Herein, we demonstrate that tuning of structural parameters and material chemistry enables control of the permeability and selectivity of gases (CO2, He, and CH4) in membranes based on poly(butyl methacrylate)-grafted nanoparticles (PGNs). Our data show that the presence of nanoparticles and the overall dense packing of grafted chains noticeable in PGNs with low grafting density have an adverse effect on the diffusivity of gases. This effect is compensated by an improvement in the solubility of CO2 gas promoted by the silica nanoparticle surface, yielding a substantial improvement in the permeability of CO2 versus CH4. In membranes with high grafting density, changes in the structural arrangements and alterations in the membrane porosity, evident from small-angle X-ray scattering and positron annihilation lifetime spectroscopy, positively influence the permeability of He and CO2 gases. In contrast, CH4 permeability in the same membranes is significantly suppressed, suggesting the formation of a unique, highly selective environment for gas separation. As a result, an improvement of up to 50% in selectivity for gas pairs containing large CH4 molecules is observed. Our studies provide fundamental insights into the role that structural parameters play in gas transport through polymer membranes, laying a foundation for the rational design of membranes with improved permeability and selectivity.

Using x-ray tomography, we experimentally investigate granular packings subject to mechanical tapping for three types of beads with different friction coefficients. We validate the Edwards volume ensemble in these three-dimensional granular systems and establish a granular version of thermodynamic zeroth law. Within the Edwards framework, we also explicitly clarify how friction influences granular statistical mechanics by modifying the density of states, which allows us to determine the entropy as a function of packing fraction and friction. Additionally, we obtain a granular jamming phase diagram based on geometric coordination number and packing fraction.

The liquid mixing process is an advantageous production method which has recently gained industrial interest for elaborating composites based on natural rubber (NR) and filler nanoparticles (NPs). Understanding how the relevant components such as polymer, fillers, as well as proteins and lipids coming from NR organize along the fabrication process is of importance for modulating material properties. Here, we successfully employed a combination of nano-imaging techniques to unravel the structure and evolution of hetero-aggregates formed by colloidal destabilization of a model NR latex - silica NPs liquid mixing process. First, field emission scanning electron microscopy (FESEM) was used to investigate the structures, from the early stage of contact between the particles until the formation of a composite. Results highlight an interaction in the liquid state between NR globules contained within the latex and silica NPs, hindering coalescence among globules. The latter can be achieved by applying shear in suspension or by solvent evaporation obtaining a dried composite. Atomic force microscopy coupled to infrared spectroscopy (AFM-IR) was employed to probe the in-depth nanoscopic distribution of silica NPs revealing a restricted mobility of the NPs during evaporation. Ultimately, the spatial distribution of proteins and lipids of NR, with respect to silica NPs, was investigated using dual color fluorescence images acquired with direct stochastic optical reconstruction microscopy (d-STORM) in a correlative light electron microscopy (CLEM) approach. The presence of silica NPs is found to influence the distribution of proteins and lipids in the composite; biomolecules form clusters of ~200 nm, which are partially colocalized with silica, highlighting an interaction between them. Our work provides comprehensive structural understanding of a model system undergoing liquid mixing, unlocking the potential of combining high-resolution imaging techniques to elucidate the structure of materials for tire applications.

Rubber-based nanocomposites prepared by solid-phase mixing with precipitated silica nanoparticlesare typically strongly aggregated systems with different levels of spatial organization. The strategy thatwe developed several years ago to investigate such systems is based on the study of simplifiedindustrial samples with ingredients limited to a strict minimum. On the scale of a micrometricsimulation box, tens of thousands of nanoparticles are embedded in the matrix, and their dispersionstrongly affects the mechanical properties of the material – and which is reflected in the scatteredintensity. A statistical method based on a reverse Monte Carlo solution of this many-parameterproblem will be presented, showing that some key features like percolation can be described. [1]Another key feature of rubber nanocomposites refers to the influence of the filler surfaces on thepolymer dynamics, and some recent progress – including incoherent neutron spin-echo measurements– will be discussed. [2] Such results may be confronted to dielectric spectroscopy measurements whichin some cases are not conclusive due the impossibility to correctly resolve the α-relaxation in presenceof strong interfacial polarization processes. An original application of dielectric spectroscopy with asurprising measurement of the adsorption isotherm of coating agents onto silica buried in the polymermatrix will also be discussed. [3][1] Musino D, Genix A-C, Chauveau E, Bizien T, Oberdisse J, Nanoscale 2020, 12:3907.[2] Musino D, Oberdisse J, Farago B, Alegria A, Genix A-C, ACS Macro Letters 2020, 9:910.[3] Musino D, Oberdisse J, Sztucki M, Alegria A, Genix A-C, Macromolecules 2020, 53:8083.

