Supersaturation Of Solution Research Articles

Polymer‐Assisted Nucleation for Stable Single‐Crystal Perovskite Thin Films

AbstractOrganic‐inorganic hybrid perovskite single crystals have emerged as a strong candidate in photovoltaic and general optoelectronic applications. However, the high supersaturation of the precursor solution leads to the rapid formation of a significant number of nuclei and a diminished concentration of perovskite solute. Consequently, the inadequate availability of precursors poses challenges in sustaining the subsequent crystal growth phase, culminating in the development of small‐sized single crystals. In this work, we report a controlled nucleation process to foster the growth of large‐size single crystals. This method through the coordination interaction between polyacrylic acid and Pb2+ ions, and substitution of the coordination with I− ions. This reduces the formation of the Pb‐I6 complex, which promptly emerges in a state of supersaturation and acts as a nucleus, thereby effectively reducing the number of nuclei formed. The single crystals produced using this method exhibit a lateral size exceeding 5 mm, an extended absorption range, a longer carrier lifetime of 10.93 ns, and enhanced stability. These crystals demonstrate the ability to remain stable even after storage in an ambient environment (T=20±5 °C, RH=60±5 %) for a period of 20 days.

Machine learning-augmented modeling on the formation of Si-dominated Non-β″ early-stage precipitates in Al-Si-Mg alloys with Si supersaturation induced by non-equilibrium solidification

Recent experiments have shown that Al-Si-Mg alloys solidified under high cooling rates may lead to the nucleation of Si-enriched clusters that are remarkably different from the conventional Mg-Si co-clusters (e.g. β″ particles), and yet the responsible mechanism remains to be elucidated. Here we tackle the problem using a multiscale modeling framework that integrates atomistic modeling, energy landscape sampling, and lattice-based kinetic Monte Carlo (kMC) simulation. The migration energy barriers for vacancy-mediated diffusion amid complex local chemical environments are predicted on-the-fly using a surrogate machine learning model. We discover that the actual vacancy-Si migration barriers are much lower than those assumed in the classic linear interpolation approximation. Such a strong deviation from conventional wisdom, in conjunction with differing Si solute composition, can lead to a great variety in the nucleated early-stage precipitates. More specifically, a high-level supersaturation of Si solute (i.e.xSi/(xSi+xMg)>0.75) would lead to an unexpectedly high enrichment of Si in the nucleated clusters with the Si:Mg ratio up to 5∼6; while at a lower-level supply of Si solute the Mg-Si co-clusters (i.e. Si:Mg ratio around 1∼2) are nucleated instead. These findings provide a viable explanation for the diverse types of early-stage precipitates observed in various experiments, from Si-enriched precipitates in high-pressure die cast Al alloys to β″ particles in conventional casting and/or heat-treated alloys. The implications of our findings are also discussed.

Crystal Growth and Color Tuning of Large Mn(PO3OH)·3H2O Crystals via an Evaporation-Assisted Aqueous Route at Room Temperature.

Large Mn(PO3OH)·3H2O crystals have been prepared from aqueous solutions containing MnCl2 and (NH4)2HPO4 by an evaporation-induced crystal growth technique. The slow solvent evaporation at room temperature maintained the supersaturation of the precursor solution for a long time, resulting in the continuous growth of Mn(PO3OH)·3H2O crystals. The addition of citric acid as a chelating agent and increasing the total volume of the precursor solutions helped to maintain the mild supersaturation conditions for a longer time period, and transparent, unbranched Mn(PO3OH)·3H2O crystals above 2 mm in size were produced by aging for 8 weeks. The large Mn(PO3OH)·3H2O single crystals exhibited a pink color, and the color became stronger by doping with Co2+ ions.

