Clay dispersibility and mechanical property of the epoxy/clay nanocomposites prepared by different treatment methods

The bisphenol‐A type epoxy resin was combined with layered clays. Three types of epoxy/clay nanocomposites were prepared by different clay pretreatment methods, that is, the slurry (clay swelling with polar solvent), organo, and solubilization (organoclay swelling with polar solvent) methods. The organo and solubilization systems showed good dispersibility. The basal spacing of the layered clays in the obtained nanocomposites was evaluated by XRD and TEM observations. The basal spacing of the nanoclay in the solubilization system drastically increased. The mechanical properties were improved with the increase in the clay dispersion. A high modulus and fracture toughness were obtained by improvement of the clay dispersion into the matrix. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1753–1761, 2009     

Exploring rheological properties of aqueous polyaniline‐PVP dispersion

Stable aqueous dispersion of polyaniline (PAn) stabilized by a hydrophilic polymer poly(vinyl pyrrolidone) (PVP) exhibits interesting rheological properties different from its components. Shear thinning observed for both PVP and PAn–PVP colloid (PP) indicates partially entangled nature of the later. Linear viscoelastic response of PVP solution exhibit strong frequency dependence of elastic (G′) and viscous (G″) modulus over the whole frequency range (0.1–100 ras/s) where G′ never exceeds G″ indicating the applicability of the Rouse‐Zimm model to this system. On the other hand, there is a crossover of G′ and G″ in the rheological profile of PP dispersion so that a single relaxation time model can be applicable. Therefore, PVP presents an entangled polymeric system and supposed to have a spectrum of relaxation times, whereas PP resembles to a physically crosslinked system with a single relaxation time. Increasing the extent of hydrogen bonding within the system (by raising the fraction of PAn or by leaving the solution undisturbed for long) relaxation time also becomes longer. The large difference in values of steady and complex shear viscosity (η and η*) within LVE regime reflects that original Cox‐Merz rule is obviously inapplicable to these systems. But at larger strain amplitude, η and η* are satisfactorily coincident that indicates a broader applicability of the modified Cox‐Merz rule. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2443–2455, 2008     

Control of amphiphilic block copolymer morphologies using solution conditions

It is well known that the morphology of block copolymer aggregates depends on polymer properties such as the molecular weight, the relative block length, and the chemical nature of the repeat unit. Recently, we have shown that if aggregates are allowed to self-assemble in solution, then in addition to the above factors, a high degree of control over the aggregate architecture can be achieved by adjusting the solution conditions. Factors such as the water content in the solvent mixture, the solvent nature and composition, the presence of additives (ions, surfactants, and homopolymer) and the polymer concentration were successfully employed to control the aggregate shape and size. In this paper, we review a series of studies performed in our group to show how solution properties can control the architecture of aggregates prepared from a given copolymer. The control mechanism is explained in terms of the effect of each property on the forces that govern the formation of any given morphology, namely the core-chain stretching, corona-chain repulsion and interfacial tension. Received 30 April 2002 and Received in final form 3 September 2002 Published online: 21 January 2003     

Elasticity,fracture and thermoreversible gelation of highly filled physical gels<Superscript>⋆</Superscript>

We describe a physically associating triblock copolymer-based gel that exhibits a reversible transition between solid and liquid states at a temperature of approximately 55^°C. The thermal transition of the gel enables us to compare the properties of liquid suspensions and elastic composites with identical particle loadings, with particle volume fractions as large as 0.55. The suspension viscosity and the composite elasticity scale in a similar manner with the overall particle volume fraction, a result that is rationalized in terms of an effective strain amplification factor that depends only on the particle loading. Measured values of the strain amplification factor are in good agreement with the expected form for well-dispersed spheres. We also find that the elastic composites are exceptionally strong, with fracture strengths that exceed the modulus of the base gel by a factor of 100 or more. Deviations from purely elastic behavior became important for high particle volume fractions, and were probed by stress relaxation experiments.     

Viscosity minimum in bimodal concentrated suspensions under shear

We study a model of concentrated suspensions under shear in two dimensions. Interactions between suspended particles are dominated by direct-contact viscoelastic forces and the particles are neutrally bouyant. The bimodal suspensions consist of a variable proportion between large and small droplets, with a fixed global suspended fraction. Going beyond the assumptions of the classical theory of Farris (R.J. Farris, Trans. Soc. Rheol. 12, 281 (1968)), we discuss a shear viscosity minimum, as a function of the small-to-large-particle ratio, in shear geometries imposed by external body forces and boundaries. Within a linear-response scheme, we find the dependence of the viscosity minimum on the imposed shear and the microscopic drop friction parameters. We also discuss the viscosity minimum under dynamically imposed shear applied by boundaries. We find a reduction of macroscopic viscosity with the increase of the microscopic friction parameters that is understood using a simple two-drop model. Our simulation results are qualitatively consistent with recent experiments in concentrated bimodal emulsions with a highly viscous or rigid suspended component. Received 28 June 2002 RID="a" ID="a"e-mail: ernesto@pion.ivic.ve     

