Silica aerogels are known to be materials with exceptional characteristics, such as ultra-low density, high surface area, high porosity, high adsorption, and low-thermal conductivity. In addition, these unique properties are mainly related to their specific processing. Depending on the aerogel synthesis procedure, the aerogels texture can be tailored with meso and/or macroporosity. Fractal geometry has been observed and used to describe silica aerogels at nanoscales in certain conditions. In this review paper, we describe the fractal structure of silica aerogels that can develop depending on the synthesis conditions. X-ray and neutron scattering measurements allow to show that silica aerogels can exhibit a fractal structure over one or even more than two orders of magnitude in length. The fractal dimension does not depend directly on the material density but can vary with the synthesis conditions. It ranges typically between 1.6 and 2.4. The effect of the introduction of silica particles or of further thermal treatment or compression of the silica aerogels on their microstructure and their fractal characteristics is also resumed.

Understanding the complex structure of polymer blends filled with nanoparticles (NPs) is the key to designing their macroscopic properties. Here, the spatial distribution of hydrogenated (H) and deuterated (D) polymer chains asymmetric in mass is studied by small-angle neutron scattering. Depending on the chain mass, a qualitatively new large-scale organization of poly(vinyl acetate) chains beyond the random-phase approximation is evidenced in nanocomposites with attractive polymersilica interactions. The silica is found to systematically induce bulk segregation. Only with long H-chains, a strong scattering signature is observed in the q-range of the NP size: it is the sign of interfacial isotopic enrichment, i.e., of contrasted polymer shells close to the NP surface. A quantitative model describing both the bulk segregation and the interfacial gradient (over ca. 10-20 nm depending on the NP size) is developed, showing that both are of comparable strength. In all cases, NP surfaces trap the polymer blend in a non-equilibrium state, with preferential adsorption around NPs only if chain length and isotopic preference towards the surface combine their entropic and enthalpic driving forces. This structural evidence for interfacial polymer gradients will open the road to quantitative understanding of the dynamics of many-chain nanocomposite systems.

Poly[R-3-hydroxybutyrate-co-(R-3-hydroxyvalerate)] (PHBVs) are promising biopolymers, which could substitute petro-based plastics for packaging applications. To anticipate the behavior of PHBVs when transformed using conventional thermo-mechanical shaping processes, it is needed to better understand the effect of processing temperature on their crystallization behavior and final properties. The objectives of the present work were thus (1) to better understand the influence of the processing temperature on the PHBV macromolecular and crystalline structures, depending on its HV content, and (2) to define a processing window guaranteeing optimized mechanical properties of PHBV films. An innovative experimental strategy was proposed, enabling the study of melting and crystallization events, crystalline structure changes, and evolution of mechanical properties of PHBV according to processing temperature, using identical thermal cycles. A comprehensive dynamic monitoring of the studied PHBVs was achieved by coupling differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), step scan DSC (SDSC), observations of isothermal crystallization under polarized optical microscopy (POM), thermo-regulated wide angle X-ray analysis (WAXS), Nuclear Magnetic Resonance (NRM), and finally mechanical tests on PHBV films. The combination of these experiments revealed how inappropriate processing temperatures can result in irreversible changes in PHBVs’ macromolecular and crystalline structures, thermal behavior and mechanical performances. When increasing the HV content of the copolymer, adjusting the processing conditions according to these results revealed to be critical to match the functional properties targeted for a specific use.

Polymers with dynamic (transient) bonds, often called associating polymers, have been attracting significant attention in recent years due to their unique viscoelastic properties, self-healing ability, and recyclability. Nevertheless, understanding the mechanisms and the factors controlling their macroscopic properties remains limited due to the higher complexity introduced by the dynamic bonds. In this study, small-angle X-ray scattering (SAXS), broadband dielectric spectroscopy (BDS), and rheology were applied to unravel the structure and dynamics of telechelic associating polymers with different molecular weights. SAXS measurements revealed phase separation of the functional end groups with an average cluster size of ∼2–3 nm and the distance between clusters controlled by the chain length. Borrowing the interfacial layer model analysis of BDS data from the polymer nanocomposite field, we demonstrated the presence of an interfacial polymer layer with a thickness of ∼0.7–0.9 nm surrounding these clusters. Rheological measurements showed quantitatively that the presence of the interfacial layer significantly alters the viscoelastic behavior of these materials, indicating the crucial role of the interfacial layer in defining the macroscopic mechanical properties of the studied telechelic materials. The presented results emphasize that phase separation of the functional groups in associating polymers leads to very significant changes of the viscoelastic properties, opening a promising avenue in the design of novel functional materials.