No abstract

Colloid-polymer mixtures may undergo either fluid-fluid phase separation or gelation. This depends on the depth of the quench (polymer concentration) and polymer-colloid size ratio. We present a real-space study of dynamics in phase separating colloid-polymer mixtures with medium-to long-range attractions (polymercolloid size ratio q R = 0.45 − 0.89), with the aim of understanding the mechanism of gelation as the range of the attraction is changed. In contrast to previous studies of short-range attractive systems, where gelation occurs shortly after crossing the equilibrium phase boundary, we find a substantial region of fluid-fluid phase separation. On deeper quenches the system undergoes a continuous crossover to gel formation. We identify two regimes, 'classical' phase separation, where single particle relaxation is faster than the dynamics of phase separation, and 'viscoelastic' phase separation, where demixing is slowed down appreciably due to slow dynamics in the colloid-rich phase. Particles at the surface of the strands of the network exhibit significantly greater mobility than those buried inside the gel strand which presents a method for coarsening. arXiv:1209.3973v1 [cond-mat.soft]

Metastable gels formed by weakly attractive colloidal particles display a distinctive two-stage time-dependent settling behavior under their own weight. Initially a space-spanning network is formed that for a characteristic time, which we define as the lag time τ d , resists compaction. This solid-like behavior persists only for a limited time. Gels whose age tw is greater than τ d yield and suddenly collapse. We use a combination of confocal microscopy, rheology and time-lapse video imaging to investigate both the process of sudden collapse and its microscopic origin in an refractiveindex matched emulsion-polymer system. We show that the height h of the gel in the early stages of collapse is well described by the surprisingly simple expression, h(τ ) = h0 − Aτ 3 2 , with h0 the initial height and τ = tw − τ d the time counted from the instant where the gel first yields. We propose that this unexpected result arises because the colloidal network progressively builds up internal stress as a consequence of localized rearrangement events which leads ultimately to collapse as thermal equilibrium is re-established.

Microgels are cross-linked polymer latex particles that can form stable colloidal dispersions. Their typical sizes range from 10 to 1000 nm and they can swell in response to their external environment (pH, temperature and solvency). This swelling behaviour is central to many potential applications for microgels. The existing literature is dominated by studies of the properties of aqueous microgel dispersions. In contrast, this review focusses on the development of microgel particles in non-aqueous systems, looking at the challenges of studying these particles as well as their swelling behaviour. The five main mechanisms of producing microgel particles will be discussed and examples of materials used for microgels that swell in non-aqueous solvents will be given. Finally some examples of applications for non-aqueous microgels are given.

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We investigate the reversible, binary gelation of poly(N-isopropylacrylamide) (pNIPAM) microgels in the presence of triblock-copolymer (PEO–PPO–PEO type) surfactant. Confocal microscopy highlights that both polymers are present in the gel network.

Colloidal gels constitute an important class of materials found in many contexts and with a wide range of applications. Yet as matter far from equilibrium, gels exhibit a variety of time-dependent behaviours, which can be perplexing, such as an increase in strength prior to catastrophic failure. Remarkably, such complex phenomena are faithfully captured by an extremely simple model—‘sticky spheres’. Here we review progress in our understanding of colloidal gels made through the use of real space analysis and particle resolved studies. We consider the challenges of obtaining a suitable experimental system where the refractive index and density of the colloidal particles is matched to that of the solvent. We review work to obtain a particle-level mechanism for rigidity in gels and the evolution of our understanding of time-dependent behaviour, from early-time aggregation to ageing, before considering the response of colloidal gels to deformation and then move on to more complex systems of anisotropic particles and mixtures. Finally we note some more exotic materials with similar properties.

Attractive colloidal particles can form a disordered elastic solid or gel when quenched into a twophase region, if the volume fraction is sufficiently large. When the interactions are comparable to thermal energies the stress-bearing network within the gel restructures over time as individual particle bonds break and reform. Typically, under gravity such weak gels show a prolonged period of either no or very slow settling, followed by a sudden and rapid collapse -a phenomenon known as delayed collapse. The link between local bond breaking events and the macroscopic process of delayed collapse is not well understood. Here we summarize the main features of delayed collapse and discuss the microscopic processes which cause it. We present a plausible model which connects the kinetics of bond breaking to gel collapse and test the model by exploring the effect of an applied external force on the stability of a gel.