Immobilization and activation of vanadium(III) and titanium(III) single‐site catalysts for ethylene polymerization using MgCl2‐based supports

Significant increases in the activity of vanadium(III) amidinate catalysts for ethylene polymerization have been obtained by immobilization on a MgCl₂‐based support prepared by reaction of AlEt₃ with a MgCl₂/ethanol adduct. Catalyst immobilization and activation on this type of support prevents the rapid decay in activity observed under homogeneous polymerization conditions with unsupported catalysts. Stable polymerization activity is also observed with analogous titanium(III) complexes. Polyethylene with narrow molecular weight distribution and spherical particle morphology is obtained without reactor fouling. Copyright © 2005 Society of Chemical Industry     

Properties of poly(ethylene terephthalate)–poly(ethylene naphthalene 2,6‐dicarboxylate) blends with montmorillonite clay

The production and properties of blends of poly(ethylene terephthalate) (PET) and poly(ethylene naphthalene 2,6‐dicarboxylate) (PEN) with three modified clays are reported. Octadecylammonium chloride and maleic anhydride (MAH) are used to modify the surface of the montmorillonite–Na⁺ clay particles (clay–Na⁺) to produce clay–C18 and clay–MAH, respectively, before they are mixed with the PET/PEN system. The transesterification degree, hydrophobicity and the effect of the clays on the mechanical, rheological and thermal properties are analysed. The PET–PEN/clay–C18 system does not show any improvements in the mechanical properties, which is attributed to poor exfoliation. On the other hand, in the PET–PEN/clay–MAH blends, the modified clay restricts crystallization of the matrix, as evidenced in the low value of the crystallization enthalpy. The process‐induced PET–PEN transesterification reaction is affected by the clay particles. Clay–C18 induces the largest proportion of naphthalate–ethylene–terephthalate (NET) blocks, as opposed to clay–Na⁺ which renders the lowest proportion. The clay readily incorporates in the bulk polymer, but receding contact‐angle measurements reveal a small influence of the particles on the surface properties of the sample. The clay–Na⁺ blend shows a predominant solid‐like behaviour, as evidenced by the magnitude of the storage modulus in the low‐frequency range, which reflects a high entanglement density and a substantial degree of polymer–particle interactions. Copyright © 2005 Society of Chemical Industry     

A shell for cooperating expert systems

Abstract: This paper describes a shell for cooperating expert systems that has been developed at the University of Porto. The main goal of this shell is two-fold: to generate a community of cooperative knowledge-based systems and to develop several special reasoning techniques which can be used under a distributed and cooperative paradigm. UPShell is able to convert a set of generated intelligent systems (ISs) into a community of cooperative ISs. In this first version it is already possible to generate different intelligent systems which are able to run 'simultaneously' as separate Unix processes and, using a message-passing mechanism, to communicate among themselves. They can be set to pursue an overall goal in a cooperative way. Moreover, several tasks can be given to each IS to be solved simultaneously, and the IS can switch from task to task according to dynamic priorities reflecting the urgency attached to the specific sub-tasks that emerge. The shell described here may also be used to test, within a distributed environment, some time-bounded reasoning techniques that are presently being developed. The paper has three main parts: a general overview of the UPShell (Section 1); a tutorial explaining, by means of examples, how to use the package (Section 2); and, finally, some considerations on the reasoning techniques used and future improvements (Sections 3–5).     

A micromechanical model for cleavage-crack reinitiation

A crack-tip screening analysis of cleavage fracture of steel is developed. The analysis incorporates evidence that reinitiation of an arrested cleavage crack requires less stress intensity than cleavage initiation from a fatigue precrack. Fractographic evidence as well as metallographic sectioning of arrested cracks have previously shown that the mechanism of rapid crack propagation by cleavage is affected strongly by partial crack-plane deflection which leaves unbroken ligaments in its wake. The tearing of these ligaments by dimple rupture is the dominant energy-absorbing mechanism. Earlier etch-pit experiments using an Fe-Si alloy showed that the crack-tip stress intensity based on plastic zone size is extremely low. These observations are incorporated into a model in which cleavage crack reinitiation is analyzed using a sharp crack that is shielded by a distribution of pinching forces along its faces. During reloading of the arrested crack, the ligaments restrict crack-tip blunting, leading to higher local stresses. As a result, lower stress intensities are needed for reinitiation than for initiation from a fatigue precrack.     

Transport of K in PVC matrix membranes containing valinomycin

We report impedance measurements on PVC matrix membranes which contain KBPh₄ with varying proportions of valinomycin. In agreement with our earlier measurements the value of the bulk membrane resistance (R_b) is much larger in the presence of valinomycin, indicating that the mobility of K⁺ is greatly reduced by the valinomycin. R_b shows a linear variation with valinomycin/K⁺ ratio between 0 and 1, but it is invariant at higher valinomycin/K⁺ ratios. Thus there is no evidence for a special transport mechanism for K⁺ in these membranes.     

Impact Fracture of Thermally Tempered Glass Helicopter Windshields

In-service fracture of helicopter windshields was studied. Simulated catastrophic fracture tests were conducted by firing alumina and steel spheres onto stationary tempered and as-received glass panels. The results were studied by Hertzian analysis and modified Auerbach's relations. Thermally tempered glass shows much higher impact resistance than that estimated from superposition of residual stresses. Subcritical impact sites exhibit slow crack growth in tempered plates, eventually leading to fracture of the entire plate.     

The function of bleaching earths in the processing of palm,palm kernel and coconut oils

The results presented in the literature, which attempt to elucidate the mechanisms by which triglyceride oils are bleached by earths, are reviewed. The impact of this work and how the mechanistic proposals affect changes in oil properties are considered, with particular emphasis on the needs of the palm oil processor. Important properties include color, metals and phosphorus content and oxidative stability of the oil. Investigations made in our own laboratories have been aimed at elucidating the effect of varying physical and chemical properties of the bleaching earth on the quality of bleached and deodorized oils. Techniques used in this work are pore-size distribution, surface area, scanning and transmission electron microscopy and a variety of chemical and X-ray analysis methods. The ability to vary such parameters in montmorillonite clays by alteration of process conditions to give materials with specific performance characteristics is demonstrated. Comparisons are made between acid-activated montmorillonites and other clay types.     

Optical networks for local loop applications

Some of the options for optical technology within the local loop environment are examined. In particular, passive shared access networks have been considered in some detail. These networks show great promise for delivering existing telephone services to small to medium business customers (4-30 lines) economically by the early 1990s. Extending fiber to the home will also be possible by virtue of a similar passive network infrastructure for customers requiring new broadband services beyond the single telephone line. For one-line plain old telephone service (POTS) customers, an intermediate approach of terminating the fiber network at the final network distribution point, with copper retained for the final leg, may be used prior to the provision of broadband services. A key feature of the passive optical network architecture is the use of wavelength-division multiplexing (WDM) as an upgrade strategy, allowing graceful upgrading from telephone services to multichannel high-definition television (HDTV) on gigabit/second bearers and full two-way switched broadband services employing wavelength routing across the network