Transitions between equilibrium and nonequilibrium phenomena in the description of crystal growth

The close intertwining of equilibrium and nonequilibrium thermodynamic representations and transitions between the two limiting principles of thermodynamics: the second beginning and the principle of least coercion (minimum entropy production in the stationary regime) constitute the main content of phenomenological theories of crystal growth. The difference of basic postulates of two sections of thermodynamics forces to discuss problems of reversibility and irreversibility of time, scales of observed phenomena and rules of conjugation of thermodynamic forces and flows in theories of crystal growth. A variant of the solution of some conjugation problems is shown on the example of the fluctuation model of dislocation crystal growth, which is based on the stationary isothermal process of thermodynamic free energy fluctuations. In the case of the limiting mode of adsorption of impurities on the crystal face according to the Langmuir model, the free energy fluctuations possessing the absence of the memory effect allow us to identify three chemical potentials of building particles that determine the corresponding values of solution supersaturations realized at different scale levels at the growing crystal face containing a helical dislocation. The supersaturations control quasi-equilibrium and nonequilibrium thermodynamic processes that constitute a single dislocation mechanism of crystal growth.

Deconstructing 3D growth rates from transmission microscopy images of facetted crystals as captured in situ within supersaturated aqueous solutions.

Here, a morphologically based approach is used for the in situ characterization of 3D growth rates of facetted crystals from the solution phase. Crystal images of single crystals of the β-form of l-glutamic acid are captured in situ during their growth at a relative supersaturation of 1.05 using transmission optical microscopy. The crystal growth rates estimated for both the {101} capping and {021} prismatic faces through image processing are consistent with those determined using reflection light mode [Jiang, Ma, Hazlehurst, Ilett, Jackson, Hogg & Roberts (2024 ▸). Cryst. Growth Des. 24, 3277-3288]. The growth rate in the {010} face is, for the first time, estimated from the shadow widths of the {021} prismatic faces and found to be typically about half that of the {021} prismatic faces. Analysis of the 3D shape during growth reveals that the initial needle-like crystal morphology develops during the growth process to become more tabular, associated with the Zingg factor evolving from 2.9 to 1.7 (>1). The change in relative solution supersaturation during the growth process is estimated from calculations of the crystal volume, offering an alternative approach to determine this dynamically from visual observations.

Ion adsorption-enrichment effect and its driving mechanism for nano-dots lithography with SPM probe on water-soluble crystal surfaces

HypothesisWater-soluble KDP (KH2PO4) crystals possess excellent optical properties and are employed as frequency converters in clean fusion energy. To improve their performances, there is an immediate necessity to lithograph surface nano-patterns on them. Although the Scanning Probe Microscope (SPM) provides a promising way to achieve this purpose through the water menisci, the driving mechanisms of the lithographic behaviors have not yet been revealed. Simulations and ExperimentsMulti-scale investigations are constructed to explore the underlying driving mechanisms. The SPM probe-induced ion diffusion-transport behaviors are investigated by molecular dynamics. The ion adsorption-enrichment mechanisms are revealed by 18 adsorption models via the ab initio. The SPM probe-induced self-assembly experiments are performed to prove the local heavy concentration. A comprehensive model is developed to describe the lithography mechanisms of the probe-induced self-assembly nano-dots on water-soluble substrates. FindingsIt is interestingly found that the KDP growth units (H2PO4−) exhibit obvious adsorption-enrichment effect at 3.16 Å from the probe surface, causing local heavy concentration. The H2PO4− would spontaneously adsorb onto the probe surface, which is dominated by the Si-O bonding reactions. The nano-dots with the height of 27 ∼ 48 nm and diameter of 2.0 ∼ 2.7 μm are lithographed on the KDP substrate. The proposed model further confirms that the lithography processes are driven by the solution supersaturation, solute diffusion, and surface free energy.

Supersaturation- and external force-engineered high-quality 2D CsCu2I3 single-crystalline film for heterogeneous integration in photodetectors

Heterogeneous integration of various crystalline materials in electronic and optoelectronic devices have fueled the development of two-dimensional (2D) perovskite single-crystalline (SC) film. However, it is still challenging to synthesize 2D CsCu2I3 SC film due to the uncontrolled nuclei/growth. In the work, the bottleneck for the synthesis of 2D CsCu2I3 SC film can be well tackled by the solution supersaturation and external pressure for the first time, meanwhile, the morphological transformation of CsCu2I3 from dendritic crystal to 2D film are firstly achieved through controlling nucleation driving force. The heterogeneous integration of 2D CsCu2I3 SCs film on various substrates was demonstrated, a self-powered GaN-CsCu2I3 SC film photodetector exhibits high rectification ratio of 1250 (±1 V) with improved responsivity of 460 mA W−1 and EQE of 163 %, which outperforms most reported 2D lead-free halide perovskite film photodetectors. Furthermore, theoretical computational calculation was employed to investigate their crystal structure and electronic distribution, evidencing that 2D CsCu2I3 SC film could facilitate the separation of photo-induced carriers. The study not only shows an in-depth mechanism for perovskite growth, but also advances the development of 2D copper-based perovskite film and hetero-integration, laying the groundwork for future commercial optoelectronics.

