Atomistic models of three fluorinated polyimides in the amorphous state

Molecular models of three fluorinated polyimides based on the 4,4′‐(hexafluoroisopropylidene)diphthalic dianhydride (6FDA) have been studied using molecular dynamics (MD) simulations. The respective diamines were 4,4′‐hexafluoroisopropylidene dianiline (6FpDA), 3,3′‐hexafluoroisopropylidene dianiline (6FmDA), and 2,4,6‐trimethyl‐1,3phenylenediamine (DAM). Thirty independent samples were prepared using a hybrid pivot Monte Carlo‐MD generation technique and average densities were found to be in very good agreement with experiment. Model structures also agreed with available wide‐angle X‐ray scattering data. Cohesive energies, Hildebrand solubility parameters, fractional free volumes (FFV), void space distributions and intermolecular as well as intramolecular interactions were analyzed. The differences in bulk properties between both 6FDA‐6FpDA and 6FDA‐6FmDA isomers remain fairly small, although the configurations of the former are more extended. 6FDA‐DAM has a lower density, larger intermolecular distances, and higher free volume than the other two polyimides. Results are discussed with respect to their use as matrices for gas separation. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1166–1180, 2009     

Initiator selectivity during free radical copolymerizations of styrene and methyl methacrylate initiated by anaerobic copper(II) oxidation of carbon‐13 labeled acetophenone

Nuclear magnetic resonance (NMR) analysis of the ¹³C‐labeled chain ends of polystyrene, polyMMA, and styrene‐MMA copolymers prepared by polymerizations initiated using ¹³C‐labeled‐phenacyl radicals were investigated. The phenacyl radicals were generated by anaerobic oxidation of acetophenone‐methyl‐¹³C using a Cu(II) octanoate‐pyridine complex in the presence of triethylamine and triphenylphosphine. NMR analysis of the ¹³C‐labeled chain ends of these polymers afforded insight into the initiation mechanism. In copolymerization experiments using ¹³C‐labeled acetophenone initiator, the NMR spectra provided evidence that the phenacyl radical reacts 2.7 times faster with styrene than with MMA. The resonances of the labeled phenacyl carbons also showed that the sequence and stereosequence distributions of monomer units at the chain ends are nearly the same as those that prevail along the polymer chains. Styrene–styrene, styrene–MMA, and MMA–styrene enchainments at the chain ends are equally likely to have meso (erythro) or racemic(threo) configurations but the ratio of meso to racemic MMA‐MMA enchainments is ～ 3/7. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2347–2356, 2008     

An Entropy-Based Approach to Measurement of Stock Market Depth

The aim of this study is to investigate market depth as a stock market liquidity dimension. A new methodology for market depth measurement exactly based on Shannon information entropy for high-frequency data is introduced and utilized. The proposed entropy-based market depth indicator is supported by an algorithm inferring the initiator of a trade. This new indicator seems to be a promising liquidity measure. Both market entropy and market liquidity can be directly measured by the new indicator. The findings of empirical experiments for real-data with a time stamp rounded to the nearest second from the Warsaw Stock Exchange (WSE) confirm that the new proxy enables us to effectively compare market depth and liquidity for different equities. Robustness tests and statistical analyses are conducted. Furthermore, an intra-day seasonality assessment is provided. Results indicate that the entropy-based approach can be considered as an auspicious market depth and liquidity proxy with an intuitive base for both theoretical and empirical analyses in financial markets.     

Force-Free States, Relative Strain, and Soft Elasticity in Nematic Elastomers

The remarkable ability of nematic elastomers to exhibit large deformations under small applied forces is known as soft elasticity. The recently proposed neo-classical free-energy density for nematic elastomers, derived by molecular-statistical arguments, has been used to model soft elasticity. In particular, the neo-classical free-energy density allows for a continuous spectrum of equilibria, which implies that deformations may occur in the complete absence of force and energy cost. Here we study the notion of force-free states in the context of a continuum theory of nematic elastomers that allows for isotropy, uniaxiality, and biaxiality of the polymer microstructure. Within that theory, the neo-classical free-energy density is an example of a free-energy density function that depends on the deformation gradient only through a nonlinear strain measure associated with the deformation of the polymer microstructure relative to the macroscopic continuum. Among the force-free states for a nematic elastomer described by the neo-classical free energy density, there is, in particular, a continuous spectrum of states parameterized by a pair of tensors that allows for soft deformations. In these force-free states the polymer microstructure is material in the sense that it stretches and rotates with the macroscopic continuum. Limitations of and possible improvements upon the neo-classical model are also discussed. This revised version was published online in July 2006 with corrections to the Cover Date.     

Fractals — An overview of potential applications to transport in porous media

We present an overview of the potential applicability of fractal concepts to various aspects of transport phenomena in heterogeneous porous media. Three examples of phenomena where a fractal approach should prove illuminating are presented. In the first example we consider pore level heterogeneities as typified by pore surface roughness. We suggest that roughness may be usefully modelled by fractal curves and surfaces and also cite experimental evidence for regarding pores as fractals. In the second example we consider a fractal network approach to modelling large-scale heterogeneities. The presence of features on all length scales in simple fractal models should capture the essential role played by the presence of heterogeneities on many scales in natural reservoirs. Studies of transport phenomena in such models may yield valuable insights into the problems of macroscopic dispersion. The final example concerns dispersion in multiphase flow. Here the fractal character is attributed to the distribution of the fluid phases rather than the porous medium itself. Again studies of transport phenomena in simple fractal models should help to clarify various problems associated with the corresponding phenomena in real reservoirs.     

