A versatile route to functional biomimetic coatings: ionomers for honeycomb-like structures.

Highly ordered films were prepared by spreading out carbon disulfide (CS) solutions of ionomers over inorganic surfaces and for the first time over an organic surface. These ionomers, hydrophobic homopolymers or copolymers end-capped by a cationic group, were easily synthesized in a one-step reaction by a control radical process called nitroxide-mediated polymerization. Optical and electronic microscopy observations of the films lead to the definition of new criteria for the formation of such structures. Firstly, the effect of a solid support on the honeycomb structure regularity was studied. By comparing two polar substrates, it was found that a more regular organization is obtained over mica than over glass. This phenomenon may be due to the electrostatic interactions between cationic ionomer ends and oxanions of the mica surface. Moreover, for the first time, highly ordered hexagonal patterns were also created on a flexible and soft polymeric surface, a poly(vinyl chloride) sheet. Secondly, it was found that the characteristics of the polymeric chain of the ionomer and mainly its glass transition temperature play an important role in the process of formation of ordered structures. The iridescent aspect of the films, due to light diffraction and optical interferences, was studied and quantified by spectrogoniometry. Finally, results of measurements of superficial tension are discussed; the presence of a honeycomb film at the surface of a material very significantly enhances its hydrophobicity. All these criteria of highly ordered structures correlated to a water repellency and iridescent behaviours lead to a functional biomimetic material.

A small-angle neutron scattering study of sodium dodecyl sulfate-poly(propylene oxide) methacrylate mixed micelles.

Mixed micelle of protonated or deuterated sodium dodecyl sulfate (SDS and SDSd25, respectively) and poly(propylene oxide) methacrylate (PPOMA) are studied by small-angle neutron scattering (SANS). In all the cases the scattering curves exhibit a peak whose position changes with the composition of the system. The main parameters which characterize mixed micelles, i.e., aggregation numbers of SDS and PPOMA, geometrical dimensions of the micelles and degree of ionisation are evaluated from the analysis of the SANS curves. The position q(max) of the correlation peak can be related to the average aggregation numbers of SDS-PPOMA and SDSd25-PPOMA mixed micelles. It is found that the aggregation number of SDS decreases upon increasing the weight ratio PPOMA/SDS (or SDSd25). The isotopic combination, which uses the "contrast effect" between the two micellar systems, has allowed us to determine the mixed micelle composition. Finally, the SANS curves were adjusted using the RMSA for the structure factor S(q) of charged spherical particles and the form factor P(q) of spherical core-shell particle. This analysis confirms the particular core-shell structure of the SDS-PPOMA mixed micelle, i.e., a SDS "core" micelle surrounded by the shell formed by PPOMA macromonomers. The structural parameters of mixed micelles obtained from the analysis of the SANS data are in good agreement with those determined previously by conductimetry and fluorescence studies.

Micellar copolymerization of associative polymers: study of the effect of acrylamide on sodium dodecyl sulfate-poly(propylene oxide) methacrylate mixed micelles.

Mixed micelles of sodium dodecyl sulfate (SDS) and poly(propylene oxide) methacrylate (PPOMA) have been studied in the presence of acrylamide using conductimetry, fluorescence spectroscopy, and small-angle neutron scattering (SANS) under the following conditions: (i) the SDS-acrylamide binary system in water; (ii) the SDS-acrylamide-PPOMA ternary system in water. The addition of acrylamide in SDS solutions perturbs the micellization of the surfactant by decreasing the aggregation number of the micelles and increasing their ionization degree. The variations of the various micellar parameters versus the weight ratio R=PPOMA/SDS are different in the presence of acrylamide or in pure water. These differences are much more pronounced for the lower than for the higher PPOMA concentrations. There is competition between acrylamide and PPOMA and at higher PPOMA concentration, acrylamide tends to be released from SDS micelles and is completely replaced by PPOMA.

Determination of the structure of the organized phase of the block copolymer PEO-PPO-PEO in aqueous solutions under flow by small-angle neutron scattering.

