The Electrical and Mechanical Characteristics of Conductive PVA/PEDOT:PSS Hydrogel Foams for Soft Strain Sensors.

Conductive hydrogels are of interest for highly flexible sensor elements. We compare conductive hydrogels and hydrogel foams in view of strain-sensing applications. Polyvinyl alcool (PVA) and poly(3,4-ethylenedioxythiophene (PEDOT:PSS) are used for the formulation of conductive hydrogels. For hydrogel foaming, we have investigated the influence of dodecylbenzenesulfonate (DBSA) as foaming agent, as well as the influence of air incorporation at various mixing speeds. We showed that DBSA acting as a surfactant, already at a concentration of 1.12wt%, efficiently stabilizes air bubbles, allowing for the formulation of conductive PVA and PVA/PEDOT:PSS hydrogel foams with low density (<400 kg/m3) and high water uptake capacity (swelling ratio > 1500%). The resulting Young moduli depend on the air-bubble incorporation from mixing, and are affected by freeze-drying/rehydration. Using dielectric broadband spectroscopy under mechanical load, we demonstrate that PVA/PEDOT:PSS hydrogel foams exhibit a significant decrease in conductivity under mechanical compression, compared to dense hydrogels. The frequency-dependent conductivity of the hydrogels exhibits two plateaus, one in the low frequency range, and one in the high frequency range. We find that the conductivity of the PVA/PEDOT:PSS hydrogels decreases linearly as a function of pressure in each of the frequency regions, which makes the hydrogel foams highly interesting in view of compressive strain-sensing applications.

Synthesis and characterization of polyaniline-silica composites: Raspberry vs core-shell structures. Where do we stand?

The synthesis of polyaniline-silica composites has been reinvestigated in view of the opposing results found in the literature. Firstly, we synthesized silica particles with tunable size using the Stöber process. These silica particles have been fully characterized before being used as solid support for the polymerization of aniline. This polymerization was performed according to a published procedure where the pH of the reaction mixture was below the pKa of aniline but at a value where the silica particles surface was still slightly negatively charged. The objective of this procedure was to favor electrostatic interactions between anilinium cations and the silica surface to lead to the formation of silica-polyaniline core-shell particles. Several sets of nanocomposites were prepared under different experimental conditions (oxidant/aniline ratio, silica concentration, temperature, silica particles diameters). The study evidenced that under all the conditions used the formation of core-shell nanoparticles is impossible. However, using different particle sizes, noticeable morphological differences were observed. The use of large silica particles led to the formation of non-uniform polyaniline-silica composites whereas the use of smaller particles always led to raspberry-like morphology as reported by other groups in highly acidic media. The difference in morphology led to different electrical properties with electrical conductivities measured at room temperature ranging from 1.6×10-3 to 2.5×10-5S cm-1.

From the solution processing of hydrophilic molecules to polymer-phthalocyanine hybrid materials for ammonia sensing in high humidity atmospheres.

We have prepared different hybrid polymer-phthalocyanine materials by solution processing, starting from two sulfonated phthalocyanines, s-CoPc and CuTsPc, and polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), poly(acrylic acid-co-acrylamide) (PAA-AM), poly(diallyldimethylammonium chloride) (PDDA) and polyaniline (PANI) as polymers. We also studied the response to ammonia (NH3) of resistors prepared from these sensing materials. The solvent casted films, prepared from s-CoPc and PVP, PEG and PAA-AM, were highly insulating and very sensitive to the relative humidity (RH) variation. The incorporation of s-CoPc in PDDA by means of layer-by-layer (LBL) technique allowed to stabilize the film, but was too insulating to be interesting. We also prepared PANI-CuTsPc hybrid films by LBL technique. It allowed a regular deposition as evidenced by the linear increase of the absorbance at 688 nm as a function of the number of bilayers. The sensitivity to ammonia (NH3) of PANi-CuTsPc resistors was very high compared to that of individual materials, giving up to 80% of current decrease when exposed to 30 ppm NH3. Contrarily to what happens with neutral polymers, in PANI, CuTsPc was stabilized by strong electrostatic interactions, leading to a stable response to NH3, whatever the relative humidity in the range 10%-70%. Thus, the synergy of PANI with ionic macrocycles used as counteranions combined with their simple aqueous solution processing opens the way to the development of new gas sensors capable of operating in real world conditions.

Overshoots of adsorption kinetics during layer-by-layer polyelectrolyte film growth: role of counterions.

