The conformation of poly(ethyl methacrylate) chains in silica–latex nanocomposites has been studied under zero average contrast conditions (ZAC) using small-angle neutron scattering (SANS). Samples have been prepared by drying colloidal suspensions of silica and polymer nanoparticles (NPs) followed by thermal annealing, for two different silica NPs (radius of 5 and 15 nm) and two chain molecular weights (17 and 100 kg/mol). By appropriate mixing of hydrogenated and deuterated polymer, chain scattering contrast is introduced, and in principle silica scattering suppressed. The silica structure consisting mostly of small fractal aggregates is characterized by transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) on the same samples. The measurement of the chain structure by SANS, however, is perturbed by unwanted silica contributions, as often reported in the literature. Here, the contribution of contrast-matched silica is evidenced as a function of system parameters, namely chain mass, silica size, and volume fraction, and a model rationalizing these contributions for the first time is proposed. On the basis of a statistical analysis, a nanometer-thick polymer shell surrounding silica NPs is shown to create contrast, which is presumably maintained by the reduced mobility of polymer close to interfaces or attractive polymer–silica interactions. This shell is proven to be quantitatively important only for the smallest silica NPs. Finally, the pure polymer scattering can be isolated, and the polymer radius of gyration is found to be independent of filler content and NP size.

We propose a simple and original way to prepare surfactant-free SWNT/hydrosoluble polymer composites with high concentrations of individual SWNT. We first disperse single-walled carbon nanotubes (SWNT) in aqueous suspensions using bile salts (BS), and we mix them with a solution of hydrosoluble polymer, poly(vinylpyrrolidone) (PVP) or poly(vinyl alcohol) (PVA). We measure the yield using visible–NIR absorption spectroscopy, and we probe both the chemical environment of the nanotubes and the effectiveness of individualization from coupled Raman/photoluminescence studies. We evidence a direct exchange of BS molecules and PVA chains at the surface of SWNT. By contrast, no direct exchange is observed with PVP. On the other hand, we show that a simple dialysis process leads to the preparation of aqueous suspensions of SWNT covered by PVP or PVA with high yields and an effective individualization of the nanotubes.

The dynamics of colloidal particles at interfaces between two fluids plays a central role in microrheology, encapsulation, emulsification, biofilm formation, water remediation and the interface-driven assembly of materials. Common intuition corroborated by hydrodynamic theories, suggests that such dynamics is governed by a viscous force lower than that observed in the more viscous fluid. Here, we show experimentally that a particle straddling an air/water interface feels a large viscous drag that is unexpectedly larger than that measured in the bulk. We suggest that such a result arises from thermally activated fluctuations of the interface at the solid/air/liquid triple line and their coupling to the particle drag through the fluctuation–dissipation theorem. Our findings should inform approaches for improved control of the kinetically driven assembly of anisotropic particles with a large triple-line-length/particle-size ratio, and help to understand the formation and structure of such arrested materials.

The dynamics of polymer and filler in simplified industrial silica-styrene-butadiene nanocomposites (silica Zeosil 1165 MP, volume fraction 0 – 21%v) have been studied with broadband dielectric spectroscopy (BDS) and nuclear magnetic resonance (NMR). The fraction of graftable matrix chains was varied from 0 – 100%D3. The introduction of silica nanoparticles is shown to leave the segmental relaxation unaffected, an observation confirmed by the measurement of only a thin (some Angstroms thick) immobilized layer by NMR. The low-frequency measurements are resolved in two distinct dielectric Maxwell-Wagner-Sillars (MWS) processes of different behavior with respect to changes of large-scale silica structures induced by variations of filler fraction and grafting. In particular, depercolation of the silica filler at constant volume fraction with increasing grafting leaves the first MWS-process unaffected, but has direct consequences on rheological reinforcement, and decreases the strength of the second MWS by about a decade. This sensitivity to large-scale reorganizations together with a characterization of local polymer dynamics provides insight over many length- and time-scales into structure and dynamics of nanocomposites, and thus the physical origin of the reinforcement effect. 

We explore the influence of particle softness and internal structure on both the bulk andinterfacial rheological properties of colloidal suspensions. We probe bulk stresses byconventional rheology, by measuring the flow curves, shear stress versus strain rate, forsuspensions of soft, deformable microgel particles and suspensions of near hard-sphere-likesilica particles. A similar behaviour is seen for both kinds of particles in suspensions atconcentrations up to the random close packing volume fraction, in agreement with recenttheoretical predictions for sub-micron colloids. Transient interfacial stresses are measured byanalyzing the patterns formed by the interface between the suspensions and their solvent, dueto a generalized Saffman–Taylor hydrodynamic instability. At odds with the bulk behaviour,we find that microgels and hard particle suspensions exhibit vastly different interfacial stressproperties. We propose that this surprising behaviour results mainly from the difference inparticle internal structure (polymeric network for microgels versus compact solid for the silicaparticles), rather than softness alone.

Due to the existence of open channels, light could theoretically be transmitted through disorderedmedia with 100% efficiency. However, because of the large number of channels to be controlledor measured, this has been never observed experimentally. To avoid this difficulty we considerobservables easier to handle experimentally. By measuring the correlations of the field transmittedthrough a disordered medium, we were able to count the number of channels involved in transmissionand to compare this number with theory. For a sample of transmission 1=25, we get a number ofmodes about 15 times smaller than for free space propagation. This figure is in good agreementwith theoretical prediction.

It is often necessary to tailor nanoparticle (NP) interactions and their compatibility with a polymer matrix by grafting organic groups, but the commonly used silanization route offers little versatility, particularly in water. Herein, alumina-coated silica NPs in aqueous sols have been modified for the first time with low molecular-weight phosphonic acids (PAs) bearing organic groups of various hydrophobicities and charges: propyl, pentyl and octyl PAs, and two PAs bearing hydrophilic groups, either a neutraldiethylene glycol (DEPA) or a potentially charged carboxylic acid (CAPA) group. The interactions and aggregation in the sols have been investigated using zeta potential measurements, dynamic light scattering, transmission electron microscopy, and small-angle scattering methods. The surface modification has been studied using FTIR and 31P MAS NMR spectroscopies. Both high grafting density r and high hydrophobicity of the groups on the PAs induced aggregation, whereas suspensions of NPsgrafted by DEPA remained stable up to the highestr . Unexpectedly, CAPA-modified NPs showedaggregation even at low r, suggesting that the carboxylic end group was also grafted to the surface. Surface modification of aqueous sols with PAs allows thus for the grafting of a higher density and a wider variety of organic groups than organosilanes, offering an increased control of the interactions between NPs, which is of interest for designing waterborne nanocomposites.