The conformation and the dilatational properties of three non-ionic triblock PEO-PPO-PEO (where PEO is polyethyleneoxide and PPO is polypropyleneoxide) copolymers of different hydrophobicity and molecular weight were investigated at the water-hexane interface. The interfacial behavior of the copolymers was studied by combining dilatational rheology using the oscillating drop method and ellipsometry. From the dilatational rheology measurements the limiting elasticity values, E_0, of the Pluronics as function of surface pressure, PI, and adsorption time were obtained, i.e. E_0(t) and E-0(PI). Here, it is shown that E_0(t) depends on the number of PEO units and on the bulk concentration, showing maximum and minimum surface elasticity values which indicate conformational changes in the interfacial layer. Furthermore, in the framework of the polymer scaling law theory, conformational transitions were discussed in E_0 vs. PI plots. In a dilute regime (PI < 14 mN m−1) at the water-hexane interface, E_0 = 2PI fits well all the data, which indicates a two-dimensional "stretched chain" conformation. Increasing PI, two other interfacial transitions could take place. The different behavior of Pluronic copolymers could be also described by the local minima of E_0, which depends on the hydrophobicity of the copolymers. Conformational transitions observed by interfacial rheology were compared to ellipsometric data. Experimental results were discussed and explained on the basis of two- and three-dimensional copolymer structure taking into account that PPO chains could be partially immersed in hexane and water.

We study the crystallization of a colloidal model system in presence of secondary nanoparticles acting as impurities. Using confocal microscopy, we show that the nanoparticles segregate in the grain boundaries of the colloidal polycrystal. We demonstrate that the texture of the polycrystal can be tuned by varying independently the nanoparticle volume fraction and the crystallization rate, and quantify our findings using standard models for the nucleation and growth of crystalline materials. Remarkably, we find that the efficiency of the segregation of the nanoparticles in the grain-boundaries is determined solely by the typical size of the crystalline grains.

By means of quasielastic neutron scattering we have investigated the hydrogen dynamics in poly(alkylene oxide)s (PAOs) with different side-chain lengths at temperatures below as well as above the glass-transition. The combination of results from three different spectrometers (a time-of-flight and two backscattering instruments) has allowed covering almost 4 orders of magnitude in timefrom the ps to ns rangewith spatial resolution. The results evidence the simultaneous occurrence of vibrations and localized side-group motions at low temperatures and additional diffusive-like (segmental) dynamics at high temperatures. The localized processes of the side groups show (i) stretching of the scattering function, (ii) associated activation energies similar to those found for single and cooperative bond rotations of polyethylene, and (iii) spatial extents that increase with increasing temperature. Compared with poly(ethylene oxide) (PEO), the diffusive segmental process in PAOs presents (i) the same spectral shape, (ii) slower characteristic timesantiplasticization(iii) similar deviations from Gaussian behavior. For comparison, we also report on backscattering results on the side-group dynamics of poly(n-hexyl methacrylate) in the same temperature range, that show evidence for confinement effects. We suggest that the dynamic asymmetry in systems with intrinsic dynamic heterogeneities between constituent parts is the key ingredient leading to both plasticization and confinement effects.

Hybrid polyion complex (HPIC) micelles are nanoaggregates obtained by complexation of multivalent metal ions by double hydrophilic block copolymers (DHBC). Solutions of DHBC such as the poly(acrylic acid)-block-poly(acrylamide) (PAA-b-PAM) or poly(acrylic acid)-block-poly(2-hydroxyethylacrylate) (PAA-b-PHEA), constituted of an ionizable complexing block and a neutral stabilizing block, were mixed with solutions of metal ions, which are either monoatomic ions or metal polycations, such as Al3+, La3+, or Al-13(7+). The physicochemical properties of the HPIC micelles were investigated by small angle neutron scattering (SANS) and dynamic light scattering (DLS) as a function of the polymer block lengths and the nature of the cation. Mixtures of metal cations and asymmetric block copolymers with a complexing block smaller than the stabilizing block lead to the formation of stable colloidal HPIC micelles. The hydrodynamic radius of the HPIC micelles varies with the polymer molecular weight as M-0.6. In addition, the variation of R-h of the HPIC micelle is stronger when the complexing block length is increased than when the neutral block length is increased. R-h is highly sensitive to the polymer asymmetry degree (block weight ratio), and this is even more true when the polymer asymmetry degree goes down to values close to 3. SANS experiments reveal that HPIC micelles exhibit a well-defined core-corona nanostructure; the core is formed by the insoluble dense poly(acrylate)/metal cation complex, and the diffuse corona is constituted of swollen neutral polymer chains. The scattering curves were modeled by an analytical function of the form factor; the fitting parameters of the Pedersen's model provide information on the core size, the corona thickness, and the aggregation number of the micelles. For a given metal ion, the micelle core radius increases as the PAA block length. The radius of gyration of the micelle is very close to the value of the core radius, while it varies very weakly with the neutral block length. Nevertheless, the radius of gyration of the micelle is highly dependent on the asymmetry degree of the polymer: if the neutral block length increases in a large extent, the micelle radius of gyration decreases due to a decrease of the micelle aggregation number. The variation of the R-g/R-h ratio as a function of the polymer block lengths confirms the nanostructure associating a dense spherical core and a diffuse corona. Finally, the high stability of HPIC micelles with increasing concentration is the result of the nature of the coordination complex bonds in the micelle core.

