expressing it in terms of primitive variables. The laws of thermodynamics have been extensively studied for centuries, accelerating societal progress through developments across several branches of science and technology. Phase nucleation can be observed in the melting and freezing of rocks and ice caps, abundant shapes of snow flocks, rain regimes, snowfall, casting, and metal forming, among other applications. The most challenging aspect of nucleation is the equilibrium shift controlled by the gradients in temperatures, species, work, and other variables, in accordance with the first law of thermodynamics, which defines the thermal field. In this study, the thermal field and thermal field tensor were defined in terms of equilibrium dislocations to assess their primitive variables. Theoretical simulations for the Gibbs–Thomson coefficients were applied to predict the experimental microstructure evolution.

Model predicted optimization of experimental set-up and process conditions for microwave-assisted synthesis of silver nanowires

This work presents simulations led optimization of choice of a reactor for an experimental set-up for the continuous production of silver nanowires with certain constraints in terms of yield, reaction time, and dimensions of nanowires. The choice of reactors based on the simulations of reaction kinetics for nucleation and growth phases of driving the optimization of an experimental set-up and subsequent optimization of process conditions to maximize the yield of nanowires of desired dimensions. The optimized reactor configuration is dictated by the reaction kinetics and using a microwave in continuous mode becomes unavoidable. This makes the approach highly reproducible as well as scalable. The integration of conventional and microwave heating is simulated and subsequently optimized experimentally to attain a significant increase in nanowire yield under steady-state conditions with less than 15 min of residence time. The precise control over the rate in different reactor configurations governing nucleation, accelerated growth followed by slow growth to complete the conversion of precursor enables higher selectivity of nanowires with controllable dimensions resulting in 100 gm production per day using simple set-up. We systematically examined key reaction parameters, including the concentration of metal ions, residence time, and different reactor configurations. Our approach successfully yielded AgNWs with 40–60 nm diameter and 15 µm length. The cost associated with this process for synthesizing AgNWs is less than 10$ per gram. This study highlights the potential of continuous, high-throughput processes for controlling nanowire size and yield through advanced reactor engineering.

Role of silicon in the growth of ZSM-5 synthesized with coal fly ash as raw materials

In this work, single-phase ZSM-5 zeolite was synthesized using solid waste coal fly ash (CFA) as raw material, providing a potential alternative for creating high-value-added products from this waste. X-ray diffraction (XRD), scanning electron microscopy, X-ray fluorescence, Fourier transform infrared spectroscopy, N2 physisorption, and other techniques were used to evaluate the crystallization and morphology of the ZSM-5 obtained. The results indicated that ZSM-5 can be synthesized by the simple method of mixing, stirring, and heating. A well-defined hexagonal shape of ZSM-5 with a specific surface area of 162 m2/g and mesoporous structure was obtained at the temperature of 160 °C during hydrothermal treatment for 72 h. Theoretically, the mechanism of crystal growth of ZSM-5, i.e. the liquid phase nucleation and step growth models, was clarified. These results open the possibility of exploring the crystallization of ZSM-5 and the utilization of CFA. Simultaneously, the critical roles of silicon in framework formation and crystallization control during the formation and growth of zeolites were elucidated.

Theoretical analysis of the initial nucleation characteristics of trace water vapor frosting on a cryogenic surface

In certain extreme conditions characterized by ultra-low water vapor content and ultra-low temperatures (e.g. cryogenic wind tunnel), trace water vapor frosting can also pose significant hazards. Considering the crucial role of initial nucleation on subsequent frosting processes, this study firstly investigated and compared the nucleation characteristics of frosting at different water vapor contents (0.1−1000 ppmv) from humid air to trace water vapor based on classical nucleation theory. The preferred nucleation phase diagrams and critical nucleation conditions were analyzed. Sensitivity of the nucleation mass transfer rate, as well as the frosting pathways were further identified. Results show that the nucleation characteristics of trace water vapor frosting (<100 ppmv) is significantly different from that of humid air frosting (>1000 ppmv). Trace water vapor frosting is more inclined towards desublimation nucleation due to its lower nucleation temperature and larger critical contact angle. The critical contact angles for 1000 ppmv, 100 ppmv and 0.1 ppmv are 49°, 75° and 120°, respectively. Furthermore, trace water vapor nucleation requires a greater subcooling degree, has a smaller critical nucleation radius, and is highly sensitive to surface contact angle and further-subcooling degree. At a surface contact angle of 120°, the nucleation subcooling degree of 0.1 ppmv is 2.9 K greater than that of 1000 ppmv. This study helps understanding the nucleation characteristics under different water vapor content conditions, which indicates that reducing subcooling degree and increasing contact angle are more effective anti-frosting methods than reducing water vapor content for trace water vapor frosting.