Polymerized ionic liquids (PolyILs) are an emerging class of polymer electrolytes which offer solutions to many problems in current battery technology. They combine the attractive features of ionic liquids with the mechanical strength of polymeric materials. However, a major obstacle in use of dry PolyILs is their low ionic conductivity at ambient temperature, which remains below the level required for many applications (ca. 10-3 S/cm). In this context, it has been shown that a significant enhancement of the ionic conductivity can be obtained by decoupling the ion motion from the segmental dynamics in polymers. We will review recent results obtained in this field using broadband dielectric spectroscopy, and discuss the microscopic parameters controlling ionic conductivity in PolyILs below Tg [1]. In particular, our detailed study of imidazolium-based PolyILs helped to unravel the interplay between nanostructure and ion conduction mechanism [2]. We also report first quasi-elastic neutron scattering experiments in these polymers suggesting the role of fast dynamics in assisting ion transport in the glassy state [3].[1] V. Bocharova and A.P. Sokolov, Macromolecules 2020, 53, 4141.[2] B. Doughty, A.C. Genix, I. Popov, B. Li, S. Zhao, T. Saito, D. Lutterman, R. Sacci, B.G. Sumpter, Z. Wojnarowska, V. Bocharova, Phys. Chem. Chem. Phys. 2019, 21, 14775.[3] V. Bocharova, A.C. Genix, A. Kisliuk, G. Sala, N.C. Osti, E. Mamontov, A. P. Sokolov, J. Phys. Chem. B 2020, 124, 10539.

The development of smart nanomaterials has attracted great attention in several fields like nanoscience, materials science,engineering and nanotechnology due to their unique response to external stimuli. Many of them are based on polymers thatcan exhibit great shape-changes when submitted to environmental modifications. Poly(N-isopropylacrylamide), PNIPAM, is sucha thermo-responsive polymer. It is water soluble at room temperature, forming gels by cross-linking but undergoes a reversiblecoil-to-globule volume phase transition (VPT) at a lower critical solution temperature (LCST) close to 32 °C due to thedehydration and subsequent collapse of its chains into compact globules.
Hybrid nanocomposite microgels associating PNIPAM and gold nanoparticles (GNP) have been designed in order to takeadvantage of the outstanding plasmonic and photo-thermal properties of GNP to promote the volume phase transition of themicrogels through an efficient photo-thermal conversion. With their strong diameter-dependent optical absorption in the nearinfrared (NIR) and their large surface area favoring photo-thermal transfer, semiconducting SWNT (s-SWNT) are goodcandidates for photo-thermal conversion in the NIR and may therefore be used to prepare multi-responsive hybrid microgels(Figure 1). However, to the best of our knowledge, no thorough studies of such nanomaterials have been reported so far.
Here we report the preparation of smart SWNT/PNIPAM nanocomposites through non-covalent functionalization techniques.These SWNT/PNIPAM hybrid microgels are stable in water and show a VPT, which can be promoted either by direct heating orby excitation of the resonant absorption of s-SWNT in the near infrared. Furthermore, the photoluminescence (PL) signal of s-SWNT is modulated at the phase transition and therefore, the PL signal can be used to monitor the VPT. This is illustrated inFigure 2, showing coupled Raman/PL measurements below and above the LCST, where a redshift of the PL bands is observedwhen crossing the LCST while the Raman signatures remain essentially the same.

Temperature is one of the basic parameters often required to characterize a system. A great demand has arisen for localmeasurements, especially in liquids or complex biological environments. Various approaches have been proposed to study thetemperature at the nano-scale level. Some of them are based on the spectroscopic properties of carbon nanotubes (CNT) usedas sensors.
Raman spectroscopy is indeed a powerful technique to identify single-walled carbon nanotubes (SWNT) and to study theirstructure, defects and electronic properties through the measurement of specific Raman signatures (RBM, D, G and 2D bands).On the other hand, individual SWNT or small bundles emit light in the near infrared and the photoluminescence (PL) spectra isvery sensitive to the quality of the dispersion and the dielectric environment of the nanotubes. In particular, when SWNT aredispersed in aqueous solutions, the PL energies are sensitive to the nature of the surfactants or polymers, to theirconcentration, and to the way they adsorb on/wrap around the nanotubes.
In this work we show that the PL/Raman spectra of SWNT dispersed with sodium dodecyl sulfate (SDS) is very sensitive to thetemperature (figure 1) in a large range of SDS concentrations. We discuss the influence of the chiral angle of the SWNT onthese PL changes, and the origin of the changes in terms of SDS reorganization at the surface of the nanotubes. Similarchanges are obtained with increasing laser power (figure 2), showing the local heating of the nanotubes. These results pavethe way for the development of SWNT-based nano-thermometers.