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When silica-filled rubber compounds are deformed, structural modifications in the material's bulk lead to irreversible damage, the most significant of which is cavitation appearing within the interfaces of interconnected polymer and filler networks. This work introduces a new method to analyze cavitation in industrial-grade rubbers based on Ultra Small-Angle X-ray Scattering. This method employs a specially designed multi-sample stretching device for high-throughput measurements with statistical relevance. The proposed data reduction approach allows for early detection and quantification of cavitation while providing at the same time information on the hierarchical filler structures at length scales ranging from the primary particle size to large silica agglomerates over four orders of magnitude. To validate the method, the scattering of SSBR rubber compounds filled with highly dispersible silica at different ratios was measured under quasi-static strain. The strain was applied in incremental steps up to a maximum achievable elongation or breakage of the sample. From the measurements performed in multiple repetitions, it was found that the minimum strain necessary for cavity formation and the size evolution of the cavities with increasing strain are comparable between these samples. The sample with the highest polymer content showed the lowest rate of cavity formation and higher durability of silica structures. The structural stability of the compounds was determined by the evolution of the filler hierarchical structures, obtained by fitting data across the available strain range., Comment: 17 pages with 2 tables and 13 figures

Industrial and model polymer nanocomposites are often formulated with coating agents to improve polymer-nanoparticle (NP) compatibility. Here the localization of silane coating agents in styrene-butadiene nanocomposite is investigated through the segmental dynamics of the polymer matrix by broadband dielectric spectroscopy (BDS), allowing the detection of silanes in the matrix through their plasticization effect. This acceleration of dynamics was followed via the shift of $\tau$max of the $\alpha$-relaxation induced by the presence of coating agents of different molecular weight and quantity, for different amounts of incorporated colloidal silica NPs (R $\approx$ 12.5 nm, polydispersity 12%). Any noteworthy contribution of interfacial polymer layers on $\tau$max has been excluded by reference measurements with bare NPs. Our approach allowed quantifying the partition between the matrix and the NP interfaces, and was confirmed independently by calorimetry. As a control parameter, the silane grafting reaction could be activated or not, which was confirmed by the absence (resp. presence) of partitioning with the matrix. Our main result is that in the first steps of material formulation, before any grafting reaction, coating agents both cover the silica surface by adsorption and mix with the polymer matrix-in particular if the latter has chemical compatibility via its functional groups. Silane adsorption was found to be comparable to the grafted amount (1.1 nm-2), and does not increase further, confirming that the plateau of the adsorption isotherm is reached in industrial formulations. These results are hoped to contribute to a better understanding of the surface reactions taking place during complex formulation processes of nanocomposites, namely the exact amounts at stake, e.g., in industrial mixers. Final material properties are affected both through NP-matrix compatibility and plasticization of the latter by unreacted molecules. 2

Monte-Carlo simulations and small-angle x-ray scattering experiments were used to determine the phase diagram of aqueous dispersions of titratable nano-colloids with a moderate size polydispersity over a broad range of monovalent salt concentrations, 0.5 mM $\leq c_s \leq$ 50 mM and volume fractions, $\phi$. Under slow and progressive increase in $\phi$, the dispersions freeze into a face-centered-cubic (fcc) solid followed unexpectedly by the formation of a body centered cubic (bcc) phase before to melt in a glass forming liquid. The simulations are found to predict very well these observations. They suggest that the stabilization of the bcc solid at the expense of the fcc phase at high $\phi$ and $c_s$ results from the interaction (charge) polydispersity and vibrational entropy., Comment: 5 pages, 4 figures, Accepted in PRL

Colloidal gels, where nanoscale particles aggregate into an elastic yet fragile network, are at the heart of materials that combine specific optical, electrical and mechanical properties. Tailoring the viscoelastic features of colloidal gels in real-time thanks to an external stimulus currently appears as a major challenge in the design of "smart" soft materials. Here we introduce "rheo-acoustic" gels, a class of materials that are sensitive to ultrasonic vibrations. By using a combination of rheological and structural characterization, we evidence and quantify a strong softening in three widely different colloidal gels submitted to ultrasonic vibrations (with submicron amplitude and frequency 20-500 kHz). This softening is attributed to micron-sized cracks within the gel network that may or may not fully heal once vibrations are turned off depending on the acoustic intensity. Ultrasonic vibrations are further shown to dramatically decrease the gel yield stress and accelerate shear-induced fluidization. Ultrasound-assisted fluidization dynamics appear to be governed by an effective temperature that depends on the acoustic intensity. Our work opens the way to a full control of elastic and flow properties by ultrasonic vibrations as well as to future theoretical and numerical modeling of such rheo-acoustic gels., Comment: 21 pages, 14 figures