Mechanisms for enhanced ferroelectric properties in ultra-thin Hf0.5Zr0.5O2 film under low-temperature, long-term annealing

To gain insight into the ferroelectric mechanisms under reduced thermal budget and thickness scaling, a 4.6 nm ultra-thin ferroelectric Hf0.5Zr0.5O2 capacitor compatible with back-end-of-line (BEOL) processes (all conducted at temperatures ≤350 °C) is investigated in this work. Through O3 pretreatment at the bottom electrode (BE) interface and controlled temperature modulation of the crystalline phase, the capacitor exhibits exceptional ferroelectric (FE) properties following low-temperature (350 °C) and long-term (300 s) rapid thermal annealing (RTA). These properties include high remanent polarization (2Pr ∼ 28.53 μC/cm2), low coercive voltage (Vc ∼ 0.43 V), effective leakage suppression, robust endurance (∼1010 cycles without hard breakdown), and a desirable high dielectric constant. The main mechanisms identified include tetragonal phase nucleation under enhanced tensile stress via the oxidized BE layer (TiO2), crystalline growth controlled through RTA temperature modulation, and phase transition to the ferroelectric orthorhombic phase under electric field cycling. This research provides valuable insights for the development of BEOL-compatible nonvolatile FE memories.

Metastable phase transformations and mechanical properties of an as-extruded TiAl-based alloy during two-step heat treatment

Metastable phase transformations of TiAl-based alloys provide a pathway for grain refinement and performance improvement. In this paper, the microstructure evolution of an as-extruded Ti-47Al-2Cr-0.2Mo alloy during quenching and tempering was investigated by scanning electron microscope (SEM), electron backscatter diffraction (EBSD) and transmission electron microscope (TEM), and the mechanical properties of the alloy were further evaluated by tensile tests. The results indicated that the analogous Σ3 coincidence site lattice (CSL) and γ/γ true twin interface appeared in both the Widmanstätten structure (γw) and feathery structure (γf), implying that sympathetic nucleation mechanism was responsible for the nucleation of the metastable phases. A 6 H intermediate phase with the long period stacking ordered structure (LPSO) was discovered after short-term water quenching, which provided an evidence supplement of the sympathetic nucleation mechanism. The transformation path of the metastable γw phase was proposed to follow the sequence of α/α2→6 H→γ. Apparent refinements of both grains and α2/γ lamellar colonies ((α2+γ)L) were exhibited after metastable phase transformation. The ultimate tensile strengths of the heat-treated alloy at whether room temperature (RT) or 800 °C were obviously improved, and the elongation at RT also kept at a considerable level.

Tailoring thermal conductivity and microstructure of Al–Fe alloys by addition of Sc2O3 and variable cooling rates

Al–Fe alloy is a kind of high thermal conductivity alloy, which are widely utilized in the communication and automobile industries. The thermal conductivity is greatly affected by the morphology, size, and distribution of iron-rich intermetallic phases (Fe-rich phases), pores, and Al grains. The evolution of microstructure and thermal conductivity of Al–Fe alloys by adding Sc2O3 particles and adjusting cooling rates are systematically studied by optical and scanning electron microscopy, and synchrotron X-ray imaging. The results show that Sc2O3 addition reduces the size and increases the number of primary Fe-rich phases, while increasing the grain size of Al matrix. The Sc2O3 promote their nucleation of primary Fe-rich phases and partial Sc solutes inhibit their growth, resulting in the improvement of thermal conductivity and mechanical properties. The remaining Sc2O3 particles have large lattice misfit with Al, led to the formation of coarsen size Al. The highest thermal conductivity is 214 W/(m·K) in the alloy with Sc2O3 and slow cooling rate. Sc2O3 addition increase the thermal conductivity of the studied alloys, i.e., an increment of 3 W/(m K) (by 1.1 %) at slow cooling rate by and an increment of 11 W/(m K) (by 6.2 %) at fast cooling rate. This study provides a new strategy to improving thermal conductivity of Al alloy for both academia and industry.

