The depolarized Raman spectra can be used as a probe to reveal the presence of non-network formers in oxide glasses. Two spectral responses involving the cations are observed below 400 cm−1 in more than 30 compositions of binary and ternary aluminosilicates. One of the two bands arises solely from cations close to non-bridging oxygen providing thereby a simple test for qualifying the polymerization state of the glass. The second feature involves all cations whatever their role in the glass and is found to be twofold: one contribution arises from cations charge compensating (AlO4)− tetrahedra and the other one from network modifier cations. These results confirm the net vibrational contrast of cations depending on their structural surrounding.

The segmental dynamics of styrene-butadiene nanocomposites with embedded silica nanoparticles (NPs, ca. 20%v) has been studied by broadband dielectric (BDS) and neutron spin-echo spectroscopy (NSE). It is shown by BDS that overlapping contributions only allow to conclude on a range of distributions of relaxation times in simplified industrial nanocomposites formed with highly polydisperse NPs. For comparison, structurally similar but less aggregated colloidal nanocomposites have a well-defined distribution of relaxation times due to the reduced influence of interfacial polarization processes. This distribution is widened with respect to the neat polymer, without change in the position of the maximum, and at most a small slowing down visible in the average time. We then demonstrate that incoherent NSE can be used to resolve small modifications of segmental dynamics of the industrial samples. By carefully choosing the q-vector of the measurement, experiments with fully hydrogenated polymer give access to the self-dynamics of the polymer in the presence of silica on the scale of approximately 1 nm. Our high resolution measurements show that the segmental motion is slightly but systematically slowed down also by the presence of the industrial filler NPs.

Despite the wide use of polymer nanocomposites (PNCs)in various applications, our understanding of the microscopic parameterscontrolling their macroscopic properties remains limited. In this study, weexamine the dielectric strength of segmental dynamics, ΔεIL(T) in theinterfacial polymer layer surrounding the nanoparticles in PNCs. Thepresented analysis reveals a significant drop in ΔεIL(T) and its anomaloustemperature dependence in the polymer layer adsorbed to nanoparticles.The drop in ΔεIL(T) was observed in all samples regardless of whethersegmental relaxation time in the interfacial layer was slower or faster thanin the bulk polymer, excluding interpretation of the “dead” layer. Weascribe the observed decrease in the dielectric strength to the restrictedamplitude of segmental relaxation in the interfacial/adsorbed layer. Ourresults provide a new perspective on discussion of dynamics in theinterfacial layer in PNCs and thin polymer films, demonstrating that notonly segmental relaxation time but also its amplitude can be strongly affected by the interface.

The addition of hard fillers to a polymer matrix is a well-known process for achieving mechanical reinforcement. With a decrease in the size of the fillers, the contribution from polymer–particle nanometer-sized interfaces becomes significant, and these interfaces affect the mechanical performance of polymer nanocomposites (PNCs) beyond the limits established for conventional composites. However, the molecular mechanisms underlying the improvement in the mechanical performance of glassy PNCs remain unresolved, necessitating a deeper understanding of the structure–property relationships in these intrinsically heterogeneous systems. In this effort, by using Brillouin light scattering (BLS) and dynamic mechanical analysis (DMA), we demonstrated that adding shorter chains to a PNC prepared with high molecular weight polymers significantly improved the mechanical properties of the PNC in the glassy state. The strongest enhancement of mechanical properties occurred at an optimum concentration of short chains. This is in contrast to the behavior of the glass transition temperature of PNCs which shows a monotonic decrease with an increase in the concentration of shorter chains. Using experimental data and coarse-grained molecular dynamics (MD) simulations, we have identified the molecular mechanism leading to the observed nonmonotonic changes in mechanical reinforcement. This mechanism includes changes in the nanoscale organization at the interface combined with chain stretching amplified by the addition of the short chains. Overall, our approach paves a simple and cost-effective pathway to fabricating glassy PNCs with significantly improved mechanical properties that will fill various practical needs.

We propose a method relying on structural measurements by small-angle scattering to quantitatively follow aggregation of nanoparticles (NPs) in concentrated colloidal assemblies or suspensions up to percolation, regardless of complex structure factors arising due to interactions. As experimental model system, the dispersion of silica NPs in a styrene-butadiene matrix has been analyzed by small-angle X-ray scattering and transmission electron microscopy (TEM), as a function of particle concentration. A reverse Monte Carlo analysis applied to the NP scattering compared favorably with TEM. By combining it with an aggregate recognition algorithm, series of representative real space structures and aggregation number distribution functions have been determined up to high concentrations, taking into account particle polydispersity. Our analysis demonstrates that the formation of large percolating aggregates on the scale of the simulation box (of linear dimension 1/qmin, here micron-sized) can be mapped onto the macroscopic percolation characterized by rheology. Our method is thus capable of determining aggregate structure in dense NP systems with strong – possibly unknown – interactions visible in scattering. It is hoped to be useful in many other colloidal systems, beyond the case of polymer nanocomposites exemplarily studied here.