Polymer networks are critically important for numerous applications including soft biomaterials, adhesives, coatings, elastomers, and gel-based materials for energy storage. One long-standing challenge these materials present lies in understanding the role of network defects, such as dangling ends and loops, developed during cross-linking. These defects can negatively impact the physical, mechanical, and transport properties of the gel. Here we report chemically cross-linked poly(ethylene glycol) (PEG) gels formed through a unique cross-linking scheme designed to minimize defects in the network. The highly resilient mechanical properties of these systems (discussed in a previous publication1), suggests that this cross-linking technique yields more homogeneous network structures. Four series of gels were formed based on chains of 35,000 g/mol, (35K), 12,000 g/mol (12K) g/mol, 8,000 g/mol (8K) and 4,000 g/mol (4K) PEG. Gels were synthesized at five initial polymer concentrations ranging from 0.077 g/mL to 0.50 g/mL. Small-angle neutron scattering (SANS) was utilized to investigate the network structures of gels in both D2O and d-DMF. SANS results show the resulting network structure is dependent on PEG length, transitioning from a more homogeneous network structure at high molecular weight PEG to a two phase structure at the lowest molecular weight PEG. Further investigation of the transport properties inherent to these systems, such as diffusion, will aid to further confirm the network structures.

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We present an X-ray photon correlation spectroscopy (XPCS) study of dynamic transitions in an anisotropic colloid-polymer dispersion with multiple arrested states. The results provide insight into the mechanism for formation of repulsive glasses, attractive glasses, and networked gels of colloids with weakly adsorbing polymer chains. In the presence of adsorbing polymer chains, we observe three distinct regimes: a state with slow dynamics consisting of finite particles and clusters, for which interparticle interactions are predominantly repulsive; a second dynamic regime occurring above the saturation concentration of added polymer, in which small clusters of nanoparticles form via a short-range depletion attraction; and a third regime above the overlap concentration in which dynamics of clusters are independent of polymer chain length. The observed complex dynamic state diagram is primarily governed by the structural reorganization of a nanoparticle cluster and polymer chains at the nanoparticle-polymer surface and in the concentrated medium, which in turn controls the dynamics of the dispersion.

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