Amphiphilic block copolymer nanocontainers as bioreactors

Self-assembly of an amphiphilic triblock copolymer carrying polymerizable end-groups is used to prepare nanometer-sized vesicular structures in aqueous solution. The triblock copolymer shells of the vesicles can be regarded as a mimetic of biological membranes although they are 2 to 3 times thicker than a conventional lipid bilayer. Nevertheless, they can serve as a matrix for membrane-spanning proteins. Surprisingly, the proteins remain functional despite the extreme thickness of the membranes and that even after polymerization of the reactive triblock copolymers. This opens a new field to create mechanically stable protein/polymer hybrid membranes. As a representative example we functionalize (polymerized) triblock copolymer vesicles by reconstituting a channel-forming protein from the outer cell wall of Gram-negative bacteria. The protein used (OmpF) acts as a size-selective filter, which allows only for passage of molecules with a molecular weight below 400 g mol^-1. Therefore substrates may still have access to enzymes encapsulated in such protein/polymer hybrid nanocontainers. We demonstrate this using the enzyme β-lactamase which is able to hydrolyze the antibiotic ampicillin. In addition, a transmembrane voltage above a given threshold causes a reversible gating transition of OmpF. This can be used to reversibly activate or deactivate the resulting nanoreactors. Received 22 August 2000     

Direct Assembly of BaTiO3‐Poly(methyl methacrylate) Nanocomposite Films

Summary: This study examines the use of a PMMA‐mediated assembly of BaTiO₃ nanoparticles directly onto Cu electrodes under an electric field. The compatibility of the interface between BaTiO₃ nanoparticles and PMMA in a mixed organic solvent system enables the homogeneous dispersion of nanoparticles in a solid polymer matrix. This results in the effective packing of particles, which is desirable from the point of view of achieving a high dielectric constant in the composite. In this study, three‐phase Al/BaTiO₃/PMMA nanocomposite films from stable colloidal suspensions containing aluminium nitrate salts were also designed using an electrodeposition process. The simultaneous formation of Al metallic inclusions in the BaTiO₃ nanoparticles in the PMMA matrix significantly improved the dielectric constant of nanocomposite films.

HRTEM micrographs of BaTiO₃ (240 nm)/PMMA and magnified view of BaTiO₃ (50 nm)/PMMA/Al(NO₃)₃ · 9H₂O composite particles in each suspension, and FESEM micrograph of electrodeposited three‐phase nanocomposite film.     

Nanocomposites of Polyaniline/Poly(2‐methoxyaniline‐5‐sulfonic acid)

Summary: Poly(2‐methoxyaniline‐5‐sulfonic acid) (PMAS) is a water‐soluble derivative of polyaniline that carries negatively charged sulfonate groups. This self‐doped conducting polymer also behaves like a polyelectrolyte that can subsequently function as a dopant in polyaniline (PAn). The chemical synthesis of PAn/PMAS is presented describing the preparation of a highly stable composite dispersion. TEM images reveal a mixture of well‐defined nanofibres and nanoparticles with diameters between 20 and 100 nm. The UV‐vis spectra of the PAn/PMAS composite in water and in alkaline media indicate that both PAn and PMAS are present in the composite. Electrochemical studies show that both of the conducting polymer components are capable of undergoing oxidation and reduction. The novel PAn/PMAS nanocomposite has enhanced electrical conductivity and stability compared to PAn/HCl nanofibres prepared under equivalent conditions, making it a promising material for applications in areas such as batteries, electronic textiles, electrochromics, and chemical sensors.

Transmission electron micrograph of a PAn/PMAS nanocomposite.     

Sub‐Micrometer Sized Hairy Latex Particles Synthesized by Dispersion Polymerization Using Hydrophilic Macromolecular RAFT Agents

Dispersion polymerization of n‐butyl acrylate has been performed in a mixture of ethanol and water in the presence of poly(N‐acryloylmorpholine) (polyNAM). These hydrophilic polymer chains are synthesized by the RAFT process and thus incorporate well‐defined chain ends. The dithioester ω‐end group is used as an efficient chain transfer agent under dispersion polymerization conditions to produce hairy poly(n‐butyl acrylate) latex particles. Moreover, pre‐functionalization of the polyNAM chains on the α‐end by a carbohydrate derivative is also achieved to obtain directly functionalized particles according to the same strategy.