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     

Morphology and properties of poly[2‐methoxy‐5‐(2′‐ethyl‐hexyloxy)‐para‐phenylene vinylene]/silica nanoparticle hybrid films

Poly[2‐methoxy‐5‐(2′‐ethyl‐hexyloxy)‐para‐phenylene vinylene] (MEH‐PPV)/silica nanoparticle hybrid films were prepared and characterised. Three kinds of materials were compared: parent MEH‐PPV, MEH‐PPV/silica (hybrid A films), and MEH‐PPV/coupling agent MSMA/silica (hybrid B films), in which MSMA is 3‐(trimethoxysilyl) propyl methacrylate. It was found that the hybrid B films could significantly prevent macrophase separation, as evidenced by scanning electron and fluorescence microscopy. Furthermore, the thermal characteristics of the hybrid films were largely improved in comparison with the parent MEH‐PPV. The UV‐visible absorption spectra suggested that the incorporation of MSMA‐modified silica into MEH‐PPV could confine the polymer chain between nanoparticles and thus increase the conjugation length. The photoluminescence (PL) studies also indicated enhancement of the PL intensity and quantum efficiency by incorporating just 2 wt% of MSMA‐modified silica into MEH‐PPV. However, hybrid A films did not show such enhancement of optoelectronic properties as the hybrid B films. The present study suggests the importance of the interface between the luminescent organic polymers and the inorganic silica on morphology and optoelectronic properties. Copyright © 2004 Society of Chemical Industry     

Properties of nanoporous organosilicate hybrid thin films with a bimodal pore size distribution

Low dielectric poly[methylsilsesquioxane‐ran‐trifluoropropylsilsesquioxane‐ran‐(2,4,6,8‐tetramethyl‐2,4,6,8‐tetraethylenecyclotetrasiloxane)silsesquioxane]s {P[M‐ran‐TFP‐ran‐(TCS)]SSQs} having various compositions were synthesized using trifluoropropyl trimethoxysilane, methyl trimethoxysilane and 2,4,6,8‐tetramethyl‐2,4,6,8‐tetra(trimethoxysilylethyl)cyclotetrasiloxane. The chemical composition of the polymers and the content of SiOH end‐groups were controlled by adjusting the reaction conditions, and they were characterized by ¹H‐NMR. The thermally decomposable trifluoropropyl groups on the P[M‐ran‐TFP‐ran‐(TCS)]SSQ backbone and heptakis(2,3,6‐tri‐O‐methyl)‐β‐cyclodextrin (CD) were employed as pore generators. The dielectric constants of the porous CD/P[M‐ran‐TFP‐ran‐(TCS)]SSQ films were in the range 2.0–2.7 (at 100 kHz) depending on the concentration of the porogens, and showed no change over 4 days under aqueous conditions. The pore size of the films showed a bimodal distribution, with diameters of ca 0.5–1.0 nm for those originating from the trifluoropropyl groups and 1.7 nm from the CD. The elastic modulus and hardness of the 30 vol% CD‐blended film with a dielectric constant of 2.26 were 2.40 and 0.38 GPa, respectively, as determined by a nanoindenter. Copyright © 2005 Society of Chemical Industry     

Dynamic control of the permanent magnet-assisted reluctance synchronous machine

A digital signal processor-based control system for the permanent magnet-assisted reluctance synchronous machine, with the emphasis on dynamic performance, is proposed. A classical design approach is used to design the current and speed controllers for the machine. The stator current of the machine is controlled in such a way that the current angle in the dq synchronous reference frame is constant. The load-torque is estimated using a state space observer and compensation current based on the estimated load is used to improve the dynamic performance of the drive. The control system design is machine specific as it relies on data from finite-element analysis. Simulated and measured results on a 110-kW power level show that the resulting control system is stable and robust with good dynamic performance     

Probing the thermal decomposition process of layered double hydroxides through in situ <Superscript>57</Superscript>Fe Mössbauer and in situ X-ray diffraction experiments

