The nature of solid-solid phase transformations has been a long-standing question spanning the fields of metallurgy and condensed-matter physics, with applications from metallic alloys and ceramics to modern shape-memory materials. In spite of the importance of solid-to-solid transformations in many areas of materials science and condensed-matter physics and the numerous experimental and theoretical studies, a deep understanding of the microstructural changes and the underlying kinetic mechanisms is still missing. In this work, we establish a versatile model system composed of micron-scale ionic microgel colloids, where we not only probe the single-particle kinetics in real space and real time but also tune the phase transition in a multiple-parameter space. In the presence of an imposed electric field, a face-centered cubic (FCC) crystal transforms diffusively into a body-centered tetragonal (BCT) crystal via nucleation and growth. In the reverse direction, however, the BCT phase transforms cooperatively into a long-lived metastable body-centered orthorhombic phase, which only relaxes back to the equilibrium FCC when annealed at higher temperatures. The kinetics is thus either diffusive or martensitic depending on the path, and we believe that these two path-dependent transitions provide the first real-space, particle-level insights of diffusive and martensitic transformations, respectively, in a single system.

Spin coating is an out-of-equilibrium technique for producing polymer films and colloidal crystals quickly and reproducibly. In this review, we present an overview of theoretical and experimental studies of the spin coating of colloidal suspensions. The dynamics of the spin coating process is discussed first, and we present insights from both theory and experiment. A key difference between spin coating with polymer solutions and with monodisperse colloidal suspensions is the emergence of long range (centimeter scale) orientational correlations in the latter. We discuss experiments in different physical regimes that shed light on the many unusual partially-ordered structures that have long-range orientational order, but no long-range translational order. The nature of these structures can be tailored by adding electric or magnetic fields during the spin coating procedure. These partially-ordered structures can be considered as model systems for studying the fundamentals of poorly crystalline and defect-rich solids, and they can also serve as templates for patterned and/or porous optical and magnetic materials.

aWe study, using fluorescent confocal laser scanning microscopy, the directed self-assembly of cross-linked ionic microgels under the influence of an applied alternating electric field at different effective packing fractions f eff in real space. We present a detailed description of the contribution of the electric field to the soft interparticle potential, and its influence on the phase diagram as a function of f eff and field strength E at a constant frequency of 100 kHz. In our previous work [Mohanty et al., Soft Matter, 2012, 8, 10819], we demonstrated the existence of field-induced structural transitions both at low and high f eff . In this work, we revisit the phase behavior at low and intermediate f eff with a focus on both structure and dynamics. We demonstrate the existence of various field induced transitions such as an isotropic fluid to string phase to body centered tetragonal (BCT) crystal phase at low concentrations and a reversible field-induced crystal (face centered cubic, FCC) to crystal (BCT) transition at intermediate concentrations. We also investigate the kinetics of the crystal-crystal transition and demonstrate that this occurs through an intermediate melting process. These results are discussed in the light of previous studies of dipolar hard and charged colloids.

Although there are numerous self-assembly techniques to prepare colloidal crystals, there is great variability in the methods used to characterize order and disorder in these materials. We assess different kinds of structural order from more than 70 two-dimensional microscopy images of colloidal crystals produced by many common methods, including spin-coating, dip-coating, convective assembly, electrophoretic assembly, and sedimentation. Our suite of analysis methods includes measures for both positional and orientational order. The benchmarks are two-dimensional lattices that we simulated with different degrees of controlled disorder. We find that translational measures are adequate for characterizing small deviations from perfect order, whereas orientational measures are more informative for polycrystalline and highly disordered crystals. Our analysis presents a unified strategy for comparing structural order among different colloidal crystals and establishes benchmarks for future studies.

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