Ref HAL: hal-01896690_v1
DOI: 10.1039/c8sm00911b
WoS: WOS:000442269000021
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1 Citation
Résumé:

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.

PMID 29758608
DOI: 10.1103/PhysRevE.97.040601
WoS: WOS:000429636700001
30 Citations
Résumé:

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.

Ref HAL: hal-01889803_v1
Ref Arxiv: 1802.03820
DOI: 10.1122/1.5025622
WoS: 000449684700010
Ref. & Cit.: NASA ADS
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10 Citations
Résumé:

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.

Commentaires: . Réf Journal: Journal of Rheology, 62, 1429-1441 (2018)

Ref HAL: hal-01881804_v1
DOI: 10.1016/j.tca.2018.07.019
WoS: 000444663600024
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9 Citations
Résumé:

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.

Ref HAL: hal-01876996_v1
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Polymer nanocomposites (PNCs) are made by dispersion of hard fillers in a polymer matrix, where the fillers are usually added to enhance mechanical properties. Thus, such materials attract industrial interest and their investigation is essential for the improvement of their performances.The present study concerns nanocomposites obtained using hydrophilic silica nanoparticles (NPs) dispersed in a soft polymer matrix of styrene-butadiene, commonly used in car tire manufacturing. The mechanical performances of such PNCs are strongly related to the structural properties: the dispersion state of silica particles in the polymer melt is governed by the mixing protocols (e.g., solid phase mixing or solvent casting) and thermodynamics of the system (i.e., particle miscibility) which influence the filler-filler and the filler-polymer interactions.We developed a new model nanocomposite system, equivalent to a simplified industrial one, made by solvent casting technique using colloidal silica NPs. In such model PNCs, the dispersion of colloidal silica is tuned via the surface-modification of silica particles by grafting hydrophobic molecules, i.e., silane coating agents, which promote the filler-polymer compatibility.To describe NP structure in solvents and after casting into polymer matrix, we propose a new method which combines Small Angle X-ray Scattering (SAXS), reverse Monte Carlo (RMC) and aggregate recognition (AR) analysis. This approach allows obtaining a detailed structural characterization of the silica NPs surface-modified with different silane grafting groups (i.e., tri-ethoxy, tri-methoxy or mono-methoxy silane). In particular, we show that silane molecules with trifunctional grafting functions may lead to the formation of polycondensed patches (i.e., reaction of lateral groups with neighboring molecules) on silica surface, favoring attractive interactions. Thus, the lowest aggregation is observed using mono-functionalized silane molecules where patches cannot form.Next, the SAXS-RMC-AR approach will be extended to investigate the structural properties of nanocomposite systems where silica NPs are surface-modified with silane molecules of various alkyl chain.

Ref HAL: hal-01876954_v1
WoS: WOS:000435537705630
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Résumé:

Tuning local nanoparticle arrangements and dynamical properties in polymer nanocomposites by grafting of small molecules

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