On‐line Determination of Particle Size Distributions in Flowing Dispersions

Emulsions are of great importance to industry. They are involved in many engineering operations, including chemical reactions, extraction, emulsification and suspension polymerization, etc. However, an important problem for these processes is how to control the size distribution of the dispersed phase. Indeed, off‐line analysis of the emulsion may generate uncertainties due to sampling and dilution of the product, which are likely to change the dispersion state and physico‐chemical properties. In this work, an on‐line optical method is proposed to characterize dispersed media in real flowing conditions. This method is based on the time‐analysis of back‐scattered light fluctuations. The present paper deals with the development of this method and its application to dispersions of alumina in water. The results obtained with the on‐line optical method are compared with those acquired by classical laser light scattering and microscopy.     

A shock tube study of the reaction of methyl radicals with hydroxyl radicals

The reaction of CH₃ with OH has been studied near 1200 K and 1 atmosphere pressure in shock tube experiments in which UV absorption was used to monitor [OH]. A rate coefficient of (1.1 ± 0.3) × 10¹³ cm³/mol-s was measured for removal of OH by CH₃. This measured value is compared with previous experimental data and calculations. Several possible reaction channels are discussed, and although products were not monitored, it seems probable, on the basis of other work and theoretical estimates, that the primary mechanism (?75%) for the removal of OH by CH₃ at these conditions is their combination to form CH₃OH. Rate coefficients of (5.3 ± 0.8) × 10¹² and (9.0 ± 1.4) × 10¹² cm³/mol-s were measured for the reactions of OH with acetone and ethane, respectively, at the same temperature and pressure.     

The effect of nanoparticle shape on polymer‐nanocomposite rheology and tensile strength

Nanoparticles can influence the properties of polymer materials by a variety of mechanisms. With fullerene, carbon nanotube, and clay or graphene sheet nanocomposites in mind, we investigate how particle shape influences the melt shear viscosity η and the tensile strength τ, which we determine via molecular dynamics simulations. Our simulations of compact (icosahedral), tube or rod‐like, and sheet‐like model nanoparticles, all at a volume fraction ? ≈ 0.05, indicate an order of magnitude increase in the viscosity η relative to the pure melt. This finding evidently can not be explained by continuum hydrodynamics and we provide evidence that the η increase in our model nanocomposites has its origin in chain bridging between the nanoparticles. We find that this increase is the largest for the rod‐like nanoparticles and least for the sheet‐like nanoparticles. Curiously, the enhancements of η and τ exhibit opposite trends with increasing chain length N and with particle shape anisotropy. Evidently, the concept of bridging chains alone cannot account for the increase in τ and we suggest that the deformability or flexibility of the sheet nanoparticles contributes to nanocomposite strength and toughness by reducing the relative value of the Poisson ratio of the composite. The molecular dynamics simulations in the present work focus on the reference case where the modification of the melt structure associated with glass‐formation and entanglement interactions should not be an issue. Since many applications require good particle dispersion, we also focus on the case where the polymer‐particle interactions favor nanoparticle dispersion. Our simulations point to a substantial contribution of nanoparticle shape to both mechanical and processing properties of polymer nanocomposites. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1882–1897, 2007     

Sums of Two Exact Powers

An asymptotic formula is obtained for the number of representations of an element of a finite field as a weighted sum of two prescribed powers of primitive elements. This generalises previous work on sums of primitive elements, including that relating to some conjectures of Golomb.     

Electrochemical reduction of Bi2Sr2Ca1Cu2O8 superconductor single crystals

Single crystals and polycrystalline pellets of the high-temperature cuprate superconductor Bi₂Sr₂Ca₁Cu₂O₈ were doped at room temperature by electrochemical reduction at > 95% Coulombic efficiency using lithium dopant ions in propylene carbonate electrolyte. Cyclic voltammetry and potential step measurements on single crystals suggest an unusual reduction mechanism, with a diffusion coefficient for Li⁺ in the c-axis direction of bulk superconductor of ca. 3 × 10⁻¹¹ cm²s⁻¹. Sintered pellets of polycrystalline powder could be doped more rapidly, with an apparent diffusion coefficient of 7 × 10⁻⁸ cm²s⁻¹. X-ray susceptibility analysis show extensive disordering occurs on heavy Li doping, with a first-order transition from a crystalline/superconducting to an amorphous/non-superconducting phase. Single, crystals of Bi₂Sr₂Ca₁Cu₂O₈ exhibited a color change on reduction from metallic gray to golden bronze. The reduced material was highly air-sensitive, forming a hydroxide surface film on exposure to ambient atmosphere.