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DOI: 10.1103/PhysRevX.6.041057
WoS: 000390287900001
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Interfacial tension between immiscible phases is a well-known phenomenon, which manifests itself in everyday life, from the shape of droplets and foam bubbles to the capillary rise of sap in plants or the locomotion of insects on a water surface. More than a century ago, Korteweg generalized this notion by arguing that stresses at the interface between two miscible fluids act transiently as an effective, nonequilibrium interfacial tension, before homogenization is eventually reached. In spite of its relevance in fields as diverse as geosciences, polymer physics, multiphase flows, and fluid removal, experiments and theoretical works on the interfacial tension of miscible systems are still scarce, and mostly restricted to molecular fluids. This leaves crucial questions unanswered, concerning the very existence of the effective interfacial tension, its stabilizing or destabilizing character, and its dependence on the fluid's composition and concentration gradients. We present an extensive set of measurements on miscible complex fluids that demonstrate the existence and the stabilizing character of the effective interfacial tension, unveil new regimes beyond Korteweg's predictions, and quantify its dependence on the nature of the fluids and the composition gradient at the interface. We introduce a simple yet general model that rationalizes nonequilibrium interfacial stresses to arbitrary mixtures, beyond Korteweg's small gradient regime, and show that the model captures remarkably well both our new measurements and literature data on molecular and polymer fluids. Finally, we briefly discuss the relevance of our model to a variety of interface-driven problems, from phase separation to fracture, which are not adequately captured by current approaches based on the assumption of small gradients.

Ref HAL: hal-01414119_v1
DOI: 10.1016/j.jfoodeng.2016.06.009
WoS: WOS:000382349300005
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Wheat flours are essential ingredients of daily food products like bread, cookies or pastries. Their quality depends on the milling process and mechanical strength of wheat grains. Although it is well known that the strength and rupture of grains are strongly controlled by the endosperm microstructure, the respective roles of the starch and polymer volume fractions and their adhesion are not yet fully understood. This typical biological microstructure can be modeled as a cemented granular material, where the two size populations of starch granules (large:A-type, small:B-type) are the particles, and the protein matrix, which partially fills the space between granules, plays the role of a cement. This structural model of wheat endosperm is used, together with mechanical characteristics of starch and proteins obtained by means of Atomic Force Microscopy (AFM) measurements, to simulate the mechanical behavior and breakage of wheat endosperm in milling process. We find that the porosity outweighs the effect of other parameters for the elastic modulus, which declines as a nearly linear function of porosity. We also show that the tensile strength is an increasing function of the amount and connectivity of starch granules with increasing concentration of stresses along chains of granules. This effect is more significant at low porosity where stress distribution is mainly controlled by the contact network between starch granules. This effect explains why the protein content is not fully correlated to vitreousness, and samples of similar protein content can be different in vitreosity. Finally, we find that the starch-granule adhesion strongly affects the tensile strength whereas the effect of starch volume fraction appears mainly at high interface adhesion, which is the case of hard type wheat grains.

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The structure of polymer nanocomposites has important consequences on final properties, like e.g.mechanical reinforcement. The structure of the hard filler phase is usually characterized by electronmicroscopy and small-angle X-ray scattering (SAXS), and we will review recent examples of fillerstructure in model and industrial nanocomposites. The chain conformation can only bemeasured by small-angle neutron scattering (SANS) with isotopic substitution. Over the past 15 years,considerable efforts have been dedicated to such measurements. Results appear to converge towardGaussian statistics of chains, unperturbed by the presence of filler NPs, and exceptions seem to be dueto system-dependent effects. In nearly all studies, however, unexplained pollution of the scatteringdata in the low-q range has been observed, in spite of careful contrast-matching.In this study, the conformation of polymer chains in silica-latex nanocomposites has been studiedunder zero-average contrast (ZAC) conditions using SANS. Samples have been prepared by dryingcolloidal suspensions of silica and polymer nanoparticles (NPs) for two different silica NPs (radius of5 and 15 nm) and two chain masses (17 and 100 kg/mol). By mixing appropriate amounts ofhydrogenated and deuterated polymer, chain scattering contrast is introduced, and in principle silicascattering is suppressed. However, the SANS scattering intensities displayed distinct deviations at lowangles. Comparison of the SANS and SAXS intensities proves that the measurement of chain structureby SANS is perturbed by unwanted silica contributions, i.e., the silica is ‘mysteriously’ visible. Aquantitative model rationalizing these contributions for the first time is proposed. It is based on astatistical H/D-mismatch in the local environment of the silica NPs. Such a mismatch leads to theexistence of a nanometer-thick polymer shell surrounding silica NPs, which carries H/D contrast andthereby produce an undesired scattering contribution. These shells are presumably maintained by thereduced mobility of polymer close to interfaces or attractive polymer-silica interactions. The effect ofunwanted filler scattering is NP size-dependent − it is pronounced only for smaller beads. This isprobably why ZAC turned out to be so difficult with polymer nanocomposites.

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Ref Arxiv: 1811.08158
DOI: 10.1016/j.eurpolymj.2016.08.028
WoS: 000390497100051
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11 Citations
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A large body of experimental work on the microstructure and dynamics of simplifiedindustrial nanocomposites made of disordered silica filler in a styrene-butadiene matrixby solid-phase mixing is regrouped and critically discussed in this feature article. Recentresults encompass systems with varying polymer mass, grafting functionality, and fillercontent. They have been obtained by simulation-based structural modelling of nanoparticleaggregate size and mass deduced from small-angle scattering and transmission electronmicroscopy. Our model has been validated by independent swelling experiments.Comparison of structurally-close nanocomposites of widely different chain mass led tothe identification of a unique structure-determining parameter, the grafting density, aswell as to a unified picture of aggregate formation mechanisms in complex nanocompositesduring mixing. In addition, low-field proton NMR allowed for the characterization ofdynamically slowed-down (‘glassy’) polymer layers, which were shown not to dominatethe rheological response, unlike the structural contribution. Finally, broadband dielectricspectroscopy was used in an innovative manner to identify filler percolation – also identifiedby rheology – via dynamics along filler surfaces.