Optic generation and perpetuation of acoustic bubble clusters

Laser-induced cavitation bubbles offer precise control of the flow in space and time, but they are rarely used for the mechanical and chemical processing of liquids. Instead, strong acoustic fields are commonly used to nucleate and drive cavitation bubbles for liquid process applications. While acoustic field creates many more cavitation events, the resulting chaotic dynamics offers little control on the fluid mechanics, i.e., where and how bubbles deliver their energy. Here we present a method that utilizes a laser to nucleate a single cavitation bubble, which is then driven into violent oscillations by the ultrasound field, resulting in splitting of the bubble followed by formation of a cluster of cavitation bubbles. This combination offers means for cavitation control not available in conventional acoustic cavitation. Here, the cavitation bubble is generated with a custom build pulsed laser that is focused below a sonotrode driven at 20 kHz. In absence of the acoustic driving the bubble reaches a maximum diameter of 130 µm with a lifetime of approximately 10 µs. In the presence of the acoustic field the first few expansions and bubble collapses are strongly affected by the phase of nucleation. Over successive acoustic cycles a small bubble cluster develops that loses its connection with the phase of generation. We study the dynamics in the free field and constrained by a rigid boundary. For both geometries the cluster over many acoustic cycles dies off, yet through repetitive optical bubble seeding the cluster lifetime and its location can be controlled.

Benchmark of Techniques for the Characterization of the Mechanism of Phase Transformations in Steel of Near-Peritectic Composition

This study addresses challenges in elucidating the mechanism of phase transformations occurring in steel of near-peritectic composition. The importance of using and integrating, complementary experimental techniques is emphasized. While thermal analysis tools such as Differential Scanning Calorimetry (DSC) and Differential Thermal Analysis (DTA) are vital, they offer limited insight on events occurring during cooling. Employing standard thermal analysis (DSC) alongside high-temperature microscopy, incorporating simultaneous thermal analysis within a high-temperature microscope, and concentric solidification, two of steels of near-peritectic composition were investigated. Key findings include the correlation between heating rates and completion temperatures of phase transformation in the DSC heating experiments; absence of a peritectic transition inferred from DSC cooling curves supported by visual observation, and insights into restricted austenite phase nucleation attributed to diffusional constraint and limited nucleation sites. This investigation not only contributes to understanding phase transformation behaviour in peritectic steels, but more generally provides a framework for utilizing different techniques synergistically to address complexities in the interpretation of the mechanism of phase development.

Impact of nickel and alkaline earth metals interaction on sustainable carbon nanotubes generation from plastic face masks via catalytic pyrolysis

The one-pot synthesis of carbon nanotubes (CNTs) emerges as a promising approach for plastic valorization, owing to its simplicity and scalability. However, limited attention has been given to catalyst design for this method, particularly regarding the influence of Group 2 alkaline earth metal elements (X) on the Ni-based catalyst activity. This study investigates the impact of X on the catalytic activity of Ni towards sustainable CNTs synthesis using plastic face masks. The findings revealed that X influenced the carbon yield of NiMo-X catalysts and the morphology of the resultant carbon nanomaterials. Notably, NiMo-Ca demonstrated the highest carbon yield, whereas NiMo-Mg and NiMo-Ba exhibited the lowest. Furthermore, NiMo-Mg tends to produce clean and thin CNTs, while NiMo-Ba tends to yield carbon flakes with numerous irregular cokes. In addition to the effect of Ni crystallite size, which influences the transition from tubular to flake-like carbon structures, environmental factors are also considered. Specifically, NiMo-Mg generated a high CO2/CH4 environment, while NiMo-Ba exhibited slower catalytic cracking of polymeric chains from face masks, both of which were unfavorable for CNTs growth. Conversely, NiMo-Ca facilitated higher carbon recovery, likely due to its creation of a low CO2/CH4 environment via CO2 methanation. Optimization studies indicated that increasing pyrolysis temperatures and durations lead to reduced carbon yield, while cyclic pyrolysis of face masks up to five iterations enhances the reusability of NiMo-X catalysts with improved carbon recovery. Overall, this study provides valuable insights into the early pyrolytic gas formation and carbon nucleation phase, which are influenced by the surface Ni fraction and Ni polarization, as well as the later CNTs growth phase, which is related to the Ni crystallite size.

Experimental characterization of two clay deposits blended with feldspar and quartz for building services and refractory applications

Clay deposits across the globe have variations in mineralogical compositions that elicit their use in numerous applications. In this study, two clay deposits were identified and blended with feldspar and quartz in various amounts to produce different samples of composites that could be used for applications in building services and refractories. Chemical analysis, mineralogical composition, microstructure, physical properties, and thermal behaviours were characterized. The X-ray fluorescence (XRF) analysis results show that the clays belong to the aluminosilicate group containing traces of other oxides which enhance strength and the crystallization of thermally stable phases. The XRD patterns confirmed the presence of dominant quartz with moderate to minor presence of kaolin, orthoclase, and albite. The texture of the clays showed particles of different sizes and shapes with uneven distribution. The EDX characteristic spectrum showed x-ray characteristic peaks of Si, Al, Fe, K, and O which affirmed their major oxide compositions. Physical properties results show that firing at various temperatures and blending resulted to increase in Bulk density and flexural strength while apparent porosity and water absorption decreased. The TGA, DTA, and DSC results show that the two clay minerals are thermally stable. This can be attributed to the nucleation and crystallization of refractory phases like cristobalite and mullite. Addition of feldspar and quartz was found to contribute significantly to improve the overall properties of the investigated clays. A comparison of the various results from the two clay deposits suggests that they could be suitable for building services and refractory applications.

