Ziren Wang

Two-step nucleation mechanism in solid–solid phase transitions

The microscopic kinetics of ubiquitous solid-solid phase transitions remain poorly understood. Here, by using single-particle-resolution video microscopy of colloidal films of diameter-tunable microspheres, we show that transitions between square and triangular lattices occur via a two-step diffusive nucleation pathway involving liquid nuclei. The nucleation pathway is favoured over the direct one-step nucleation because the energy of the solid/liquid interface is lower than that between solid phases. We also observed that nucleation precursors are particle-swapping loops rather than newly generated structural defects, and that coherent and incoherent facets of the evolving nuclei exhibit different energies and growth rates that can markedly alter the nucleation kinetics. Our findings suggest that an intermediate liquid should exist in the nucleation processes of solid-solid transitions of most metals and alloys, and provide guidance for better control of the kinetics of the transition and for future refinements of solid-solid transition theory.

Imaging the homogeneous nucleation during the melting of superheated colloidal crystals

Homogeneous Melting The nucleation and melting of crystals are primarily driven by surfaces and defects, which can lower the thermodynamic barrier to a phase transition. A harder problem to study is when the transition occurs uniformly. Wang et al. (p. 87; see the Perspective by Weeks) imaged the homogeneous melting of superheated colloidal crystals using a laser to initiate the melting at the interior of the crystal. The authors were then able to track nucleation precursors and nucleus evolution and to find where defects and instabilities limited the homogeneous melting process. Uniform colloidal crystals are used to study the effects of superheating on homogeneous melting. The nucleation process is crucial to many phase transitions, but its kinetics are difficult to predict and measure. We superheated and melted the interior of thermal-sensitive colloidal crystals and investigated by means of video microscopy the homogeneous melting at single-particle resolution. The observed nucleation precursor was local particle-exchange loops surrounded by particles with large displacement amplitudes rather than any defects. The critical size, incubation time, and shape and size evolutions of the nucleus were measured. They deviate from the classical nucleation theory under strong superheating, mainly because of the coalescence of nuclei. The superheat limit agrees with the measured Born and Lindemann instabilities.

Two-dimensional freezing criteria for crystallizing colloidal monolayers

Video microscopy was employed to explore crystallization of colloidal monolayers composed of diameter-tunable microgel spheres. Two-dimensional (2D) colloidal liquids were frozen homogenously into polycrystalline solids, and four 2D criteria for freezing were experimentally tested in thermal systems for the first time: the Hansen-Verlet freezing rule, the Lowen-Palberg-Simon dynamical freezing criterion, and two other rules based, respectively, on the split shoulder of the radial distribution function and on the distribution of the shape factor of Voronoi polygons. Importantly, these freezing criteria, usually applied in the context of single crystals, were demonstrated to apply to the formation of polycrystalline solids. At the freezing point, we also observed a peak in the fluctuations of the orientational order parameter and a percolation transition associated with caged particles. Speculation about these percolated clusters of caged particles casts light on solidification mechanisms and dynamic heterogeneity in freezing.

Melting in two-dimensional Yukawa systems: a Brownian dynamics simulation.

We studied the melting behavior of two-dimensional colloidal crystals with a Yukawa pair potential by Brownian dynamics simulations. The melting follows the Kosterlitz-Thouless-Halperin-Nelson-Young (KTHNY) scenario with two continuous phase transitions and a middle hexatic phase. The two phase-transition points were accurately identified from the divergence of the translational and orientational susceptibilities. Configurational temperatures were employed to monitor the equilibrium of the overdamped system and the strongest temperature fluctuation was observed in the hexatic phase. The inherent structure obtained by rapid quenching exhibits three different behaviors in the solid, hexatic, and liquid phases. The measured core energy of the free dislocations, E(c) = 7.81 ± 0.91 k(B)T, is larger than the critical value of 2.84 k(B)T, which consistently supports the KTHNY melting scenario.

Direct observation of liquid nucleus growth in homogeneous melting of colloidal crystals

The growth behaviour of liquid nucleus is crucial for crystal melting, but its kinetics is difficult to predict and remains challenging in experiment. Here we directly observed the growth of individual liquid nuclei in homogeneous melting of three-dimensional superheated colloidal crystals with single-particle dynamics by video microscopy. The growth rate of nucleus at weak superheating is well fitted by generalizing the Wilson–Frenkel law of crystallization to melting and including the surface tension effects and non-spherical-shape effects. As the degree of superheating increases, the growth rate is enhanced by nucleus shape fluctuation, nuclei coalescence and multimer attachment. The results provide new guidance for the refinement of nucleation theory, especially for the poorly understood strong-superheating regime. The universal Lindemann parameter observed at the superheat limit and solid–liquid interfaces indicates a connection between homogeneous and heterogeneous melting.

Two features at the two-dimensional freezing transitions.

We studied the two-dimensional freezing transitions in monolayers of microgel colloidal spheres with short-ranged repulsions in video-microscopy experiments, and monolayers of hard disks, and Yukawa particles in simulations. These systems share two common features at the freezing points: (1) the bimodal distribution profile of the local orientational order parameter; (2) the two-body excess entropy, s(2), reaches -4.5±0.5 k(B). Both features are robust and sensitive to the freezing points, so that they can potentially serve as empirical freezing criteria in two dimensions. Compared with the conventional freezing criteria, the first feature has no finite-size ambiguities and can be resolved adequately with much less statistics; and the second feature can be directly measured in macroscopic experiments without the need for microscopic information.

Melting of microgel colloidal crystals

We experimentally studied the melting of colloidal crystals composed of diameter-tunable microgel spheres by bright-field and confocal video microscopies at the single-particle level. Thick (> 4 layers) and thin (? 4 layers) films exhibited dramatically different melting kinetics. Thick films melted heterogeneously from grain boundaries in polycrystals and from surfaces in single crystals, while thin films melted homogeneously even in polycrystals. A novel heterogeneous melting at dislocation was observed in 5- to 12-layer films. The equilibrium phase behaviors in three thickness regimes were all different: thick films had a crystal-liquid coexistence regime which decreased with the film thickness and vanished at 4 layers, thin crystalline films melted into liquids in one step, while monolayers melted in two steps with an intermediate hexatic phase.

Homogeneous melting of 3D superheated colloidal crystals

We directly observed the kinetics of homogeneous melting in 3D superheated colloidal crystals at single-particle resolution by video microscopy. We found that the precursor of nuclei is in fact local particle exchanges surrounded by particles with large displacement amplitudes rather than any types of defects. The critical size, incubation time, shape evolution of nucleus were measured under different degrees of superheating.