This review collects and describes experiments that employ colloidal suspensions to probe physics in ordered and disordered solids and related complex fluids. The unifying feature of this body of work is its clever usage of poly(N-isopropylacrylamide) (PNIPAM) microgel particles. These temperature-sensitive colloidal particles provide experimenters with a 'knob' for in situ control of particle size, particle interaction and particle packing fraction that, in turn, influence the structural and dynamical behavior of the complex fluids and solids. A brief summary of PNIPAM particle synthesis and properties is given, followed by a synopsis of current activity in the field. The latter discussion describes a variety of soft matter investigations including those that explore formation and melting of crystals and clusters, and those that probe structure, rearrangement and rheology of disordered (jammed/glassy) and partially ordered matter. The review, therefore, provides a snapshot of a broad range of physics phenomenology which benefits from the unique properties of responsive microgel particles.
We investigate the influence of particle shape on the bending rigidity of colloidal monolayer membranes (CMMs) and on evaporative processes associated with these membranes. Aqueous suspensions of colloidal particles are confined between glass plates and allowed to evaporate. Confinement creates ribbonlike air-water interfaces and facilitates measurement and characterization of CMM geometry during drying. Interestingly, interfacial buckling events occur during evaporation. Extension of the description of buckled elastic membranes to our quasi-2D geometry enables the determination of the ratio of CMM bending rigidity to its Young's modulus. Bending rigidity increases with increasing particle anisotropy, and particle deposition during evaporation is strongly affected by membrane elastic properties. During drying, spheres are deposited heterogeneously, but ellipsoids are not. Apparently, increased bending rigidity reduces contact line bending and pinning and induces uniform deposition of ellipsoids. Surprisingly, suspensions of spheres doped with a small number of ellipsoids are also deposited uniformly.
We study phonon modes in two-dimensional colloidal crystals composed of soft microgel particles with hard polystyrene particle dopants distributed randomly on the triangular lattice. This experimental approach produces close-packed lattices of spheres with random bond strength disorder, i.e., the effective springs coupling nearest neighbors are very stiff, very soft, or of intermediate stiffness. Particle tracking video microscopy and covariance matrix techniques are then employed to derive the phonon modes of the corresponding "shadow" crystals with bond strength disorder as a function of increasing dopant concentration. At low frequencies, hard and soft particles participate equally in the phonon modes, and the samples exhibit Debye-like density of states behavior characteristic of crystals. For mid- and high-frequency phonons, the relative participation of hard versus soft particles in each mode is found to vary systematically with dopant concentration. Additionally, a few localized modes, primarily associated with hard particle motions, are found at the highest frequencies.
We investigate the vibrational modes of quasi-two-dimensional disordered colloidal packings of hard colloidal spheres with short-range attractions as a function of packing fraction. Certain properties of the vibrational density of states (vDOS) are shown to correlate with the density and structure of the samples (i.e., in sparsely versus densely packed samples). Specifically, a crossover from dense glassy to sparse gel-like states is suggested by an excess of phonon modes at low frequency and by a variation in the slope of the vDOS with frequency at low frequency. This change in phonon mode distribution is demonstrated to arise largely from localized vibrations that involve individual and/or small clusters of particles with few local bonds. Conventional order parameters and void statistics did not exhibit obvious gel-glass signatures as a function of volume fraction. These mode behaviors and accompanying structural insights offer a potentially new set of indicators for identification of glass-gel transitions and for assignment of gel-like versus glass-like character to a disordered solid material.
We study connections between vibrational spectra and average nearest neighbor number in disordered clusters of colloidal particles with attractive interactions. Measurements of displacement covariances between particles in each cluster permit calculation of the stiffness matrix, which contains effective spring constants linking pairs of particles. From the cluster stiffness matrix, we derive vibrational properties of corresponding "shadow" glassy clusters, with the same geometric configuration and interactions as the "source" cluster but without damping. Here, we investigate the stiffness matrix to elucidate the origin of the correlations between the median frequency of cluster vibrational modes and average number of nearest neighbors in the cluster. We find that the mean confining stiffness of particles in a cluster, i.e., the ensemble-averaged sum of nearest neighbor spring constants, correlates strongly with average nearest neighbor number, and even more strongly with median frequency. Further, we find that the average oscillation frequency of an individual particle is set by the total stiffness of its nearest neighbor bonds; this average frequency increases as the square root of the nearest neighbor bond stiffness, in a manner similar to the simple harmonic oscillator. We study connections between vibrational spectra and average nearest neighbor number in disordered clusters of colloidal particles with attractive interactions. Measurements of displacement covariances between particles in each cluster permit calculation of the stiffness matrix, which contains effective spring constants linking pairs of particles. From the cluster stiffness matrix, we derive vibrational properties of corresponding "shadow" glassy clusters, with the same geometric configuration and interactions as the "source" cluster but without damping. Here, we investigate the stiffness matrix to elucidate the origin of the correlations between the median frequency of cluster vibrational modes and average number of nearest neighbors in the cluster. We find that the mean confining stiffness of particles in a cluster, i.e., the ensemble-averaged sum of nearest neighbor spring constants, correlates strongly with average nearest neighbor number, and even more strongly with median frequency. Further, we find that the average oscillation frequency of an individual particle is set by the total stiffness of its nearest neighbor bonds; this average frequency increases as the square root of the nearest neighbor bond stiffness, in a manner similar to the simple harmonic oscillator. Disciplines Physical Sciences and Mathematics | Physics
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