Crystallization is one of the most important phase transformations of first order. In the case of metals and alloys, the liquid phase is the parent phase of materials production. The conditions of the crystallization process control the as-solidified material in its chemical and physical properties. Nucleation initiates the crystallization of a liquid. It selects the crystallographic phase, stable or meta-stable. Its detailed knowledge is therefore mandatory for the design of materials. We present techniques of containerless processing for nucleation studies of metals and alloys. Experimental results demonstrate the power of these methods not only for crystal nucleation of stable solids but in particular also for investigations of crystal nucleation of metastable solids at extreme undercooling. This concerns the physical nature of heterogeneous versus homogeneous nucleation and nucleation of phases nucleated under non-equilibrium conditions. The results are analyzed within classical nucleation theory that defines the activation energy of homogeneous nucleation in terms of the interfacial energy and the difference of Gibbs free energies of solid and liquid. The interfacial energy acts as barrier for the nucleation process. Its experimental determination is difficult in the case of metals. In the second part of this work we therefore explore the potential of colloidal suspensions as model systems for the crystallization process. The nucleation process of colloids is observed in situ by optical observation and ultra-small angle X-ray diffraction using high intensity synchrotron radiation. It allows an unambiguous discrimination of homogeneous and heterogeneous nucleation as well as the determination of the interfacial free energy of the solid-liquid interface. Our results are used to construct Turnbull plots of colloids, which are discussed in relation to Turnbull plots of metals and support the hypothesis that colloids are useful model systems to investigate crystal nucleation.
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http://dx.doi.org/10.1063/1.4963684 | DOI Listing |
J Chem Phys
January 2025
Department of Chemistry, Indian Institute of Science Education and Research (IISER) Tirupati, Tirupati, Andhra Pradesh 517619, India.
Although impurities are unavoidable in real-world and experimental systems, most numerical studies on nucleation focus on pure (impurity-free) systems. As a result, the role of impurities in phase transitions remains poorly understood, especially for systems with complex free energy landscapes featuring one or more intermediate metastable phases. In this study, we employed Monte Carlo simulations to investigate the effects of static impurities (quenched disorder) of varying length scales and surface morphologies on the crystal nucleation mechanism and kinetics in the Gaussian core model system-a representative model for soft colloidal systems.
View Article and Find Full Text PDFAdv Mater
January 2025
Department of Chemistry, City University of Hong Kong, Kowloon, 999077, Hong Kong.
Perovskite/silicon tandem solar cells (TSCs) are promising candidates for commercialization due to their outstanding power conversion efficiencies (PCEs). However, controlling the crystallization process and alleviating the phases/composition inhomogeneity represent a considerable challenge for perovskite layers grown on rough silicon substrates, ultimately limiting the efficiency and stability of TSC. Here, this study reports a "halide locking" strategy that simultaneously modulates the nucleation and crystal growth process of wide bandgap perovskites by introducing a multifunctional ammonium salt, thioacetylacetamide hydrochloride (TAACl), to bind with all types of cations and anions in the mixed halide perovskite precursor.
View Article and Find Full Text PDFSci Rep
January 2025
Condensed Matter Physics & Nanoscience Research Laboratory, Department of Physics and Material Science, Madan Mohan Malaviya University of Technology, Gorakhpur, 273010, U.P, India.
Nat Commun
January 2025
Faculty of Materials Science and Energy Engineering, Shenzhen University of Advanced Technology, Shenzhen, China.
Aqueous zinc ion batteries exhibit great prospects due to their low cost and high safety, while their lifespan is limited by severe dendritic growth problems. Herein, we develop an anti-dendrite hot-pressing separator interlayer through a mass-producible hot-pressing strategy, by spreading metal-organic framework (MOF) precursor on nonwoven matrix followed by a simple hot-pressing process. The in situ modification of MOF crystals on fiber surface processes abundant nitrogenous functional groups and high specific surface area (190.
View Article and Find Full Text PDFNat Commun
January 2025
Department of Civil & Environmental Engineering, University of California Los Angeles (UCLA), Los Angeles, CA, USA.
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