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The real-space structure of hard-sphere glasses quenched from colloidal liquids in thermodynamic equilibrium has been determined. Particle coordinates were obtained by combining the optical sectioning capability of confocal fluorescence microscopy with the structure of specially prepared fluorescent silica colloids. Both the average structure and the local structure of glasses, with volume fractions ranging from 0.60 to 0.64, were in good agreement with glasses and random close packings generated by computer simulations. No evidence of a divergent correlation length was found. The method used to obtain the three-dimensional particle coordinates is directly applicable to other colloidal structures, such as crystals, gels, and flocs. dius of 200 nm, a total radius of 525 nm, and a polydispersity in size of 1.8%. The synthesis and characterization of these hybrid organic-inorganic spheres are described in (1 7). The hard-sphere potential was created by dispersing the particles in dimethvlformamide (in which the refractive index ~ -was almost matched) to decrease the van der Waals forces and bv addine 0.1 M LiCl w to decrease the double layer to a very small value relative to the radius. As measured bv confocal microscopy, the average distance of closest approach of the particles was 1052 nm in a dried glass and 1082 nm in the glass with solvent; the difference is probably attributable to a solvation laver that Drotects the particles from aggregation. The crystallization and melting volume fractions calDespite recent progress, neither the glass computer simulations can become imporculated from this interaction distance of transition nor the structure of glasses is fully tant, especially if the goal is to find a diverclosest approach were 0.50 and 0.55

We use substrates chemically micropatterned with anionic and cationic regions to govern the deposition of charged colloidal particles. The direct observation of the colloidal assembly suggests that this process includes two steps: an initial patterned attachment of colloids to the substrate and an additional ordering of the structure upon drying. The driving forces of the process, i.e. , screened electrostatic and lateral capillary interactions, are discussed. This approach makes it possible to fabricate complex, high-resolution two-dimensional arrays of colloidal particles.

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Measurement of the fractal dimension, D, of colloidal aggregates of small silica particles is reported. We observe power-law decay of the structure factor [S(k) -k o] by both light and x-ray scattering showing that the aggregates are fractal. D is found to be 2.12+0.05, which is intermediate between recent numerical results for the kinetic models of diffusionlimited aggregation (D = 2.5) and cluster aggregation (D = 1.75), but is rather close to the value for lattice animals (D = 2.0), which are equilibrium structures. PACS numbers: 64.60.Cn, 05.40.+j, 61.10.Fr Understanding aggregation has been a primary goal in the field of colloidal physics for many years. 'In addition to its importance in commercial processes, aggregation is a prototypical example of a complicated random process which may display such features as self-similarity, scaling, and universality. 2 These features have been revealed by computer simulations.It has been shown recently, for example, that the two most popular models, diffusion-limited aggregation3 4 (DLA) and cluster-cluster aggregation 6 (CA), produce ramified structures that are self-similar in that the two-point density-density correlation function p2(r) is of a power-law form, p, (r) -r ", for values of r intermediate between the lattice constant or monomer size a and the cluster size R. Structures described by Eq. (1) are self-similar and are known as fractals; their essential geometric properties are independent of length scale. In ddimensional space, they are characterized by a fractal or Hausdorff-Besicovitch dimension D related to A by D = d -A. An immediate consequence of Eq.(1) is that the radius of gyration of a cluster RG is related to the number of particles it contains N, by N, -RD (2) A uniform object has D = d, while more open structures in which the density decreases with distance from the center have D & d. Numerical simulations have shown D to be -Sd/6 for DLA in d dimensions for both lattice (2~d~6) and nonlattice (d=2, 3) diffusion, independent of sticking coefficient s (0. 1» s~1). Cluster aggregation in which many particles diffuse and stick together to form clusters which also diffuse and stick yields self-similar aggregates having D =1.45 and 1.75 in two and three dimensions, respectively.

