Polymer nanocomposites are mixtures of nanoparticles and polymer chains, where the filler particles are usually added to enhance mechanical properties, e.g. of car tire materials. Performance depends to a great extent on the structure of the filler, i.e. its dispersion state in the polymer matrix, which itself depends on mixing protocols, but also on the thermodynamics of the system. The latter can be tuned by performing either chemical surface modifications of the nanoparticles, or by playing with the mass and/or grafting properties of the polymer chains. Some straightforward ways to obtain information from small-angle scattering on the filler structure of nanocomposites will be presented. In particular, we recently developed a quantitative analysis of the scattered intensity in the intermediate q range. It is based on the similarity in local structure between infinitely large homogeneous assemblies of hard spheres or moderately sticky hard spheres with any finite-sized nanoparticle assembly dominated by hard sphere interactions. This method provides direct information on the local volume fraction of particles. It will then be applied to the impact of small molecules on the silica structure in nanocomposites close to industrial applications.Finally, a second issue for the mechanical response of nanocomposites relates to the polymer dynamics, which may also be governed by the filler dispersion. We will present first quasi-elastic neutron scattering results showing the impact of the aggregation state on the segmental dynamics of the same samples by means of incoherent neutron spin-echo.

In this talk, some straightforward ways to obtain information from small-angle scattering on the structure of complex systems, in particular nanocomposites, will be given [1]. Polymer nanocomposites are mixtures of nanoparticles and polymer chains, where the particles – called filler – are usually added to enhance mechanical properties, like e.g. in car tires. Performances depend to a great extent on the structure of the filler, i.e. their dispersion state in the polymer matrix, which itself depends on mixing protocols, but also on the thermodynamics of the system. The latter can be tuned by performing either chemical surface modifications of the nanoparticles, or by playing with the mass and/or grafting properties of the polymer chains.We will present recent results on nanocomposites close to industrial applications, including what is probably one of the first quantitative analyses of such disordered structures by a combination of SAXS, TEM and numerical simulations [2]. The study led to the identification of a unique structure-determining parameter [3]. The generalization of the above-mentioned approach – the correlation hole analysis – will furthermore be illustrated by structural studies by small angle scattering of well-defined model systems, showing the influence of chain mass [4] or surface grafting of small molecules [5]. Finally, if the chairman is nice, a quick outlook on why contrast-matching with SANS in nanocomposites often fails will be proposed [6].[1] A.-C. Genix and J. Oberdisse, Structure and dynamics of polymer nanocomposites studied by X-ray and neutron scattering techniques. Current Opinion in Colloid & Interface Science, 2015, 20, 293-303.[2] G. P. Baeza, A. C. Genix, C. Degrandcourt, L. Petitjean, J. Gummel, M. Couty and J. Oberdisse, Macromolecules, 2013, 46, 317-329.[3] G. P. Baeza, A.-C. Genix, C. Degrandcourt, J. Gummel, A. Mujtaba, K. Saalwächter, T. Thurn-Albrecht, M. Couty, and J. Oberdisse, ACS MacroLetters, 2014, 3 (5), 448–452[4] A. Banc, A. C. Genix, M. Chirat, C. Dupas, S. Caillol, M. Sztucki and J. Oberdisse, Macromolecules, 2014, 47, 3219–3230.[5] C. Schmitt Pauly, A.-C. Genix, J. G. Alauzun, M. Sztucki, P. H. Mutin and J. Oberdisse, Polymer, in press.[6] A. Banc, A.-C. Genix, C. Dupas, M. Sztucki, R. Schweins, M.-S. Appavou, J. Oberdisse, Macromolecules 2015, 48, 6596−6605.

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.