The addition of water to native cellulose/1-ethyl-3methylimidazolium acetate solutions catalyzes the formation of gels, where polymer chain-chain intermolecular associations act as cross-links. However, the relationship between water content (Wc), polymer concentration (Cp), and gel strength is still missing. This study provides the fundamentals to design water-induced gels. First, the sol-gel transition occurs exclusively in entangled solutions, while in unentangled ones, intramolecular associations hamper interchain cross-linking, preventing the gel formation. In entangled systems, the addition of water has a dual impact: at low water concentrations, the gel modulus is water-independent and controlled by entanglements. As water increases, more cross-links per chain than entanglements emerge, causing the modulus of the gel to scale as Gp ∼ C p^2 Wc^3.0±0.2. Immersing the solutions in water yields hydrogels with noncrystalline, aggregate-rich structures. Such water-ionic liquid exchange is examined via Raman, FTIR, and WAXS. Our findings provide avenues for designing biogels with desired rheological properties.

Monodispersed hollow periodic mesoporous organosilica nanoparticles (HPMO-NPs) with a controlled core cavity and a periodic mesoporous organosilica (PMO) shell are successfully synthesized using a dual templating approach. The PMO shell synthesized by the sol–gel route exhibits a hybrid organic-inorganic framework based on phenylene bridges. The HPMO spherical nanoparticles with a diameter above 500 nm were characterized using a multiscale approach through TEM, BET, SAXS, and FT-IR. They are shown to offer an open periodic mesoporosity, a hollow cavity with a size tailored by thediameter of the core template, and finally, a high surface area (833 m 2 · g−1 ). In addition, we demonstrate that, through the same approach, the size of these hollow spherical nanoparticles can be tuned. Indeed, sub-50-nm hollow nanoparticles with mesoporous shells have also been obtained. The differences observed in the textural properties of these two sizes of hollow mesoporous nano-objects are discussed.

Fundamental understanding of macroscopic properties of polymer nanocomposites (PNCs) remains difficult due to the complex interplay of microscopic dynamics and structure, namely interfacial layer relaxations and three-dimensional nanoparticle arrangements. The effect of surface modification by alkyl methoxysilanes at different grafting densities has been studied in PNCs made of poly(2-vinylpyridine) and spherical 20 nm silica nanoparticles (NPs). The segmental dynamics has been probed by broadband dielectric spectroscopy, and the filler structure by small-angle X-ray scattering and reverse Monte Carlo simulations. By combining the particle configurations with the interfacial layer properties, it is shown how surface modification tunes the attractive polymer-particle interactions: bare NPs slow down the polymer interfacial layer dynamics over a thickness of ca. 5 nm, while grafting screens these interactions. Our analysis of interparticle spacing and segmental dynamics provides unprecedented insight into the effect of surface modification on the main characteristics of PNCs: particle interactions and polymer interfacial layers.

Both the dispersion state of nanoparticles (NPs) within polymer nanocomposites (PNCs) and the dynamical state of the polymer altered by the presence of the NP/polymer interfaces have a strong impact on the macroscopic properties of PNCs. In particular, mechanical properties are strongly affected by percolation of hard phases, which may be NP networks, dynamically modified polymer regions, or combinations of both. In this article, the impact on dispersion and dynamics of surface modification of the NPs by short monomethoxysilanes with eight carbons in the alkyl part (C8) is studied. As a function of grafting density and particle content, polymer dynamics is followed by broadband dielectric spectroscopy and analyzed by an interfacial layer model, whereas the particle dispersion is investigated by small-angle X-ray scattering and analyzed by reverse Monte Carlo simulations. NP dispersions are found to be destabilized only at the highest grafting. The interfacial layer formalism allows the clear identification of the volume fraction of interfacial polymer, with its characteristic time. The strongest dynamical slow-down in the polymer is found for unmodified NPs, while grafting weakens this effect progressively. The combination of all three techniques enables a unique measurement of the true thickness of the interfacial layer, which is ca. 5 nm. Finally, the comparison between longer (C18) and shorter (C8) grafts provides unprecedented insight into the efficacy and tunability of surface modification. It is shown that C8-grafting allows for a more progressive tuning, which goes beyond a pure mass effect.

So as to investigate structure-activity relationships in hydrogen bonded liquid crystals, a new short-chained (7 carbon atoms) fluorinated hydrogen-bonded liquid crystal 4-heptyloxy-2-fluorobenzoic acid, 7OBAF, is prepared. Differential scanning calorimetry, polarized optical microscopy and X-ray diffraction disclose a phase sequence as two crystalline, a nematic and the isotropic phases. Dielectric spectroscopy of the nematic phase in the frequency range of 1 Hz–6 MHz reveals a low frequency mode ascribed to ferroelectric clusters. A high polarization is induced by an external electric field, in agreement with results of dielectric measurements. Such polarization increases as the alkyl chain length is shorter. Results of DFT calculations using the Maier–Meier relationship are consistent with the dielectric measurements; they reveal the parallel molecular distribution and provide the dipole moment, polarization anisotropy, birefringence and dielectric anisotropy. Intermolecular hydrogen bonds linking the fluorine substituent and the aromatic hydrogen atoms are also disclosed.

This work focuses on the temperature-dependent structural and rheological characterization of polystyrene-b-poly(n-butyl acrylate)-b-polystyrene triblock copolymers (PS-b-PnBA-b-PS) in the melt and, in particular, on their ability to show a lower disorder-to-order temperature (LDOT). To this aim, copolymers of varying block lengths, but keeping the PnBA block as a major component, were synthesized. Smallangle x-ray scattering revealed that the copolymers with short PS blocks (∼10 kg/mol) approach an LDOT but do not cross it. At room temperature, these copolymers exhibit higher moduli compared to a PnBA homopolymer due to the reinforcing effect of the PS but are flowing at temperatures above the glass transition of the PS. Increasing the PS and PnBA block length, to keep the same PS fraction, induces more profound changes in the structural and viscoelastic behaviors. Such a copolymer crosses the LDOT, leading to a microphase-separated and ordered state at high temperature. Contrary to the copolymers with short PS blocks, the flow regime was not reached, even at temperatures well above the glass transition of the PS. Instead, a low-frequency plateau was observed in rheology, showing the increased lifetime of the microphase-separated PS domains. ABA triblock copolymers exhibiting an LDOT behavior could, thus, be of interest for the design of thermoplastic elastomers or pressure-sensitive adhesives that can resist the flow at high temperatures