Anomalous temperature-dependent strength of copper alloy manufactured by laser-beam powder bed fusion

This study reports an anomalous temperature-dependent tensile behavior of laser-beam powder bed fusion (PBF-LB) processed Cu–Cr–Zr alloy. The yield strength of the alloy initially decreases as the temperature increases to 200±5 MPa and then increases to 350±11 MPa at 500°C before reducing to 234±6 MPa at 600°C. The microstructure consists of elongated Cu grains with a high concentration of Cr solute (∼1 mass%), resulting from rapid solidification during the PBF-LB process. Transmission electron microscopy for the specimens deformed at 500°C revealed the presence of numerous nanoscale Cr-rich particles embedded inside the supersaturated solid solution of the Cu matrix. Nanoscale particles can act as barriers to dislocation motion, leading to an increase in internal stress during plastic deformation at elevated temperatures. This work provides the high potential of post heat treatments for achieving superior mechanical performance using high solute supersaturation formed by the PBF-LB process.

Ultra-antiwetting Membrane for Hypersaline Water Crystallization in Membrane Distillation.

Membrane distillation (MD) has great potential in the management of hypersaline water for zero liquid discharge (ZLD) due to its high salinity tolerance. However, the membrane wetting issue significantly restricts its practical application. In this study, a composite membrane tailored for extreme concentrations and even crystallization of hypersaline water is synthesized by coating a commercial hydrophobic porous membrane with a composite film containing a dense polyamide layer, a cation exchange layer (CEL), and an anion exchange layer (AEL). When used in direct contact MD for treating a 100 g L-1 NaCl hypersaline solution, the membrane achieves supersaturation of feed solution and a salt crystal yield of 38.0%, with the permeate concentration at <5 mg L-1. The composite membrane also demonstrates ultrahigh antiwetting stability in 360 h of long-term operation. Moreover, ion diffusion analysis reveals that the ultrahigh wetting resistance of the composite membrane is attributed to the bipolar AEL and CEL that eliminate ion crossover. The literature review elucidates that the composite membrane is superior to state-of-the-art membranes. This study demonstrates the great potential of the composite membrane for direct crystallization of hypersaline water, offering a promising approach to filling the gap between reverse osmosis and conventional thermal desalination processes for ZLD application.

Unraveling the mechanics of directional coarsening in single crystal Ni-based superalloys via laser peening: Insights from experimental characterization and microstructural analysis

Surface treatment techniques, like laser peening, enhance the longevity of Ni-based superalloy components by reinforcing their microstructure against surface-initiated damage. Recent findings suggest that these methods may also influence precipitate coarsening behavior at high temperatures, leading to rafting phenomena. This study extensively examined γ’ rafting in single crystal Ni-based superalloy CMSX-4 post laser peening and heat treatment. X-ray diffraction revealed surface compressive stresses (-400 MPa to -800 MPa), transitioning to tensile stresses at greater depths before returning to an unstressed state. Correlation with electron microscopy indicated horizontal coarsening in compressive regions and vertical coarsening in tensile regions due to misfit and residual stresses aiding diffusion. Plastic strain near the LPed surface was measurably increased with lattice misorientation values around 5° before returning to an unstrained state after heat treatment due to rafting-aided recovery and defect reorganization. Secondary γ’ precipitates with a radius of approximately 10 nm occupied γ channels between rafted precipitates, indicating solute element diffusion and supersaturation. Energy dispersive x-ray spectroscopy showed a significant depletion of γ’-forming elements around rafted primary precipitates, highlighting preferential solute diffusion.

