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We describe the creation of hollow tubular hydrogels in which different zones along the length of the tube are composed of different gels. Our method to create these gels is adapted from a technique developed previously in our lab for creating solid hybrid hydrogels. The zones of our tubular gel are covalently bonded at the interfaces; as a result, these interfaces are highly robust. Consequently, the tube can be picked up, manipulated and stretched without suffering any damage. The hollow nature of these gels allows them to respond 2⁻30-fold faster to external stimuli compared to a solid gel of identical composition. We study the case where one zone of the hybrid tube is responsive to pH (due to the incorporation of an ionic monomer) while the other zones are not. Initially, the entire tube has the same diameter, but when pH is changed, the diameter of the pH-responsive zone alone increases (i.e., this zone bulges outward) while the other zones maintain their original diameter. The net result is a drastic change in the shape of the gel, and this can be reversed by reverting the pH to its original value. Similar localized changes in gel shape are shown for two other stimuli: temperature and solvent composition. Our study points the way for researchers to design three-dimensional soft objects that can reversibly change their shape in response to stimuli.

Polymer hydrogels synthesized by chemical cross-linking of acrylate or acrylamide monomers can absorb more than 100 times their weight in water. However, such gels are usually fragile and rupture when stretched to moderate strains (∼50%). Many strategies have been developed to create tougher gels, including double-networking, incorporation of nanoparticles as cross-linkers, etc., but these strategies typically retard the water absorbency of the gel. Here, we present a new approach that gives rise to superabsorbent hydrogels having superior mechanical properties. The key to our approach is the self-cross-linking ability of N,N-dimethylacrylamide (DMAA). That is, we conduct a free-radical polymerization of DMAA (along with an ionic comonomer such as sodium acrylate) but without any multifunctional monomers. A hydrogel still forms due to interchain covalent bonds between the growing linear polymer chains. Gels formed by this route can be stretched up to 1350% strain in the unswollen state. The same gels are ...

We present a simple method to improve the transparency and rheological properties of polystyrene/organoclay nanocomposites. Such composites are typically prepared using organophilic derivatives of commercial montmorillonite (MMT) clays that contain a wide range of particle sizes. Our approach is to fractionate the native MMT clay to exclude large aggregates and then modify the fractionated clay (FMT) by a surfactant treatment (the resulting organoclay is termed o-FMT). Polystyrene nanocomposites made from the o-FMT are then compared with those made from a commercial organoclay having the same surfactant treatment. The o-FMT-based composites exhibit much better rheological properties (e.g., their elastic moduli at low frequencies are approximately 10 times higher) at equivalent mass loadings. Moreover, the o-FMT-based materials also have better transparency: e.g., a 10% o-FMT sample transmits as much light as a sample with 5% commercial clay. Transmission electron microscopy confirms that these differences in properties are related to microstructural differences; i.e., large aggregates are generally absent in the o-FMT samples. Clay fractionation may thus be a general strategy to enhance the properties of polymer/clay nanocomposites.

Previous work has shown that the formation of a network structure of nanoparticles within a polymer matrix can significantly reduce nanocomposite flammability and that viscoelastic properties could be utilized to predict their flammability reduction. The present work extends this type of investigation to the study of clay and carbon nanotube nanocomposites. In particular, we study PS/clay, PS/MWNT, PMMA/clay, and PMMA/SWNT nanocomposites. At a clay level of about 10% by mass, the network structure is formed for the PS and the PMMA clay nanocomposites; it requires a level of about 0.5% with the SWNT and 2% with the MWNT. These samples showed significantly reduced mass loss rates of PS and PMMA. However, the solid residues collected from radiative gasification tests of PS/clay and PMMA/clay showed many small cracks, despite the network formation within the initial sample. This is in contrast to the smooth, continuous residues (no cracks or openings) for PS/MWNT and PMMA/SWNT nanocomposites. The cracks in the clay samples are probably formed due to weaker network at elevated temperatures due to weaker bridging interaction between clay platelets as compared to stronger network resulting from dense entanglement and bridging of carbon nanotubes.

A systematic electrical and rheological characterization of percolation in commercial polydisperse polystyrene (PS) nanocomposites containing multiwall carbon nanotubes (MWCNTs) is presented. The MWCNTs confer appreciable electrical conductivities (up to ca. 1 S/m) to these nanocomposites at a concentration of 8 vol %. In addition to enhancing the electrical properties, even at small concentrations (ca. 2 vol %), MWCNTs significantly enhance the rheological properties of PS melts. At concentrations exceeding 2 vol %, a plateau appears in the storage modulus G‘ at low frequencies, indicating the formation of a percolated MWCNT network that responds elastically over long timescales. Network formation, in turn, implies a diverging complex viscosity vs complex modulus curve. A focus of this study is on the correlation between electrical and rheological properties at the onset of percolation. The experimental results indicate that the elastic load transfer and electrical conductivity are far more sensitive to ...

