Investigation of crystal structure formation by electropulse treatment of amorphous Ti50Ni25Cu25 alloy ribbons

The study of the effect of electropulse treatment with a variable duration on the crystallization processes and the structure of a amorphous TiNiCu alloy with 25 at.% Cu in comparison with isothermal annealing and heating at a constant speed was carried out. The alloy was fabricated by rapid-quenching from the liquid state (melt spinning technique) at the cooling rate of the melt of about 106 °C/s in the form of a ribbon with a thickness of 28 μm with a surface crystal layer with a thickness of about 2-3 μm. To remove the crystal layer, the method of double-sided electrochemical polishing was used. The studies were carried out by methods of differential scanning calorimetry, metallography and scanning electron microscopy. It was established that the formation of the crystalline phase in the electropulse treatment of the amorphous ribbon occurs from the surface to the inner part due to the predominant formation and growth of columnar crystals with subsequent nucleation and growth of crystals in the rest of the ribbon.

Polymorphic crystalline wetting layers on crystal surfaces

Analogous to surface premelting, we propose that a crystal surface can undergo a pre-solid-solid transition, i.e. developing a thin polymorphic crystalline layer before reaching the solid-solid transition temperature if two crystals can form a low-energy coherent interface. We confirm this in simulations and colloid experiments at single-particle resolution. The power-law increase of surface layer thickness is analogous to premelting. Different kinetics and reversibilities of surface-crystal growth are observed in various systems. Surface crystals exist not only under thermal equilibrium, but also during melting, crystallization, and grain coarsening. Furthermore, the premelting and pre-solid-solid transition can coexist, resulting double surface wetting layers. We hypothesize that such surface phenomena exist in atomic and molecular crystals, which provide a novel way to tune material properties.

Bubble-induced fast crystal growth of indomethacin polymorphs in a supercooled liquid

Physical stability is one of the main challenges when developing robust amorphous pharmaceutical formulations. This article reports fast crystal growth behaviors of the γ and α forms of indomethacin (IMC) initiated by bubbles in the interior of a supercooled liquid. Bubble-induced crystal growth of γ-IMC exhibits approximately the same kinetics as its surface crystal growth, supporting the view that bubble-induced crystal growth is a surface-facilitated process. In contrast, the rates of bubble-induced crystal growth of α-IMC are much faster than those of its surface crystal growth. These results indicate that the bubble-induced crystal growth not only depends on the interface created by the bubble but also strongly correlates with the true cavitation of the bubble. Moreover, bubble-induced fast crystal growth of γ- and α-IMC can be terminated at different temperatures by cooling. These outcomes are meaningful for the in-depth understanding of physical stability and pre-formulation study of amorphous pharmaceutical solids showing surface-facilitated crystal growth.

Surface Crystal Nucleation and Growth in Poly (ε-caprolactone): Atomic Force Microscopy Combined with Fast Scanning Chip Calorimetry

By using an atomic force microscope (AFM) coupled to a fast scanning chip calorimeter (FSC), AFM-tip induced crystal nucleation/crystallization in poly (ε-caprolactone) (PCL) has been studied at low melt-supercooling, that is, at a temperature typically not assessable for melt-crystallization studies. Nanogram-sized PCL was placed on the active/heatable area of the FSC chip, melted, and then rapidly cooled to 330 K, which is 13 K below the equilibrium melting temperature. Subsequent isothermal crystallization at this temperature was initiated by a soft-tapping AFM-tip nucleation event. Crystallization starting at such surface nucleus led to formation of a single spherulite within the FSC sample, as concluded from the radial symmetry of the observed morphology. The observed growth rate in the sub-micron thin FSC sample, nucleated at its surface, was found being much higher than in the case of bulk crystallization, emphasizing a different growth mechanism. Moreover, distinct banding/ring-like structures are observed, with the band period being less than 1 µm. After crystallization, the sample was melted for gaining information about the achieved crystallinity and the temperature range of melting, both being similar compared to much slower bulk crystallization at the same temperature but for a much longer time.

Faceted-rough surface with disassembling of macrosteps in nucleation-limited crystal growth

To clarify whether a surface can be rough with faceted macrosteps that maintain their shape on the surface, crystal surface roughness is studied by a Monte Carlo method for a nucleation-limited crystal-growth process. As a surface model, the restricted solid-on-solid (RSOS) model with point-contact-type step–step attraction (p-RSOS model) is adopted. At equilibrium and at sufficiently low temperatures, the vicinal surface of the p-RSOS model consists of faceted macrosteps with (111) side surfaces and smooth terraces with (001) surfaces (the step-faceting zone). We found that a surface with faceted macrosteps has an approximately self-affine-rough structure on a ‘faceted-rough surface’; the surface width is strongly divergent at the step-disassembling point, which is a characteristic driving force for crystal growth. A ‘faceted-rough surface’ is realized in the region between the step-disassembling point and a crossover point where the single nucleation growth changes to poly-nucleation growth.

Diffusion-controlled and `diffusionless' crystal growth: relation between liquid dynamics and growth kinetics of griseofulvin

Understanding how liquid dynamics govern crystallization is critical for maintaining the physical stability of amorphous pharmaceutical formulations. In the present study, griseofulvin (GSF), a classic antifungal drug, was used as the model system to investigate the correlations between crystal growth kinetics and liquid dynamics. The temperature dependence of the kinetic part of the bulk crystal growth in a supercooled liquid of GSF was weaker than that of the structural relaxation time τα and scaled as τα −0.69. In the glassy state, GSF exhibited the glass-to-crystal (GC) growth behavior, whose growth rate was too fast to be under the control of the α-relaxation process. Moreover, from the perspective of τα, the GC growth of GSF also satisfied the general condition for GC growth to exist: D/u < 7 pm, where D is the diffusion coefficient and u the speed of crystal growth. Also compared were the fast surface crystal growth rates u s and surface relaxation times τsurface predicted by the random first-order transition theory. Here, the surface crystal growth rate u s of GSF exhibited a power-law dependence upon the surface structural relaxation time: u s ∝ τsurface −0.71, which was similar to that of the bulk growth rate and τα. These findings are important for understanding and predicting the crystallization of amorphous pharmaceutical solids both in the bulk and at the surface.

Crystal growth of the core and rotated epitaxial shell of a heterometallic metal-organic framework revealed with atomic force microscopy

Atomic force microscopy has been used to determine the surface crystal growth of two isostructural metal-organic frameworks, [Zn2(ndc)2(dabco)] (ndc = 1,4-naphthalene dicarboxylate, dabco = 4-diazabicyclo[2.2.2]octane) (1) and [Cu2(ndc)2(dabco)] (2) from...