Carbon nanotubes (CNTs) are under intense investigation in materials science owing to their potential for modifying the electrical conductivity sigma, shear viscosity eta, and other transport properties of polymeric materials. These particles are hybrids of filler and nanoscale additives because their lengths are macroscopic whereas their cross-sectional dimensions are closer to molecular scales. The combination of extended shape, rigidity and deformability allows CNTs to be mechanically dispersed in polymer matrices in the form of disordered 'jammed' network structures. Our measurements on representative network-forming multiwall nanotube (MWNT) dispersions in polypropylene indicate that these materials exhibit extraordinary flow-induced property changes. Specifically, sigma and eta both decrease strongly with increasing shear rate, and these nanocomposites exhibit impressively large and negative normal stress differences, a rarely reported phenomenon in soft condensed matter. We illustrate the practical implications of these nonlinear transport properties by showing that MWNTs eliminate die swell in our nanocomposites, an effect crucial for their processing.
Dielectric properties of model BaTiO3/polymer composites were measured over a broad frequency and temperature range. A series of BaTiO3/monomer suspensions were photocured into thin wafers. The wafers were equipped with aluminum electrodes, and the dielectric permittivity of the composites was investigated at frequencies from 100 Hz to 10 GHz and at temperatures from -140 to +150 °C. It has been found that for the same BaTiO3 loading dielectric characteristics of the composites strongly depend of the type of polymer. Polar polymers increase dielectric constant of the composites at low frequencies but have little effect at gigahertz frequencies. Dielectric losses of the composites show a maximum at some intermediate frequency within megahertz to gigahertz range that reflects the relaxation behavior of the polymer matrix. The magnitude of the losses increases with increasing polarity of the polymer component. At constant frequency and temperature, the composites follow a linear relationship between logarithm of their dielectric constant and volume fraction of the ferroelectric filler. Practical implications of such composites behavior are discussed.
We study the optical and electrical properties of transparent conducting films made from length-sorted single-wall carbon nanotubes (SWCNT). Thin films of length-sorted SWCNTs, formed through filtration from a dispersing solvent onto a filter substrate ("buckypaper"), exhibit sharp changes in their optical properties and conductivity (sigma) with increasing SWCNT surface concentration. At a given surface concentration, tubes longer than 200 nm are found to form networks that are more transparent and conducting. We show that changes of sigma with SWCNT concentration can be quantitatively described by the generalized effective medium (GEM) theory. The scaling universal exponents describing the "percolation" transition from an insulating to a conducting state with increasing concentration are consistent with the two-dimensional (2D) percolation model. Shorter tubes and mixed length tubes form 3D networks. Furthermore, we demonstrate that the conductivity percolation threshold (x(c)) varies with the aspect ratio L as, x(c) approximately 1/L, a result that is also in accordance with the percolation theory. These findings provide a framework for engineering the optical and electrical properties of SWCNT networks for technological applications where flexibility, transparency, and conductivity are required.
Recent measurements have suggested that the antiplasticizing effect of glycerol on trehalose can significantly increase the preservation times of proteins stored in this type of preservative formulation. In order to better understand the physical origin of this phenomenon, we examine the nature of antiplasticization in trehalose-glycerol mixtures by dielectric spectroscopy. These measurements cover a broad frequency range between 40 Hz to 18 GHz (covering the secondary relaxation range of the fragile glass-former trehalose and the primary relaxation range of the strong glass-former glycerol) and a temperature (T) range bracketing room temperature (220 K to 350 K). The Havriliak-Negami function precisely fits our relaxation data and allows us to determine the temperature and composition dependence of the relaxation time tau describing a relative fast dielectric relaxation process appropriate to the characterization of antiplasticization. We observe that increasing the glycerol concentration at fixed T increases tau (i.e., the extent of antiplasticization) until a temperature dependent critical "plasticization concentration" xwp is reached. At a fixed concentration, we find a temperature at which antiplasticization first occurs upon cooling and we designate this as the "antiplasticization temperature," Tant. The ratio of the tau values for the mixture and pure trehalose is found to provide a useful measure of the extent of antiplasticization, and we explore other potential measures of antiplasticization relating to the dielectric strength.
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