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A nearly symmetric critical mixture (φc=0.486) of perdeuterated and protonated 1,4-polybutadiene exhibiting an upper critical solution temperature Tc=61.5±1.5 °C has been quenched from the homogeneous state (≂75 °C) to various temperatures between 25 and 57.5 °C. Light scattering measurements document the subsequent spinodal decomposition process which we describe based on a four-stage model: early, intermediate, transition, and final. The early stage is accounted for by the Cahn theory, yielding initial correlation lengths and effective diffusion coefficients in quantitative agreement with mean-field predictions. Nonlinear effects mark the beginning of the intermediate stage, which exhibits a simple power-law growth of heterogeneity length Lm(t)∼tneff, but with a temperature dependent exponent neff. As the composition fluctuation amplitude approaches the equilibrium values, the spinodal decomposition process enters the transition stage, characterized by a decreasing interfacial thickness and an increasing Lm(t). Once the interfacial profile equilibrates, a crossover to the final stage occurs. Subsequent growth of L(t) leaves the morphology unaffected as evidenced by a universal structure factor. These findings are discussed in the context of the current theory and are compared with prior studies involving polymer–polymer and simple liquid mixtures.

The ability to pattern soft materials at the microscale is critical for several emerging technologies, including tissue-engineering scaffolds, [1][2][3] photonic crystals, [4][5][6] sensors, [7][8][9] and self-healing materials.[10] Hydrogels are an important class of soft materials that can be fabricated in the form of 3D microperiodic structures by colloidal templating [3,[7][8][9]11] or interference lithography.[12]However, neither approach allows one to omnidirectionally vary the spacing between patterned features over length scales ranging from sub-micrometer to tens of micrometers. By contrast, direct-write assembly enables a wide array of materials to be patterned in nearly arbitrary shapes and dimensions. [13][14][15] Here, we report the fabrication of 1D and 3D microperiodic hydrogel scaffolds by direct-write assembly of an acrylamide-based ink. For the first time, we combine direct ink writing with in situ photopolymerization to obtain hydrogel scaffolds with micrometer-sized features (see Fig. 1). By plating 3T3 murine fibroblasts onto one-, two-, and four-layer hydrogel scaffolds, we demonstrate their cytocompatibility and, hence, potential suitability for tissue-engineering applications.Direct ink writing (DIW) is a layer-by-layer assembly technique in which materials are patterned in both planar and 3D forms with lateral feature sizes that are at least an order of magnitude smaller than those achieved by ink-jet printing [16][17][18] and other rapid prototyping approaches, [19][20][21][22][23][24] and nearly comparable in size to those produced by two-photon polymerization [25] and interference holography.[12] Central to our approach is the creation of concentrated inks that can be extruded through fine deposition nozzles in filamentary form, and then undergo rapid solidification to maintain their shape even as they span gaps in the underlying layer(s). Unlike prior efforts on polyelectrolyte inks that required reservoir-induced coagulation to enable 3D printing, [14] we report the creation of hydrogel inks that can be printed directly in air, where they undergo solidification via photopolymerization (see Fig. 1a and b).The ink is created by first mixing monomeric acrylamide, glycerol, and water. Upon ageing for several hours under ambient conditions, the monomeric species polymerizes to yield a gel composed of 30 w/o polyacrylamide chains.[26] 1 H NMR reveals that peaks associated with acrylamide, which are initially present, disappear after polymerization, followed by the emergence of two new peaks that correspond to alkyl chains (data not shown). Concomitantly, as the solution ages, sharp rises in both the shear elastic, G 0 , and loss, G 00 , moduli are observed, suggesting that the resulting gel is composed of physically entangled polyacrylamide chains (see Fig. 2a). To determine their degree of polymerization, N, the intrinsic viscosity, [h] 0 , of diluted polymer solutions is measured by capillary viscometry, and found to be [h] 0 % 270 mL g À1 (see Fig. 2b). [27,28] Using the Mark-Houwink re...