We report small-angle x-ray scattering (SAXS) experiments on aqueous dispersions of colloidal silica with a broad monomodal size distribution (polydispersity 18%, size 8 nm). Over a range of volume fractions the silica particles segregate to build first one, then two distinct sets of colloidal crystals. These dispersions thus demonstrate fractional crystallization and multiple-phase (bcc, Laves AB$_2$, liquid) coexistence. Their remarkable ability to build complex crystal structures from a polydisperse population originates from the intermediate-range nature of interparticle forces, and suggests routes for designing self-assembling colloidal crystals from the bottom-up., Comment: 5 pages, 3 figures and 2 tables + supplemental analysis (5 pages, 1 figure, 3 tables)

The structure of silica-latex nanocomposites of three matrix chain masses (20, 50, and 160 kg/mol of poly(ethyl methacrylate)) are studied using a SAXS/TEM approach, coupled via Monte Carlo simulations of scattering of fully polydisperse silica nanoparticle aggregates. At low silica concentrations (1 vol. %), the impact of the matrix chain mass on the structure is quantified in terms of the aggregation number distribution function, highest mass leading to individual dispersion, whereas the lower masses favor the formation of small aggregates. Both simulations for SAXS and TEM give compatible aggregate compacities around 10 vol. %, indicating that the construction algorithm for aggregates is realistic. Our results on structure are rationalized in terms of the critical collision time between nanoparticles due to diffusion in viscous matrices. At higher concentrations, aggregates overlap and form a percolated network, with a smaller and lighter mesh in the presence of high mass polymers. The linear rheology is investigated with oscillatory shear experiments. It shows a feature related to the silica structure at low frequencies, the amplitude of which can be described by two power laws separated by the percolation threshold of aggregates.

Aqueous colloidal dispersions of silica particles become anisotropic when they are dried through evaporation. This anisotropy is generated by a uniaxial strain of the liquid dispersions as they are compressed by the flow of water toward a solidification front. Part of the strain produced by the compression is relaxed, and part of it is stored and transferred to the solid. This stored elastic strain has consequences for the properties of the solid, where it may facilitate the growth of shear bands, and generate birefringence., Comment: 6 pages, 6 figures

We report on a joint experimental-theoretical study of collective diffusion in, and static shear viscosity of solutions of bovine serum albumin (BSA) proteins, focusing on the dependence on protein and salt concentration. Data obtained from dynamic light scattering and rheometric measurements are compared to theoretical calculations based on an analytically treatable spheroid model of BSA with isotropic screened Coulomb plus hard-sphere interactions. The only input to the dynamics calculations is the static structure factor obtained from a consistent theoretical fit to a concentration series of small-angle X-ray scattering (SAXS) data. This fit is based on an integral equation scheme that combines high accuracy with low computational cost. All experimentally probed dynamic and static properties are reproduced theoretically with an at least semi-quantitative accuracy. For lower protein concentration and low salinity, both theory and experiment show a maximum in the reduced viscosity, caused by the electrostatic repulsion of proteins. The validity range of a generalized Stokes-Einstein (GSE) relation connecting viscosity, collective diffusion coefficient, and osmotic compressibility, proposed by Kholodenko and Douglas [PRE 51, 1081 (1995)] is examined. Significant violation of the GSE relation is found, both in experimental data and in theoretical models, in semi-dilute systems at physiological salinity, and under low-salt conditions for arbitrary protein concentrations.

The relevance of anisotropic interactions in colloidal systems has recently emerged in the context of the rational design of new soft materials. Patchy colloids of different shapes, patterns and functionalities are considered the new building blocks of a bottom-up approach toward the realization of selfassembled bulk materials with predefined properties. The ability to tune the interaction anisotropy will make it possible to recreate molecular structures at the nano- and microscales (a case with tremendous technological applications), as well as to generate new unconventional phases, both ordered and disordered. Recent theoretical studies suggest that the phase diagram of patchy colloids can be significantly altered by limiting the particle coordination number (that is, valence). New concepts such as empty liquids-liquid states with vanishing density-and equilibrium gels arrested networks of bonded particles, which do not require an underlying phase separation to form-have been formulated. Yet no experimental evidence of these predictions has been provided. Here we report the first observation of empty liquids and equilibrium gels in a complex colloidal clay, and support the experimental findings with numerical simulations., Comment: 7 pages, 3 figures