Development and Mechanical Characterization of a CoCr-Based Multiple-Principal-Element Alloy

The development and mechanical characterization of a CoCr-based multiple-principal-element alloy are presented and discussed. In this work, ab initio synthesis and mechanical characterization of the (CoCr)100-x(TiNbZr)x (x = 0, 48 60, 78 and 100 % at) alloy family is reported; these include the calculation of thermodynamic parameters such as mixing entropy (ΔSmix), mixing enthalpy (ΔHmix), valence electron concentration (VEC), Ω and δ factors. The alloys were melted in a vacuum arc furnace; rod-shaped ingots were produced by suction casting. Phase characterization was carried out using optical microscopy, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), and X-ray diffraction. Mechanical characterization was done via compressive and hardness tests. Calculation of phase diagrams was performed using Thermo-Calc © software. Yang’s model for phase prediction predicted a BCC solid solution. Multicomponent simulations predicted a more complex structure, with Laves (C14 and C15), Theta (C16), BCC 1, 2 and 3, Mu, CoTi2, CoZr3 and TiZr2. Contrary to Yang’s model for phase prediction, the experimentally obtained phases agreed reasonability well with those obtained by the Thermo-Calc simulation. The suction cast process cooling rate suppressed the nucleation and growth of some equilibrium phases, i.e., Laves (C14) or BCC 3 for the (CoCr)100-x(TiNbZr)x (x = 0, 48 60, 78 and 100 % at) alloys. The hardness test results were strongly related to the intermetallic phase formation, showing an increase of 331% with the x = 78 alloy. The BCC 1 phase played an important role in the yield strength behavior, as the (CoCr)22(TiNbZr)78 alloy, with a considerable amount of this phase, showed the highest yield strength value.

Atomic-scale heterointerfacial engineering of multilayered structures in Fe-Cr-based alloys revealed through LRLM model and its modified model

Two Fe-Cr-based alloy foils, denoted as Y2 and MY1 samples, were prepared, as well as transmission electron microscope (TEM) was used to investigate the atomic matching and orientation relationships (ORs) across the interfaces in these samples. From the analyses of the interfaces, the ORs and atomic matching modes between adjacent phases are revealed. Furthermore, the reconstructed multilayer models for each interface have been established on the basis of the ORs, and it is found that the formation of stable interfaces is conductive to the nucleated phases nucleating on the surfaces of the substrates. As for the OR verification, parallel ORs are verified effective through long-range lattice matching (LRLM) model, while non-parallel OR is verified through modified LRLM model. Finally, the sequential atomic heterogeneous nucleation behaviors of TiN and δ-Fe originated from Mg- /Y-bearing oxides have been reconstructed.

Atomic Simulation of Deformation Behavior of Polycrystalline Co30Fe16.67Ni36.67Ti16.67 High Entropy Alloy Under Uniaxial Loading

Mechanical behavior and plastic deformation mechanism of a new type of Co30Fe16.67Ni36.67Ti16.67 high entropy alloys (HEAs) have been calculated by the molecular dynamics method. The results show that the polycrystalline Co30Fe16.67Ni36.67Ti16.67 HEA has remarkable tensile plasticity and anisotropy. When the crystallographic orientation of the grain is &lt;001&gt;, the plastic deformation mechanism is face‐centered cubic (FCC)→body‐centered cubic (BCC) transformation and deformation twins. Grain boundary and vacancy reduce the nucleation energy of FCC→BCC phase transition, making BCC phase nucleation easy and growing in a shear manner, eventually forming deformation twins in the BCC phase. When the crystallographic orientation of grain is &lt;110&gt; and &lt;111&gt;, the plastic deformation mechanism is stacking faults, FCC→hexagonal‐close‐packed (HCP) phase transformation, and deformation twins. The motion of Shockley dislocation leads to the stacking fault, intrinsic stacking fault leads to the FCC→HCP phase transition, extrinsic stratification fault leads to the twin deformation, and the grain refining occurs during the tension process. Temperature and strain rate also have strong effects on tensile strength and elastic modulus. These results will provide a theoretical basis for the development of the HEAs and expand their application.