Effect of friction-stir processing and subsequent aging treatment on microstructure and service properties of Cu-Cr-Zr alloy

The effect of friction-stir processing (FSP) and the subsequent aging treatment on the microstructure, electrical conductivity, and mechanical properties of a Cu-0.3%Cr-0.5%Zr alloy was studied. FSP promoted complex microstructural changes, including significant grain refinement and dissolution of secondary particles within the stir zone and particle coarsening within the heat-affected zone. The particle phenomena resulted in the essential material softening and degradation of electrical conductivity. The subsequent aging treatment provided particle reprecipitation within the stir zone and thus essentially recovered material properties in this area. In the heat-affected zone, however, the recovery effect was less pronounced, thus leading to the characteristic W-shaped profiles of microhardness and electrical conductivity. This result was attributed to the insufficient degree of supersaturation of the solid solution in this microstructural region, which, in turn, promoted the relatively slow precipitation kinetics.

Understanding the differential precipitation behavior of friction stir welded Al-Zn-Mg-Fe alloy during long-term natural aging

Al-Zn-Mg-Fe (HE700) is a new generation cast alloy based on dilute Al-Fe hypoeutectic system. Being a new member, the precipitation behavior of the HE700 alloy is not fully understood unlike its conventional 7xxx series counterparts. Moreover, presence of Fe and friction stir welding (FSW) used to join such alloys add to the complexity of the precipitation phenomenon. The present study captured the microstructural features with atomic-scale resolution that provided new insights into the nature, distribution, and evolution of precipitates in this alloy. The stir zone (SZ) and heat-affected zone (HAZ) exhibited significantly different natural aging behavior. Finer precipitates identified as GPI and GPII (Guinier Preston zones) were found to coexist with very fine zinc-rich solute clusters in the SZ. The GP zones evolved gradually and transitioned into strengthening precipitates. The HAZ, on other hand, exhibited heterogeneous distribution of coarse pre-existed particles and fine MgZn2 precipitates that were heterogeneously nucleated by localized solute supersaturation and thermally induced dislocations. Hardness variations can be correlated to precipitates evolution thereby helping design a suitable post-weld heat treatment (PWHT) process.

Modeling of isothermal supersaturation of solutions in a porous medium: estimation of it’s possible degree

Modeling of isothermal supersaturation of solutions in a porous medium: estimation of it’s possible degree

Innovative synthesis of high-strength α-hemihydrate gypsum: Effects and mechanisms of TA modification under microwave hydrothermal conditions

Titanium gypsum (TG), a byproduct of the titanium dioxide industry, is recognized as a significant contributor to environmental pollution due to high water content, poor crystallinity and other characteristics that make it difficult to be reused/recycled effectively. This study evaluated the feasibility to recycle TG to produce α-hemihydrate gypsum via microwave hydrothermal method, wherein tricarballylic acid (TA) was employed as modifier to modulate the crystallization of α-HH. The impact of TA dosage on the characteristics of α-HH crystals is comprehensively assessed through a series of microscale analyses. The findings reveal a notable reduction in the Length/Diameter ratio (L/D ratio) of α-HH crystals, diminishing from 17.79 to 0.96, in response to the incremental introduction of TA, ranging from 0 % to 0.13 %. An optimum TA dosage of 0.1 % is found to yield a commendable compressive strength of 37.4 MPa. Additionally, this study validates the interaction between TA and α-HH crystals. Based on the experimental results, it is further postulated that microwave heating is conducive to expediting the rate of Ca2+ and SO42− ion accumulation at the (002) surface, thus altering the degree of solution supersaturation and consequently accelerating the growth kinetics of α-HH crystals. This study offers valuable insights into the utilisation of this methodology in various industrial and scientific applications.

