We study the form factor of thermoresponsive microgels based on poly(N-isopropylacrylamide) at high generalized volume fractions, ζ, where the particles must shrink or interpenetrate to fit into the available space. Small-angle neutron scattering with contrast matching techniques is used to determine the particle form factor. We find that the particle size is constant up to a volume fraction roughly between random close packing and space filling. Beyond this point, the particle size decreases with increasing particle concentration; this decrease is found to occur with little interpenetration. Noteworthily, the suspensions remain liquid-like for ζ larger than 1, emphasizing the importance of particle softness in determining suspension behavior.

We independently determine the bulk and shear moduli of compressed microgel suspensions and the bulk modulus of individual microgel particles and find that the elastic behavior of the suspension reflects the degree of compression of the particles. This feature, which is distinct from other soft materials such as emulsions or foams, can give rise to an unusually large difference between the bulk and shear moduli of the suspension. Our results extend our understanding of soft materials to systems based on compressible objects, opening up possibilities for engineering materials with drastically different responses to shear and compression.

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We present a small-angle x-ray scattering study of crystals formed by temperature-sensitive, swollen microgel particles consisting of poly(N-isopropylacrylamide) copolymerized with acrylic acid and 5 mol % of a cross-linker. As for hard spheres, the random hexagonal close-packed structure is predominant during crystal growth and slowly transforms toward the face-centered-cubic structure. However, a transient phase of body-centered-cubic crystal is observed in an intermediate range of effective volume fractions. We estimate that the studied suspensions are close to a transition from face-centered-cubic to body-centered-cubic structure that can be understood by the tendency of the system to maximize the excluded volume and minimize the contact area between the particles.

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