Dielectric transition of polyacrylonitrile derived carbon nanofibers

The dielectric behavior of polyacrylonitrile derived carbon nanofibers formed at different carbonization temperatures was investigated using impedance spectroscopy. The impedance data are presented in the form of Cole-Cole plots and four equivalent electrical circuits are derived. It is found that by increasing carbonization temperature from 500 to 800 °C, a strong capacitive element in the parallel equivalent circuit is transformed into an inductive element, while the contact resistance and parallel resistance are significantly decreased. Along with the morphological and chemical structural evolution, respectively witnessed by scanning electron microscopy and Raman spectroscopy, the dielectric transition deduced from the transformation of electrical circuits can be correlated to the proposed microstructural changes of polyacrylonitrile derived carbon nanofibers and the interaction/interference among them.

Isotropic compression of mixtures of hard and soft spheres

The compaction behaviour of powders with soft and hard components is of particular interest to the paint processing industry. Unfortunately, at the present time, very little is known about the internal mechanisms within such systems and therefore suitable tests are required to help in the interpretative process. The TRUBAL, Distinct Element Method (D.E.M.) program was the method of investigation used in this study. Steel (hard) and rubber (soft) particles were used in the randomly-generated, binary assemblies because they provided a sharp contrast in physical properties. For reasons of simplicity, isotropic compression of two-dimensional assemblies was also initially considered. The assemblies were first subject to quasi-static compaction, in order to define their behaviour under equilibrium conditions. The stress-strain behaviour of the assemblies under such conditions was found to be adequately described by a second-order polynomial expansion. The structural evolution of the simulation assemblies was also similar to that observed for real powder systems. Further simulation tests were carried out to investigate the effects of particle size on the compaction behaviour of the two-dimensional, binary assemblies. Later work focused on the quasi-static compaction behaviour of three-dimensional assemblies, because they represented more realistic particle systems. The compaction behaviour of the assemblies during the simulation experiments was considered in terms of percolation theory concepts, as well as more familiar macroscopic and microstructural parameters. Percolation theory, which is based on ideas from statistical physics, has been found to be useful in the interpretation of the mechanical behaviour of simple, elastic lattices. However, from the evidence of this study, percolation theory is also able to offer a useful insight into the compaction behaviour of more realistic particle assemblies.

On the active site in H3PW12O40/SiO2 catalysts for fine chemical synthesis

The surface environment and structural evolution of silica supported phosphotungstic acid (H3PW12O40) catalysts have been investigated as a function of acid loading. H3PW12O40 clusters are deposited intact upon the silica surface, adopting a Stranksi-Krastanov growth mode forming a two-dimensional adlayer which saturates at 45wt% acid. Intimate contact with the silica support perturbs the local chemical environment of three tungstate centres, which become inequivalent with those in the remaining cluster, suggesting an adsorption mode involving three terminal W==O groups. Above the monolayer, H3PW12O40 clusters form three-dimensional crystallites with physico-chemical properties indistinguishable from those in the bulk heteropoly acid. These H3PW12O40/SiO2 materials are efficient for the solventless isomerisation of α-pinene under mild reaction conditions. Activity scales directly with the number of accessible perturbed tungstate sites at the silica interface; these are the active species.

Structure-reactivity correlations in the selective aerobic oxidation of cinnamyl alcohol:in situ XAFS

The structural evolution of a Pd/C catalyst during the liquid phase selective aerobic oxidation of cinnamyl alcohol has been followed by in situ XAFS and XPS. The fresh catalyst comprised highly dispersed, heavily oxidised Pd particles. Cinnamyl alcohol oxidation resulted in the rapid reduction of surface palladium oxide and a small degree of concomitant particle growth. These structural changes coincided with a large drop in catalytic activity. Prereduced Pd/C exhibited a significantly lower initial oxidation rate demonstrating the importance of surface metal oxide in effecting catalytic oxidation. Use of a Pd black model system confirmed that the oxide→metal transformation was the cause, and not result, of catalyst deactivation.

A post-structural analysis of perceptions and experiences of continuity and change within the UK automotive supplier base

Firms acting as suppliers to the British automotive industry have a long history of so doing, with some evidencing histories that predate even the invention of the motor car. In exploring the challenges faced by the descendants of these firms in the 1990s, a review is undertaken of the bodies of literature surrounding the changes wrought through the increased globalisation of the industry; the impact of new manufacturing technologies and techniques; the rising levels of co-operation between firms; and the growing impact of the automotive 'service sector'. Moreover, an exploration is undertaken of the perceived 'realities' of the automotive industry as constructed through discourse, including the ways in which discourse effects a continual reinterpretation and re-evaluation of the historical evolution of the industry. Attention is focused on the implications of the above for the automotive supply chain, and the means for its rationalisation proposed by the major car manufacturers and their partner-suppliers. Post-structuralist approaches are introduced as part of an attempt to establish and appropriate research methodology that can explore and deconstruct the discourses surrounding 'modernity', 'supply chain rationalisation', 'flexible specialisation' and 'globalisation' within the automotive industry. Analytical research is conducted into the small- to medium-sized business that constitute the majority of the supplier base in the United Kingdom, and the findings of this research are compared with those of a similar study conducted a quarter-century ago. In this way, the relationships of these firms with their customers, suppliers, and peers are investigated, as are their perceptions of a changing marketplace and their reactions to the impact of policies such as the 'supply chain rationalisation' pursued by the major automotive manufacturers. Authoritative discourses of industry form, function, and structure are challenged, with voice being granted to the marginalised: small suppliers, 'service sector' firms, or those only partly involved in the automotive industry.