Electrochemical Liquid‐Liquid‐Solid Growth of Ag‐In Crystals with Liquid Indium Alloy Electrodes

AbstractSynthesis of intermetallic crystals by electrodeposition of Ag from alkaline aqueous electrolytes containing AgCN onto liquid metal electrodes via an electrochemical liquid‐liquid‐solid (ec‐LLS) process has been performed. X‐ray diffraction, scanning electron microscopy, and transmission electron microscopy were performed to identify crystalline products. Ec‐LLS experiments performed with pure liquid Hg and Ga electrodes resulted in the formation of polycrystalline Ag2Ga and Ag2Hg3. Experiments performed with In‐containing liquid metals preferentially yielded Ag9In4 and AgIn2 products with liquid Hg0.35In0.65 and Ga0.86In0.14, respectively. The product distribution with liquid Hg0.35In0.65 depended on the level of Ag supersaturation during the electrodeposition. A mechanism that accounts for the aforementioned observations is presented and discussed. This work described the formation of Ag−In intermetallic phases by the isothermal electroreduction of Ag into different liquid metal solvents via ec‐LLS. Electrodeposition of Ag into a pure Ga or pure Hg liquid metal pool yielded precisely the compounds predicted from isothermal cross‐sections of the respective binary phase diagrams. These compounds were not found when using liquid Hg or Ga containing appreciable In. The smaller enthalpy of formation for AgIn2 was consistent with its synthesis in Ga0.86In0.14. However, the observed product of Ag9In4 in Hg‐containing liquid metals could not be rationalized solely from thermodynamic factors. Instead, this observation was consistent with a kinetic pathway based on the lability of Hg‐metal bonds and nearly identical crystal structures of Ag9In4 and Ag2Hg3. Site exchange of Hg for In is consistent with our prior observations[23] of In exchange into Hg−Pd structures during Pd electrodeposition. This mechanism is not based on any direct role of electrochemistry other than aspects that dictate the operative supersaturation of the metal solute.

Nucleation Control and Isolation of Polymorphic Forms of Aspirin through an Efficient Template‐Assisted Swift Cooling Process

AbstractAspirin, a commonly used pharmaceutical therapeutic pharmacological substance, exhibits cross‐nucleation (intergrowth or overgrowth) of stable polymorphic Form‐I over the preferably required metastable polymorphic Form‐II, which creates a bottleneck issue in the solution crystallization of aspirin in most organic solvents and their mixtures. Controlling the overgrowth phenomenon is a key factor for designing the pharmaceutical drug material aspirin with desired properties. Hence, our present work chose a novel template‐assisted swift cooling crystallization with selected templates like copper‐wire and nylon 6/6 polymer, and also N‐N‐Dimethylformamide (DMF) as a solvent. The pure solution in the absence and the presence of a nylon 6/6 template in all the experimental supersaturation ranges achieves only thermodynamically stable polymorphic Form‐I of aspirin with slightly different morphologies. Contrarily, the presence of a copper‐wire template induces both stable and metastable polymorphs of aspirin depending on the level of supersaturation in the mother solution. The effect of templates on the nucleation kinetics of aspirin polymorphs is estimated using classical nucleation theory, and the determined values exactly match with experimental results. The polymorphic nature of the grown crystals is ascertained by powder X‐ray diffraction (PXRD), single crystal X‐ray diffraction (SCXRD), and differential scanning calorimetry (DSC) analyses.

Influence of the Isothermal Transformation Temperature on the Structure and Properties of Low-Carbon Steel

Purpose. The study is aimed at evaluating the effect of the isothermal transformation temperature on the structure and properties of low-carbon steel. Methodology. The material for the study was a 3 mm diameter wire made of mild steel with the following chemical composition: 0.21% C, 0.47% Mn, 1.2% Si, 0.1% Cr, 0.03% S, 0.012% P. The 0.3 m long wire samples were subjected to austenitizing at 920 °C for 8...9 min, after which they were held isothermally for 11 min at temperatures of 650...200 °C, followed by cooling in air. The strength, plastic properties, and strain hardening coefficient were determined from the analysis of tensile curves. Findings. It was found that a decrease in the temperature of isothermal transformation, starting from 450...400 °C, increases the amount of Widmannstätten ferrite due to the disappearance of polyhedral ferrite grains. At the same time, the number of areas with locally located dispersed cementite particles similar to pearlite colonies increases, and bainite crystals appear. Against the background of a sharp decrease in the strain hardening coefficient in the range of 450...400 °C, the ability of the bainite phase to undergo plastic deformation should be considered one of the reasons for the delay in density reduction. Originality. The effect of steel hardening with a decrease in the pearlite transformation temperature is based on the grinding of ferrite grains, an increase in the amount of Widmannstätten ferrite, and the dispersion of pearlite colonies. The strengthening effect of steel with a bainite structure is based on an increase in the degree of supersaturation of the solid solution with carbon atoms and dispersion hardening by particles of the carbide phase. Practical value. The optimal structural state of steel intended for the manufacture of such critical elements as a support beam, railroad car bogie, etc. is a mixture of phase components with different dispersion and morphology, and their quantitative ratio is determined by the operating conditions of a particular product.