The thermal decomposition properties of Mg–Fe hydrotalcites were studied through in situ ⁵⁷Fe Mössbauer spectroscopy and in situ X-ray diffraction. Abrupt changes in the quadrupolar splitting measured in the Mössbauer spectra revealed a phase transition from the starting lamellar structure to a new crystalline arrangement. By analyzing the Mössbauer parameters we show that the material is highly disordered in the 300–400 °C temperature range. This hypothesis is confirmed by the X-ray results whose diffractograms indicated the collapse of the lamellar structure and the formation of a solid solution.     

Atmospheric corrosion of reference metals in Antarctic sites

This paper presents the results obtained at three Antarctic test sites participating in the “Ibero-American Map of Atmospheric Corrosiveness” (MICAT), a project on atmospheric corrosion carried out during the period 1988–1994 at some 70 sites distributed across 12 countries of the Latin-American region, Spain and Portugal. The three Antarctic sites are located near the coastline.The singular climatic characteristics of Antarctic regions are related with the purity of the air, the absence of rainfall and the formation of ice on the metallic surface during an important part of the exposure time. However, electrochemical activity is possible below ice layers. This situation affects the structure and morphology of corrosion product films and the resulting corrosion rates of metallic surfaces.     

Modeling and Analysis of a Long Thin Conducting Stripline

A long thin conducting stripline embedded in a dielectric and centered between two large conducting plates, i.e., the stripline environment, is considered. The stripline is modeled as infinitely long, infinitely thin, and perfectly conducting by first considering a stripline of finite length, thickness, and conductivity in a dielectric layer. Starting from Maxwell's equations and assuming that the current on the stripline is a propagating wave in length direction, asymptotic expressions for the fields inside and in the neighbourhood of the stripline are deduced. These expressions are used to model the stripline in the stripline environment, which leads to a boundary-value problem for the electric potential. This problem is solved by two different approaches, leading to integral equations for the current and for an auxiliary function describing the electric potential. A relation between the current and the auxiliary function is deduced, which is used to obtain asymptotic expressions for current and impedance. Results are compared with a numerical solution of the integral equation for the current and with results in literature.     

Strategies to improve the performance of very low bit rate speech coders and application to a variable rate 1.2 kb/s codec

This paper presents several strategies to improve the performance of very low bit rate speech coders and describes a speech codec that incorporates these strategies and operates at an average bit rate of 1.2 kb/s. The encoding algorithm is based on several improvements in a mixed multiband excitation (MMBE) linear predictive coding (LPC) structure. A switched-predictive vector quantiser technique that outperforms previously reported schemes is adopted to encode the LSF parameters. Spectral and sound specific low rate models are used in order to achieve high quality speech at low rates. An MMBE approach with three sub-bands is employed to encode voiced frames, while fricatives and stops modelling and synthesis techniques are used for unvoiced frames. This strategy is shown to provide good quality synthesised speech, at a bit rate of only 0.4 kb/s for unvoiced frames. To reduce coding noise and improve decoded speech, spectral envelope restoration combined with noise reduction (SERNR) postfilter is used. The contributions of the techniques described in this paper are separately assessed and then combined in the design of a low bit rate codec that is evaluated against the North American Mixed Excitation Linear Prediction (MELP) coder. The performance assessment is carried out in terms of the spectral distortion of LSF quantisation, mean opinion score (MOS), A/B comparison tests and the ITU-T P.862 perceptual evaluation of speech quality (PESQ) standard. Assessment results show that the improved methods for LSF quantisation, sound specific modelling and synthesis and the new postfiltering approach can significantly outperform previously reported techniques. Further results also indicate that a system combining the proposed improvements and operating at 1.2 kb/s, is comparable (slightly outperforming) a MELP coder operating at 2.4 kb/s. For tandem connection situations, the proposed system is clearly superior to the MELP coder.