Layer-by-layer adsorption of polycation poly(trimethylammonium ethyl methacrylate chloride) (MADQUAT) and polyanion poly(acrylic acid, sodium salt) (PAA) on silicon oxide substrates was studied in order to understand non-regular multilayer buildup. Indeed during MADQUAT adsorption, a special variation in the signal, called overshoots, was monitored with stagnation point adsorption reflectometry (SPAR). These overshoots were observed under different experimental conditions (pH, polymer concentration, salt concentration and molecular weight variations). A method called "substrate thickness method" was applied to determine the thickness, the refractive index and the adsorbed amount variation during the overshoot. Results clearly showed a decrease in the adsorbed amounts, but which does not necessarily indicate dissolution of the adsorbed multilayer. Therefore we also investigated layer-by-layer adsorption on colloidal silica particles (SiO2) under the same conditions as those in reflectometry. Indeed the high specific surface area of particles allowed titration of chloride ions and unadsorbed polymer in the bulk during the adsorption process. An increase in chloride ions concentration with no increase in the polymer concentration was observed. Accordingly, overshoots in cases of MADQUAT/PAA multilayer are not due to desorption of cationic polyelectrolyte but to desorption of chloride ions from the adsorbed multilayer film.

Charge properties of membranes modified by multilayer polyelectrolyte adsorption.

Alternate adsorption of polyanions and polycations on a polyethersulfone (PES) membrane was studied by the tangential streaming potential method using a parallel-plate channel to investigate the properties of the outer surface of the membrane. These streaming potential data were complemented by diffusion experiments and by membrane potential measurements in order to characterize the inner surface of the membrane. Tangential streaming potential measurements demonstrated that after completing a bilayer of poly(allylamine hydrochloride) (PAH) and poly(sodium 4-styrene sulfonate) (PSS), periodic variations in the zeta potential between positive and negative values appeared for multilayer films obtained from membrane dipped in polyelectrolyte (PE) solutions at 10 g/L. On the contrary, the zeta potential was always positive when multilayer films were obtained from 1 and 5 g/L polyelectrolyte concentration solutions. Diffusion experiments carried out with unmodified and modified membranes showed a decrease in the solute flux after functionalization of the membrane by several polyelectrolyte bilayers, indicating that the diffusional resistance of the PE layers contributes significantly to the overall resistance to diffusion of the modified membrane. By means of membrane potential measurements the pore walls of the membrane were functionalized since the charge of its pore walls was modified even if it is difficult to discriminate between the contribution of the membrane and that of the multilayer buildup.

Guiding the self-assembly of a second-generation polyphenylene dendrimer into well-defined patterns.

A second-generation polyphenylene dendrimer 1 is shown to self-assemble into nanofibers. To guide the formation of the dendrimer fibers into well-defined patterns, 1H,1H,2H,2H-perfluorodecyltrichlorosilane is grafted in the gas phase onto a silicon substrate. De-wetting of the solution on the nanopatterned surface results in the formation of a nanostructured template, into which fiber growth subsequently occurs under the constraints set by the de-wetted morphology.

Resistance of poly(ethylene oxide)-silane monolayers to the growth of polyelectrolyte multilayers.

The ability of poly(ethylene oxide)-silane (PEO-silane) monolayers grafted onto silicon surfaces to resist the growth of polyelectrolyte multilayers under various pH conditions is assessed for different pairs of polyelectrolytes of varying molar mass. For acidic conditions (pH 3), the PEO-silane monolayers exhibit good polyelectrolyte repellency provided the polyelectrolytes bear no moieties that are able to form hydrogen bonds with the ether groups of the PEO chains. At basic pH, PEO-silane monolayers undergo substantial hydrolysis leading to the formation of negatively charged defects in the monolayers, which then play the role of adsorption sites for the polycation. Once the polycation is adsorbed, multilayer growth ensues. Because this is defect-driven growth, the multilayer is not continuous and is made of blobs or an open network of adsorbed strands. For such conditions, the molar mass of the polyelectrolyte plays a key role, with polyelectrolyte chains of larger molar mass adsorbing on a larger number of defects, resulting in stronger anchoring of the polyelectrolyte complex on the surfaces and faster subsequent growth of the multilayer. For polyelectrolytes of sufficiently low molar mass at pH 9, the growth of the multilayer can nevertheless be prevented for as much as five cycles of deposition.