Self‐Regulated Growth of Large‐Grain Sb2S3 Thin Films for High‐Efficiency Solar Cells

AbstractAntimony sulfide (Sb2S3) has attracted extensive attention due to its excellent photoelectric characteristics, including a high absorption coefficient (α &gt; 104 cm−1) and a suitable bandgap (≈1.7 eV). However, due to its Q1D (quasi‐1D) structure, numerous deep‐level defects are identified in the Sb2S3 film, limiting the device's performance, and necessitating more efforts to overcome this situation. In this context, an ethanol solvent‐assisted chemical bath deposition (S‐CBD) strategy, a novel high‐quality thin film manufacturing technique is presented that modifies the supersaturation of the precursor solution by varying the boiling point and solvent polarity. This approach enables the effective regulation of the correlation between the crystal nucleation and growth rates, resulting in Sb2S3 films with large grains (≈4.25 µm, 37.5% ethanol), excellent crystallinity, well‐oriented structures (TC(211)/TC(020) = 2.39), low defect density, and prolonged carrier lifetimes (τAve ≈ 12.1 ns). Consequently, the final Sb2S3‐based solar device (FTO/CdS/Sb2S3/Spiro‐OMeTAD/Au) shows significant improvements in both FF (61.63%) and JSC (17.61 mA cm−2), yielding an excellent power conversion efficiency (PCE) of 7.84%. This research gives particular insights into the growth mechanism of high‐quality Sb2S3 thin films by CBD method as well as a potential route for enhancing Sb2S3 solar cell performance.

Cholesterol plus dietary tannins play a key role in formation of urinary stone

The incidence of urolithiasis has been rising worldwide for several decades, but the main aetiological factors remain unknown. It was found that the prevalence of urolithiasis was correlated with intakes of high fat plus fruits rich in tannins through questionnaire-based dietary consumption surveys and epidemiological analysis. Cholesterol and polyphenols were also found in various renal stones of human. Cholesterol could co-precipitate with polyphenols extracted from various food materials in vitro, particularly condensed tannins. Therefore, prepared tannins from fruit were isolated by gel filtration column and characterized by high performance liquid chromatography. Mice gavaged with apple tannins and cholesterol caused remarkable cholesterol/tannins deposits, glomerular atrophy as well as increasing urine proteins, creatinine and electrolytes. Mice gavaged with ethylene glycol, tannins and cholesterol showed stronger nephrotoxicity, caused urine solute supersaturation in renal tubules, less urine and more deposits in urinary system, forming bladder stones (41.6% morbidity). Molecular dynamics simulation suggested that tannins and cholesterol formed complexes through van der Waals forces and hydrogen bonds. These findings indicated that interaction of cholesterol and tannins is a key factor in the formation of urinary stones, providing a clear explanation of urolithiasis formation. This study should help to design the strategies for prevention and control of various urinary stones as well as reveal the crucial reason for the increasing prevalence of urinary stones.

Thermodynamic modelling application for prediction of diffusion formation of supersaturation solution

Abstract In this paper the effect of diffusion formation of supersaturated solid solution in the Al–Ge system is discussed. It was shown that at relatively low temperatures of diffusion annealing, Ge concentration in Al-based solid solution became higher than the solubility limit at given temperatures. The maximal concentration of Ge was determined by extrapolation of the diffusion profile on the Ge/Al interface. Analysis of diffusivity of Al in Ge allowed to suggest that slow diffusion in Ge restricts the formation of Ge-based solid solution. Qualitative approach confirmed this suggestion.