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.

The hysteretic softening at small dynamic strains (Payne effect) related to the rolling resistance and viscoelastic losses of tires was studied as a function of particle size, filler volume fraction, and temperature for carbon black (CB) reinforced uncrosslinked styrene-butadiene rubber (SBR) and a paste-like material composed of CB-filled paraffin oil. The low strain limit for dynamic storage modulus was found to be remarkably similar for CB-filled oil compared to CB-filled SBR. Small-angle X-ray scattering (SAXS) measurements on the simple composites and detailed data analysis confirmed that the aggregate structures and nature of filler branching/networking of carbon black were virtually identical within oil compared to the high molecular weight polymer matrix. The combined dynamic rheology and SAXS results provide clear evidence that the deformation-induced breaking (unjamming) of the filler network – characterized by filler-filler contacts that are percolated throughout the material – is the main cause for the Payne effect. However, the polymer matrix does play a secondary role as demonstrated by a reduction in Payne effect magnitude with increasing temperature for the CB-reinforced rubber, which was not observed to a significant extent for the oil-CB system.

This paper presents an efficient way to measure the curing kinetics and gel point, αgel, in epoxy resins from one single experiment. The epoxy curing reaction is herein monitored using in situ and time-resolved near-infrared absorption spectroscopy (NIR). The curing profiles over different isothermal conditions are in good agreement with DSC. Furthermore, the increase of the NIR absorption bands of aromatic rings (unreactive throughout curing) probe the cure shrinkage, as more and more aromatic rings are localized within the fixed sample volume. Therefore, the gel point is determined using the onset of the aromatic absorption increase. The results are in good agreement with the theoretical gel point, as well as DMA results. This innovative approach enables gelation measurements on epoxy neat resins and film composites with an easy-to-perform, accurate, robust, and versatile method.

Polymerized ionic liquids (PolyILs) are promising materials for applications in electrochemical devices spanning from fuel cells to capacitors and batteries. In principle, PolyILs have a competitive advantage over traditional electrolytes in being single ion conductors and thus enabling a transference number close to unity. Despite this perceived advantage, surprisingly low room temperature ionic conductivities measured in the lab raise an important fundamental question: how does the molecular structure mediate conductivity? In this work, wide-angle X-ray scattering (WAXS), vibrational sum frequency generation (vSFG), and density functional theory (DFT) calculations were used to study the bulk and interfacial structure of PolyILs, while broad band dielectric spectroscopy (BDS) was used to probe corresponding dynamics and conductive properties for a series of the PolyIL samples with tunable chemistries and structures. Our results reveal that the size of the mobile anions has a tremendous impact on chain packing in PolyILs that wasn’t addressed previously. Larger mobile ions tend to create a well-packed structure, while smaller ions frustrate chain packing. The magnitude of these changes and level of structural heterogeneity are shown to depend on the chemical functionality and flexibility of studied PolyILs. Furthermore, these experimental and computational results provide new insight into the correlation between conductivity and structure in PolyILs, suggesting that structural heterogeneity helps to reduce the activation energy for ionic conductivity in the glassy state.

A combined small-angle scattering of neutrons (SANS) and X-rays (SAXS) study of thestructure of polymer layers pre-adsorbed on silica nanoparticles (NP) which are subsequentlyincorporated into polymer nanocomposites (PNCs) is presented. Pre-adsorbed chains are foundto promote ideal dispersion, before desorption in the late stages of nanocomposite formation.The microstructure of the interfacial polymer layer is characterized by detailed modeling of X-rayand neutron scattering. Only in ideally well-dispersed systems a static interfacial layer ofreduced polymer density over a thickness of ca. 2 nm is evidenced based on the analysis with aform-free density profile optimized using reverse Monte Carlo simulations. This interfacialgradient layer is found to be independent of the thickness and mass of the initially adsorbedpolymer, but appears to be generated by out-of-equilibrium packing and folding of the preadsorbedlayer. The impact of annealing is investigated to study the approach of equilibrium,showing that initially ideally well-dispersed systems adopt a repulsive hard-sphere structure,while the static interfacial layer disappears.In parallel, SANS and the use of zero average contrast conditions allow the measurement ofchain conformation in the PNCs with and without pre-adsorption. Surprisingly, we evidenced thespontaneous formation of thermally-stable adsorbed layers in PNCs containing matrix chains ofdifferent mass, whereas a symmetric matrix of identical chain masses does not show this effect.This study contributes thus to the fundamental understanding of the interplay betweeneffects which are decisive for macroscopic material properties: polymer-mediated interparticleinteractions, and particle interfacial effects on surrounding polymer.

The dynamic and static properties of the interfacial region between polymer and nanoparticles have wide-ranging consequences on performances of nanomaterials. The thickness and density of the static layer are particularly difficult to assess experimentally due to superimposing nanoparticle interactions. Here, we tune the dispersion of silica nanoparticles in nanocomposites by pre-adsorption of polymer layers in the precursor solutions, and by varying the molecular weight of the matrix chains. Nanocomposite structures ranging from ideal dispersion to repulsive order or various degrees of aggregation are generated and observed by small-angle scattering. Pre-adsorbed chains are found to promote ideal dispersion, before desorption in the late stages of nanocomposite formation. The microstructure of the interfacial polymer layer is characterized by detailed modeling of X-ray and neutron scattering. Only in ideally well-dispersed systems a static interfacial layer of reduced polymer density over a thickness of ca. 2 nm is evidenced based on the analysis with a form-free density profile optimized using numerical simulations. This interfacial gradient layer is found to be independent of the thickness of the initially adsorbed polymer, but appears to be generated by out-of-equilibrium packing and folding of the pre-adsorbed layer. The impact of annealing is investigated to study the approach of equilibrium, showing that initially ideally well-dispersed systems adopt a repulsive hard-sphere structure, while the static interfacial layer disappears. This study thus promotes the fundamental understanding of the interplay between effects which are decisive for macroscopic material properties: polymer-mediated interparticle interactions, and particle interfacial effects on surrounding polymer.