Sheet AA2024‐T3: a new investigation of microstructure and composition

Sheet AA2024‐T3 is probably one of the most studied aluminium alloys in the corrosion field, because, with copper as an alloying addition, it is one of the most corrosion‐prone aluminium alloys. This paper reports new findings on the composition and distribution of intermetallic (IM) particles in AA2024‐T3 through the examination of over 80 000 compositional domains in nearly 18 000 IM particles. This work was achieved by using an electron microprobe to map out 2 × 2 mm² at a step size of 400 nm. This study revealed that the composition of individual particles can vary considerably from ‘accepted’ compositions. Domains within particles were extensive across the surface. Because such a large area was mapped, it was possible to subdivide this area and to look at the variation of particle statistics from region to region, providing some information on the statistical variation for small electrodes. Copyright © 2010 John Wiley & Sons, Ltd.     

The Design of Biodegradable Microcarriers for Induced Cell Aggregation

PLLA microspheres were aminolyzed in hexanediamine/propanol solution to introduce free amino groups on their surface, which were further transferred into aldehyde groups by a treatment of glutaraldehyde. Chitosan‐graft‐lactose was then covalently coupled via Schiff base formation. Morphological variation and chitosan‐graft‐lactose immobilization were characterized. In vitro culture of rabbit auricular chondrocytes demonstrated that the PLLA microcarriers could effectively support the cell attachment and particularly induce cell aggregation on their surface. The formed cell aggregates/microcarriers composite showed higher viability and extracellular matrix production. Thus, the PLLA microcarriers can be potentially used as an injectable delivery system for cartilage repair.

     

Hot deformation in nanocrystalline Ndben Feben B backward extruded rings

Radially oriented Nd-Fe-B rings are prepared by backward extrusion of fine grained melt-spun powder. Melt-spun powder with the nominal composition of Nd_30.5Fe_bal.Co_6.0Ga_0.6Al_0.2B_0.9 (wt%) is used as starting material. The effects of process variables, such as deformation temperature (T_d), strain rate (ε) and height reduction (Δh%), on the magnetic properties of the rings are investigated. A scanning electron microscope (SEM) equipped with an energy spectrum device is used to study the metallograph and microfracture of the extruded rings. The B_r and (BH)_max reach the optimum values at T_d=800℃, ε =0.01 mm/s, and Δh% =70%. It is found by SEM observations that the particle boundaries, which seemingly correspond to the interfaces of the starting melt-spun powders, emerge after the corrosion of metallography specimens. This is helpful for studying the effects of powder-powder interface on the local deformation and deformation homogeneity in the rings. For different spatial positions of the extruded rings, there are characteristic metallographies and microfractures. The upper end of the rings has the least deformation and worst texture, and therefore the worst magnetic properties. The magnetic properties in the radial direction increase slightly along the axis from the bottom to the middle, then steeply decrease at the upper end of the ring. The deformation and the formation-of-texturing processes are discussed. The deformation and the texturing formation of melt-spun Nd-Fe-B alloys probably involve grain boundary sliding and grain rotation, the solution-precipitation process and preferential growth of Nd₂Fe₁₄B nanograins along the easy growth a-axis.     

Effect of substrate temperature on microstructure and optical properties of single-phased Ag20 film deposited by using radio-frequency reactive magnetron sputtering method

Using a radio-frequency reactive magnetron sputtering technique, a series of the single-phased Ag20 films are deposited in a mixture of oxygen and argon gas with a flow ratio of 2：3 by changing substrate temperature （Ts）. Effects of the Ts on the microstructure and optical properties of the films are investigated by using X-ray diffractometry, scanning electron microscopy and spectrophotometry. The single-phased Ag20 films deposited at values of Ts below 200℃ are （111） preferentially oriented, which may be due to the smallest free energy of the （111） crystalline face. The film crystallization becomes poor as the value of Ts increases from 100℃ to 225℃. In particular, the Ag20 film deposited at Ts=225℃ loses the （111） preferential orientation. Correspondingly, the film surface morphology obviously evolves from a uniform and compact surface structure to a loose and gullied surface structure. With the increase of Ts value, the transmissivity and the reflectivity of the films in the transparent region are gradually reduced, while the absorptivity gradually increases, which may be attributed to an evolution of the crystalline structure and the surface morphology of the films.     

Growth and magnetic properties of single crystalline Ni nanowire arrays prepared by pulse DC electrodeposition

Highly textured Ni nanowire arrays were fabricated into anodic aluminum oxide(AAO) templates by pulse DC electrodeposition.The applied voltage and pH value of electrolytes were found strongly affecting the microstructure and magnetic properties of Ni nanowire arrays.Low applied potential and pH value both prefer to form polycrystalline fcc Ni nanowires.Increasing the applied potential or pH value favors the Ni [220] texture and even eventually forms the [220] oriented single crystal Ni wires,while exorbitan...