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     

Gas solubility of carbon dioxide in poly(lactic acid) at high pressures: Thermal treatment effect

The sorption of carbon dioxide in glassy Poly(lactic acid) (PLA) films was studied by quartz crystal microbalance (QCM) at high pressures. Two thermal treatments, melted and quenched, were performed in PLA with two different L:D contents, 80:20 and 98:2, films and compared with a third thermal protocol, annealed, and used in a previous work. The results obtained show that for pressures higher than 2 MPa, the carbon dioxide solubility is larger in PLA 80:20 than in PLA 98:2, indicating that the L:D plays a dominant role on this property. The thermal treatments only affect the gas solubility in PLA 98:2. Sorption isotherms at temperatures 303, 313, and 323 K, below the glass transition temperature of the polymer, and pressures up to 5 MPa were measured and analyzed with three different models, the dual‐mode sorption model, the Flory–Huggins equation, and a modified dual‐mode sorption model where the Henry's law term was substituted by the Flory–Huggins equation. This last model performs especially well for CO₂ in PLA 80:20, due to the convex upward curvature of the solubility isotherms for that system. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 616–625, 2007     

Ionic relaxation in nematic liquid crystal cells

We investigate the dependence of the relaxation time of the current flowing in a nematic cell submitted to an external dc voltage on the physical properties of the substrate. We show that previously presented analyses of the same problem are not very useful for practical applications. We compare our theoretical predictions with experimental data, and show that the agreement is rather good. The influence of the adsorption-desorption phenomenon on the relaxation time is also discussed.     

Applications of fast atom bombardment mass spectrometry (FAB MS) to organometallic and coordination chemistry

This article describes the technique of fast atom bombardment mass spectrometry (FAB MS) and its applications to the analysis of organometallic and coordination complexes. Sections on ion generation and matrices are followed by a Periodic Group-based review of FAB MS results obtained from Transition Metal and Main Group compounds, organometallic cluster carbonyls and their derivatives, and salts of poly-oxo-anions. The literature has been surveyed from 1981 to approximately mid-1986.     

Korrosionstests an magnetischen Schichten und deren Beurteilung mit Hilfe ausgew?hlter oberfl?chenanalytischer Verfahren

Summary Besides functional behaviour of coatings their resistivity against corroding attack is a crucial criterion for quality. The application of special corroding and abrading tests yields after short times predictions about stability of the product in practical use. A number of tests have been applied to thin magnetic storage media. Besides tests of function and visual observations with light- and scanning electron microscopes, AES- and XPS-investigations were applied to discuss corrosion resistivity.     

A supramolecular hydrogen‐bonded complex between 1,3,5‐tris(diisobutylhydroxysilyl)benzene and trans‐bis(4‐pyridyl)ethylene

The trisilanol 1,3,5‐(HOi‐Bu₂Si)₃C₆H₃ ( 7 ), prepared in three steps from 1,3,5‐tribromobenzene via the intermediates 1,3,5‐(Hi‐Bu₂Si)₃C₆H₃ ( 8 ) and 1,3,5‐(Cli‐Bu₂Si)₃C₆H₃ ( 9 ) forms an equimolar complex with trans‐bis(4‐pyridyl)ethylene (bpe), 7 ·bpe, whose structure was investigated by X‐ray crystallography. The hydrogen‐bonded network features a number of SiO? H(H)Si and SiO? H hydrogen bridges. Evidence was found for cooperative strengthening within the sequential hydrogen bonds. Copyright © 2007 John Wiley & Sons, Ltd.     

Supercompactness and measurable limits of strong cardinals II: Applications to level by level equivalence

We construct models for the level by level equivalence between strong compactness and supercompactness in which for κ the least supercompact cardinal and δ ≤ κ any cardinal which is either a strong cardinal or a measurable limit of strong cardinals, 2^δ > δ ⁺ and δ is < 2^δ supercompact. In these models, the structure of the class of supercompact cardinals can be arbitrary, and the size of the power set of κ can essentially be made as large as desired. This extends and generalizes [5, Theorem 2] and [4, Theorem 4]. We also sketch how our techniques can be used to establish a weak indestructibility result. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)