We present a study on the structure and dynamics of poly(ethyl methacrylate) (PEMA), one of the polymers with shortest side-group in the poly(n-alkyl methacrylate)s (PnMAs) series. The contributions to the structure factor have been unveiled by combining T-dependent X-ray and neutron diffraction with polarization analysis on samples with different deuteration labelings, accessing thereby different partial structure factors of PEMA. We find clear hints for strong structural ordering with anticorrelated side-groups and main-chain locations, fitting thus in the general scenario of nanosegregation of main chains and side groups found in higher order PnMAs members. Backscattering measurements on a PEMA sample with deuterated side-group have revealed the dynamics of main-chain and α-methyl group hydrogens. The characterization of the rotations of the latter indicates highly disordered environments in the glassy state. Above the glass transition, the incoherent scattering function related to segmental relaxation shows stretching and clear deviations from Gaussian behavior in the accessed window. We also present results on the dynamic structure factor (collective dynamics) at the peaks characteristic (i) for the intermain-chain and interside-group-domain correlations and (ii) for the side-group/side-group atomic correlations within the domains. Viscosity dictates the temperature dependence in both cases, and also that of the dielectric spectroscopy results at high temperatures. However, the α-process followed by dielectric relaxation deviates from the rheological behavior when approaching the calorimetric glass-transition, indicating a strong influence of the faster side-group motions on the dynamics of the dielectric probes.

The evolution of the polymer structure during nanocomposite formation and annealing of silica-latex nanocomposites is studied using contrast-variation small angle neutron scattering. The experimental system is made of silica nanoparticles (Rsi ≈ 8 nm) and a mixture of purpose-synthesized hydrogenated and deuterated nanolatex (Rlatex ≈ 12.5 nm). The progressive disappearance of the latex beads by chain interdiffusion and release in the nanocomposites is analyzed quantitatively with a model for the scattered intensity of hairy latex beads and an RPA description of the free chains. In silica-free matrices and nanocomposites of low silica content (7%v), the annealing procedure over weeks at up to Tg + 85 K results in a molecular dispersion of chains, the radius of gyration of which is reported. At higher silica content (20%v), chain interdiffusion seems to be slowed down on time-scales of weeks, reaching a molecular dispersion only at the strongest annealing. Chain radii of gyration are found to be unaffected by the presence of the silica filler.

A set of 55 clarinet reeds is observed by holography, collecting 2 series of measurements made under 2 different moisture contents, from which the resonance frequencies of the 15 first modes are deduced. A statistical analysis of the results reveals good correlations, but also significant differences between both series. Within a given series, flexural modes are not strongly correlated. A Principal Component Analysis (PCA) shows that the measurements of each series can be described with 3 factors capturing more than $90\%$ of the variance: the first is linked with transverse modes, the second with flexural modes of high order and the third with the first flexural mode. A forth factor is necessary to take into account the individual sensitivity to moisture content. Numerical 3D simulations are conducted by Finite Element Method, based on a given reed shape and an orthotropic model. A sensitivity analysis revels that, besides the density, the theoretical frequencies depend mainly on 2 parameters: $E_L$ and $G_{LT}$. An approximate analytical formula is proposed to calculate the resonance frequencies as a function of these 2 parameters. The discrepancy between the observed frequencies and those calculated with the analytical formula suggests that the elastic moduli of the measured reeds are frequency dependent. A viscoelastic model is then developed, whose parameters are computed as a linear combination from 4 orthogonal components, using a standard least squares fitting procedure and leading to an objective characterization of the material properties of the cane \textit{Arundo donax}.