The effects of thermally reduced graphene sheets (TRG) on the phase separation in poly[(α-methyl styrene)-co-(acrylonitrile)]/poly(methyl-methacrylate) blends were monitored using melt rheology, conductivity spectroscopy, and electron microscopic techniques. The TRG were incorporated in the single-phase material by solution mixing. The composite samples were then allowed to phase separate in situ. The thermodynamics of phase separation have been investigated by monitoring the evolution of the storage modulus (G') as a function of temperature as the system passes through the binodal and the spinodal lines of the phase diagram. The phase separation kinetics were probed by monitoring the evolution of G' as a function of time at a quench depth well in the spinodal region. It was observed that TRG significantly influenced the phase separation temperature, the shape of the phase diagram and the rate of phase separation. The state of dispersion of TRG in the blends was assessed using electron microscopy and conductivity spectroscopy measurements. Interestingly, the composite samples (monophasic) were virtually insulators at room temperature, whereas highly conducting materials were obtained as a result of phase separation in the biphasic materials.

In this work, we investigate the shear rheology of Carbopol 981 microgel particle suspensions, confined between shearing plates with gap separations from 5 to 100 μm. We show that even for confining gaps smaller than that of the gel particle size, the yielding of concentrated microgel suspensions is delayed to stress levels above the bulk yield stress. Furthermore, for stresses below this new yield point, slip is described by elastohydrodynamic lubrication theory as long as the direct confinement of the single gel particles between the shearing surfaces is limited to a Hertzian deformation. For a strong, non-Hertzian particle deformation, the slip layer breaks down and leads to a frictional interaction of the single confined particle with the two shearing surfaces, depending on their surface roughness. Lubrication pressures and friction coefficients have been quantified with in situ normal force measurements on the confined particles, which have also been utilized to unambiguously determine the relevant swollen particle dimensions.

Microrheology probes the mesoscale between bulk rheology, which provides an integral sample response, and nanorheology, which refers to a local response at a molecular confinement level. The term 'microrheology' is often used to refer to optical particle tracking methods that measure a local response of a sample. In contrast to this, non-optical microrheology techniques generally allow two different effects to be studied: actual confinement effects on the rheology and boundary effects such as slip. Investigating the mesoscale range has additional advantages such as the possibility to perform measurements with small sample volumes and at high shear rates. This review bundles the wide array of non-optical techniques into five categories: adaptations to a conventional rotational rheometer, sliding plate rheometry on a micrometer scale, microfluidics, piezo vibrators and radial channel flows. The concept of each set of techniques is described, together with their operational window and examples of recent studies.

An X-ray flexure-based microgap rheometer (X-FMR) has been designed for combining rheology and in situ small-angle X-ray scattering from the vorticity plane. The gap distance can be varied continuously from 500 μm down to several μm, which provides the unique possibility to generate a strong confinement for many complex fluids. A singular advantage of this setup is the possibility to directly probe the vorticity direction of the flow field with a microfocus X-ray beam and to probe the structural response of the fluid to combined shear and confinement in the vorticity plane. The sliding-plate setup operates over a wide range of shear rates of γ = 10(-3)-10(3) s(-1) and strains in the range of 10(-4)-10(2). The flexure-based bearing maintains the plate parallelism within 10(-5) rad. The X-FMR requires very small sample volumes on the order of 10 μl. The applicability of the device is demonstrated here with limited examples of a nematic suspension of fd virus (rods), and a crystalline suspension containing sterically stabilized polystyrene-butylacrylate latex particles.

In this paper we determine the effect of confinement on the shear flow of concentrated soft microgel particle suspensions. Utilizing a Flexure-based Microgap Rheometer (FMR), aqueous suspensions of swollen P(NIPAM-co-AA) microgel particles of 4 µm diameter at different volume fractions larger than 64 vol% are subjected to shearing deformations between plates separated by gaps of 5 −120 µm while monitoring the stress response at different rates. Describing the stress evolution from a balance of elastohydrodynamic lubrication and elastic forces following the approach of Cloitre and Bonnecaze, it could be shown that already below a critical confinement level on the order of 10 particle diameters an increase of the interparticle pressure leads to a rising shear stress at a given rate in the yielded regime. This effect is strongest for particle volume fractions close to the critical closest packing, with two orders of magnitude increase in flow resistance when approaching the single particle confinement level, whereas this confinement effect on the flow decreases when raising the concentration. Furthermore, it could be shown that, at the onset of the yielding of the suspensions, the confinement is increasing the effective modulus, but not the yield strain. 2 Giovanni Vleminckx et al. Rheologica Acta manuscript No.