The organization of Tetronic 908 (T908), a star copolymer of poly(ethylene oxide) (PEO) and poly(propylene oxide) (PPO) blocks, has been examined. Above critical conditions of temperature and concentration, the micelles formed by the aggregation of PPO units self-organize into particular structures. While small-angle neutron scattering (SANS) characterizations performed with static conditions demonstrate the organization of the medium, the experimental results do not allow us to make a distinction between simple cubic and body-centered-cubic structures. However, SANS measurements realized under shear produce characteristic diffraction diagrams. In this paper, an accurate methodology is proposed to identify, without ambiguity, the exact nature of the organized phase. Applied to our system, indexing of the diffraction pattern spots reveals that the organization of T908 is of bcc type oriented with the [111] direction parallel to the direction of flow, but the crystals can present any orientation about this direction. The lattice size has been estimated and compared to previous published results.

Structure and properties of hydrophobically end-capped poly(ethylene oxide) solutions in the presence of monovalent and divalent cations.

Hydrophobically modified poly(ethylene oxide), HMPEO, was studied in concentrated salt solutions. The influence of salts was compared to the effect of temperature on poly(ethylene oxide), PEO. As expected, the addition of monovalent cations (Na(+), K(+)) has the same effect as an increase in temperature in agreement with the thermodynamic properties of PEO: a decrease in solubility, micelle size, and viscosity was observed. Moreover, the intensity of neutron scattering peaks (characteristic of the semi-dilute solutions of these associative polymers) increases due to the collapse of PEO coronae in micelles. Very peculiar behavior was observed in the presence of divalent cations (Ca(2+), Mg(2+)): larger micelle aggregates and higher viscosities, relaxation times, and activation energies were observed by dynamic rheology. This behavior is attributed to interactions between divalent cations and oxygen in PEO backbones close to the micelle core, which may reinforce intermicellar bridges.

Study of a nanocomposite based on a conducting polymer: polyaniline.

A simple way to obtain a conducting nanocomposite is described, and the conducting particles are characterized. Core-shell particles [polystyrene-polyaniline (PANI)] have been obtained by the dispersion process from three types of polystyrene latexes: a no-cross-linked core stabilized by a nonylphenolethoxylate (NP40) and two cross-linked cores stabilized by NP40 and a mixture NP40/Surfamid (a surfactant bearing an amide group). The surface of these particles has been extensively characterized by X-ray photoelectron spectroscopy (XPS), atomic force microscopy, and scanning electron microscopy. A maximum coverage of 94% was obtained for the high PANI content as revealed by XPS analysis. A better coverage was obtained for the cross-linked polystyrene latex stabilized by the Surfamid. The amide group of this surfactant allows the H-bonding formation with the PANI backbone and, thus, improves the conductivity. It was shown that a uniform coverage of the core particles was not required to ensure a good conductivity.

Study of sodium dodecyl sulfate-poly(propylene oxide) methacrylate mixed micelles.

Sodium dodecyl sulfate (SDS)-poly(propylene oxide) methacrylate (PPOMA) (of molecular weight M(w) = 434 g x mol(-1)) mixtures have been studied using conductimetry, static light scattering, fluorescence spectroscopy, and 1H NMR. It has been shown that SDS and PPOMA form mixed micelles, and SDS and PPOMA aggregation numbers, N(ag SDS) and N(ag PPOMA), have been determined. Total aggregation numbers of the micelles (N(ag SDS) + N(ag PPOMA)) and those of SDS decrease upon increasing the weight ratio R = PPOMA/SDS. Localization of PPOMA inside the mixed micelles is considered (i) using 1H NMR to localize the methacrylate function at the hydrophobic core-water interface and (ii) by studying the SDS-PPO micellar system (whose M(w) = 400 g x mol(-1)). Both methods have indicated that the PPO chain of the macromonomer is localized at the SDS micelle surface. Models based on the theorical prediction of the critical micellar concentration of mixed micelles and structural model of swollen micelles are used to confirm the particular structure proposed for the SDS-PPOMA system, i.e., the micelle hydrophobic core is primarily composed of the C12 chains of the sodium dodecyl sulfate, the hydrophobic core-water interface is made up of the SDS polar heads as well as methacrylate functions of the PPOMA, the PPO chains of the macromonomer are adsorbed preferentially on the surface, i.e., on the polar heads of the SDS.