Mesozoic to recent evolution of the Andean forearc of northern Chile (22-24 s)

The Andean forearc of northern Chile comprises four morphotectonic units, which include from east to west: 1) The Cordillera de la Costa: composed of Jurassic granites and andesites, thought to represent a volcanic arc, the Mejillones terrane, an accreted allochthonous terrane, and the Lower Cretaceous Coloso basin, which formed through forearc extension along the suture between the Mejillones terrane and the Jurassic arc. Palaeomagnetic studies of the above units have identified approximately 29+/-11 degrees of clockwise rotation. Rotation is due to extension (caused by subduction roll back and slab pull), at an angle to the direction of absolute motion of the South American Plate. 2) The Central Depression: a large arid basin containing isolated fault-bounded blocks of pre-Mesozoic metamorphosed igneous rocks, Triassic sediments and volcanics, and Jurassic carbonates, deposited in a. back-arc basin setting. The isolated blocks formed through extension along previous thrust faults, these originated through compression of the back-arc basin due to accretion of the Jurassic volcanic arc. 3) The Precordillera.: composed of Permian-Triassic rift-related sediments and volcanics, Jurassic continental sediments synchronous with back-arc basin sedimentation, and Cretaceous and Oligo-Miocene continental sediments deposited in foreland basins. Palaeomagnetism has identified clockwise rotation in rocks ranging in age from Jurassic-Miocene. Rotation in the Precordillera. affected larger structural blocks than in the Cordillera de la Costa. 4) The Salar Depression: a. series of arid continental basins developed on continental crust. These basins nay have originated in the Triassic, when rifting of the South American craton is thought to have taken place. In conclusion, palaeomagnetic and geological evidence is consistent with the view that the north Chilean forearc was largely under an extensional stress regime. However, the presence of extensive compressional structures in Palaeocene and older rocks in the forearc together with the currently active foreland thrust belt of Argentina. indicate that throughout the evolution of the Andean Orogen, a delicate balance between compressional and extensional tectonic regimes has existed.

Impact of third-order fibre dispersion on the evolution of parabolic optical pulses

We develop a perturbation analysis that describes the effect of third-order dispersion on the similariton pulse solution of the nonlinear Schrodinger equation in a fibre gain medium. The theoretical model predicts with sufficient accuracy the pulse structural changes induced, which are observed through direct numerical simulations.

Deindustrialisation and structural change during the post-Communist transition

The aim of this paper is to model the evolution of employment structure in post-communist economies in the broader context of deindustrialisation. The paper builds on the model of structural change developed by Rowthorn and Wells (1987). We show that the starting point of high industry sector share in total employment and its direct fall when productivity of sectors changes in favour of services can be explained in terms of this framework. Moreover, the model can also describe the phenomenon of a further expansion of the agriculture, observed in countries classified as "less consistent" in the reforms implementation. Hence, we distinguish two development paths, the efficient one, called "horizontal", and the inefficient one called "vertical". We illustrate it with empirical data, using alternative measures of structural change and patterns of structural evolutions during transition. Finally, we discuss the link between the EBRD indicators of reforms and structural change. We show that the "quality" of reforms, not the initial GDP level determines a country's development path.

On the structural repertoire of pools of short, random RNA sequences

A detailed knowledge of the mapping between sequence and structure spaces in populations of RNA molecules is essential to better understand their present-day functional properties, to envisage a plausible early evolution of RNA in a prebiotic chemical environment and to improve the design of in vitro evolution experiments, among others. Analysis of natural RNAs, as well as in vitro and computational studies, show that certain RNA structural motifs are much more abundant than others, pointing out a complex relation between sequence and structure. Within this framework, we have investigated computationally the structural properties of a large pool (10 molecules) of single-stranded, 35 nt-long, random RNA sequences. The secondary structures obtained are ranked and classified into structure families. The number of structures in main families is analytically calculated and compared with the numerical results. This permits a quantification of the fraction of structure space covered by a large pool of sequences. We further show that the number of structural motifs and their frequency is highly unbalanced with respect to the nucleotide composition: simple structures such as stem-loops and hairpins arise from sequences depleted in G, while more complex structures require an enrichment of G. In general, we observe a strong correlation between subfamilies-characterized by a fixed number of paired nucleotides-and nucleotide composition. Our results are compared to the structural repertoire obtained in a second pool where isolated base pairs are prohibited. © 2008 Elsevier Ltd. All rights reserved.

Impact of third-order dispersion on the evolution of parabolic pulses

We present a perturbation analysis that describes the effect of third-order dispersion on the similariton pulse solution of the nonlinear Schrödinger equation in a fibre gain medium. The theoretical model predicts with sufficient accuracy the pulse structural changes induced, which are observed through direct numerical simulations.

Impact of third-order dispersion on the evolution of parabolic pulses

We present a perturbation analysis that describes the effect of third-order dispersion on the similariton pulse solution of the nonlinear Schrödinger equation in a fibre gain medium. The theoretical model predicts with sufficient accuracy the pulse structural changes induced, which are observed through direct numerical simulations.