The thermal and flammability properties of polyamide 6/clay (2 and 5% by mass fraction) nanocomposites were measured to determine their flame retardant (FR) performance. The gasification process of the nanocomposite samples at an external radiant flux of 50 kW/m 2 in a nitrogen atmosphere was observed, and the residues collected at various sample mass losses were analyzed by thermogravimetric analysis, transmission electron microscopy, and X-ray diffraction to determine the content of the residue and to understand the FR mechanism of the nanocomposites. The analysis of the floccules of blackened residues shows that up to 80% by mass of the residues consists of clay particles and the remainder is thermally stable organic components with possible graphitic structure. Furthermore, clay particles are stacked in the carbonaceous floccule residues and the d-spacing of the clay platelets is in the range of 1.3 – 1.4 nm as compared to the well exfoliated original sample. The accumulation of the initially well-dispersed clay particles in the sample on the burning/gasifying sample surface are due to two possible mechanisms. One is recession of the polymer resin from the surface by pyrolysis with the de-wetted clay particles left behind. Another mechanism is the transportation of clay particles pushed by numerous rising bubbles of degradation products and the associated convection flow in the melt from the interior of the sample toward the sample surface. Numerous rising bubbles may have another effect on the transport of clay particles. Bursting of the bubbles at the sample surface pushes the accumulated clay particles outward from the bursting area and forms the island-like floccules instead of forming a continuous net-like structure of a clay filled protective layer. Therefore, both PA6/clay nanocomposite samples did not produce sufficient amounts of protective floccules to cover the entire sample surface and vigorous bubbling was observed over the sample surface which was not covered by the protective floccules. q 2003 Elsevier Ltd. All rights reserved.

We describe the remarkable capabilities of polymer–nanoparticle hybrids for cation binding and separation. The materials investigated here are hydrogels of N-isopropylacrylamide (NIPA) prepared using nanoparticles of the synthetic clay, Laponite® RD, as the crosslinkers. When immersed into an aqueous solution containing a cationic amine-based dye (methylene blue), the gel rapidly soaks up the dye from solution. Additionally, the gel is able to selectively extract the above cationic dye from a mixture of cationic and anionic dyes. These ion-exchange properties are driven by the strong binding affinity of certain cations for the anionic surfaces of the clay nanoparticles within the gel matrix. A comparison of the nanostructured gel with a typical cation-exchange resin (polystyrene-sulfonate) shows that the former is quicker and more efficient at extracting cationic species from solution. We also show that the solute adsorbed within the gel can be further concentrated by exploiting the shrinking property of NIPA gels when heated. Additionally, we demonstrate the disassembly of Laponite-crosslinked gels by exposure to an organic solvent or a hydrophilic oligomer, which allows the adsorbed solute to be released and thereby recovered.

For the first time, an interpenetrating phase polymer nanocomposite formed by the percolation of multiwalled carbon nanotubes (MWCNTs) in polystyrene (PS) has been quantitatively characterized through electrical conductivity measurements and melt rheology. Both sets of measurements, in conjunction with scanning electron microscopy (SEM) images, indicate the presence of a continuous phase of percolated MWCNTs appearing at particle concentrations exceeding 2 vol% MWCNTs in PS. To quantify the amount of this continuous phase present in the PS/MWCNT composite, electrical conductivity data at various MWCNT concentrations, β, are correlated with a proposed degree of percolation, , developed using a conventional power-law formula with and without a percolation threshold. To quantify the properties of the interpenetrating phase polymer nanocomposite, the PS/MWCNT composite is treated as a combination of two phases: a continuous phase consisting of a pseudo-solid-like network of percolated MWCNTs, and a continuous PS phase reinforced by non-interacting MWCNTs. The proposed degree of percolation is used to quantify the distribution of MWCNTs among the phases, and is then used in a rule-of-mixtures formulation for the storage modulus, , and the loss modulus, , to quantify the properties of the continuous phase consisting of percolated MWCNTs and the continuous PS phase reinforced by non-interacting MWCNTs from the experimental melt rheology data. The properties of the continuous phase of percolated MWCNTs are indicative of a scaffold-like microstructure exhibiting an elastic behavior with a complex modulus of 360 kPa at lower frequencies and viscoplastic behavior with a complex viscosity of 6 kPa s rad−1 at higher frequencies, most likely due to a stick–slip friction mechanism at the interface of the percolated MWCNTs. Additional evidence of this microstructure was obtained via scanning electron microscopy. This research has important implications in providing a new methodology based on the electrical and rheological properties of the polymer nanocomposite for quantifying the continuous phase formed by the percolation of new functionalized nanostructures being developed for: (a) controlling the percolation of the nanostructures through self-assembly, (b) enhancing their interaction with the continuous reinforced polymer phase, (c) enhancing the cohesion between nanostructures.