We use space-resolved dynamic light scattering in the highly multiple scattering regime (Photon Correlation Imaging Diffusing Wave Spectroscopy, PCI-DWS) to investigate temperature-induced phase transitions in polymorphic materials. We study paraffin wax as a simple model system and chocolate, a prototypical example of fat-based products exhibiting complex, history-dependent phase transitions. We find that microscopic dynamics measured using PCI-DWS show remarkable, non-monotonic behavior upon heating: they transiently accelerate when crossing phase transition and slow down above the transition temperature. Sub-micron resolution measurements of the local drift of the sample surface reveal that the speed-up of the dynamics is due to the strain field induced by the change in density at transition temperature. The transition temperatures obtained from PCI-DWS are found to be in excellent agreement with those inferred from complementary differential scanning calorimetry and X-ray scattering experiments, thereby validating PCI-DWS as a new, powerful tool for the characterization of phase transitions in complex soft matter. Finally, we demonstrate the unique possibilities afforded by space-resolved DWS by investigating the spatially heterogeneous response of poorly manufactured or composite chocolate samples.

We explore the glassy dynamics of soft colloids using microgels and charged particles interacting by steric and screened Coulomb interactions, respectively. In the supercooled regime, the structural relaxation time τα of both systems grows steeply with volume fraction, reminiscent of the behavior of colloidal hard spheres. Computer simulations confirm that the growth of τα on approaching the glass transition is independent of particle softness. By contrast, softness becomes relevant at very large packing fractions when the system falls out of equilibrium. In this nonequilibrium regime, τα depends surprisingly weakly on packing fraction, and time correlation functions exhibit a compressed exponential decay consistent with stress-driven relaxation. The transition to this novel regime coincides with the onset of an anomalous decrease in local order with increasing density typical of ultrasoft systems. We propose that these peculiar dynamics results from the combination of the nonequilibrium aging dynamics expected in the glassy state and the tendency of colloids interacting through soft potentials to refluidize at high packing fractions.

Power law rheology is of widespread occurrence in complex materials that are characterized by the presence of a very broad range of microstructural length and time scales. Although phenomenological models able to reproduce the observed rheological features exist, in general a well-established connection with the microscopic origin of this mechanical behavior is still missing. As a model system, this work focuses on a fractal colloidal gel. We thoroughly characterize the linear power law rheology of the sample and its age dependence. We show that at all sample ages and for a variety of rheological tests the gel linear viscoelasticity is very accurately described by a Fractional Maxwell (FM) model, characterized by a power law behavior. Thanks to a unique set-up that couples small-angle static and dynamic light scattering to rheological measurements, we demonstrate that the power law rheology observed in the linear regime originates from reversible non-affine rearrangements and discuss the possible relationship between the FM model and the microscopic structure of the gel.

Despite an abundant literature on epoxy-amine systems, a complete description of the curing kinetics in epoxy-phenol composites was still lacking. In this study, the curing kinetics of an epoxy-phenol composite relevant to microelectronics industry is probed by isothermal and non-isothermal differential scanning calorimetry. An isoconversional analysis of the data reveals a significant contribution of the diffusion of molecular species to the activation energy, at low temperature and high degrees of curing. A model-fitting of the kinetics is performed in two successive steps: high-temperatures data are fitted with Arrhenius law and nth order autocatalytic model (where the diffusion contribution is neglected), whereas low-temperature data are fitted using Rabinowitch and modified-Williams-Landel-Ferry models (considering a diffusion contribution related to the glass transition). The chemical and diffusion contributions to the rate constants are calculated at various temperatures, clarifying the kinetics regimes with precision. Finally, the kinetics regimes are summarized in an improved time-temperature-transformation diagram.

Contact-resonance atomic force microscopy (CR-AFM) is of great interest and very valuable for a deeper understanding of the mechanics of biological materials with moduli of at least a few GPa. However, sample surfaces can present a high topography range with significant slopes, where the local angle can be as large as ± 50°. The non-trivial correlation between surface slope and CR-frequency hinders a straightforward interpretation of CR-AFM indentation modulus measurements on such samples. We aim to demonstrate the significant influence of the surface slope on the CR-frequency that is caused by the local angle between sample surface and the AFM cantilever and present a practical method to correct the measurements. Based on existing analytical models of the effect of the AFM set-up's intrinsic cantilever tilt on CR-frequencies, we compute the non-linear variation of the first two (eigen)modes CR-frequency for a large range of surface angles. The computations are confirmed by CR-AFM experiments performed on a curved surface. Finally, the model is applied to directly correct contact modulus measurements on a durum wheat starch granule as an exemplary sample.

Recent experimental results using in particular small-angle scattering to characterize the self-assembly of mainly hard spherical nanoparticles into higher ordered structures ranging from fractal aggregates to ordered assemblies are reviewed. The crucial control of interparticle interactions is discussed, from chemical surface-modification, or the action of additives like depletion agents, to the generation of directional patches and the use of external fields. It is shown how the properties of interparticle interactions have been used to allow inducing and possibly controlling aggregation, opening the road to the generation of colloidal molecules or potentially metamaterials. In the last part, studies of the microstructure of polymer nanocomposites as an application of volume-spanning and stress-carrying aggregates are discussed.

Non-aqueous Taylor dispersion analysis (TDA) was used for the size-characterization of natural and synthetic polyisoprenes (4 × 103–2 × 106 g/mol molar mass). Not only the weight-average hydrodynamic radius (Rh), but also the probability distribution of the hydrodynamic radius, were both derived from the Taylorgrams by a simple integration of the elution profile and by a more sophisticated constrained regularized linear inversion of the Taylorgram, respectively. Results in terms of size characterization (hydrodynamic radii between 2 and 100 nm) were compared to size exclusion chromatography coupled to a refractive index-based mass detector. Multimodal size distributions were resolved by TDA for industrial and natural polyisoprenes, with the advantage over the chromatographic technique that, in TDA, there is no abnormal elution of microaggregates (hydrodynamic radii ∼ 40–50 nm). Considering the importance and the difficulty of characterizing polyisoprene microaggregates, TDA appears as a promising and simple technique for the characterization of synthetic and natural rubber.