Spin probe study of semi‐interpenetrating polymer networks based on polyurethane and polymethacrylate functional prepolymers

The motional transition and heterogeneity of semi‐interpenetrating networks (SIPNs) based on polyurethane (PU) with carboxylic groups and methacrylic copolymer (PM) with tertiary amine groups were studied by the electron spin resonance (ESR) spin probe method. The concentration of functional groups in both prepolymers varied from 0 to 0.45 mmol g^?1. Spin‐probed SIPNs show that the temperature‐dependent spectra are sensitive to polymer interactions imposed by functional groups. These interactions determine the free volume distribution in the matrix and temperature at which motional transition takes place. The fraction of free volume increases with functional group concentration and reaches its maximum at 0.25 mmol g^?1. Further increases in the functional group concentration reduce the free volume. The results of the networks with strong interactions are discussed in terms of the interference of the plasticizing effect of the PU component and the formation of possible cluster cross‐links, which restricts segmental motions. Copyright © 2003 Society of Chemical Industry     

The effect of segment length on some properties of thermoplastic poly(ester–siloxane)s

A series of novel thermoplastic elastomers, based on poly(dimethylsiloxane) (PDMS) as the soft segment and poly(butylene terephthalate) (PBT) as the hard segment, were synthesized by catalyzed two‐step, melt transesterification reactions of dimethyl terephthalate and methyl esters of carboxypropyl‐terminated poly(dimethylsiloxane)s (M?_n = 550–2170 g mol^?1) with 1,4‐butanediol. The lengths of both the hard and soft segments were varied while the weight ratio of the hard to soft segments in the reaction mixture was maintained constant (57/43). The molecular structure, composition and molecular weights of the poly(ester–siloxane)s were examined by ¹H NMR spectroscopy. The effectiveness of the incorporation of the methyl‐ester‐terminated poly(dimethylsiloxane)s into the copolymer chains was verified by chloroform extraction. The effect of the segment length on the transition temperatures (T_m and T_g) and the thermal and thermo‐oxidative degradation stability, as well as the degree of crystallinity and hardness properties of the synthesized TPESs, were studied. Copyright © 2003 Society of Chemical Industry     

Chemische Zusammensetzung und Mikrostruktur polymerabgeleiteter Gläser und Keramiken im System Si–C–O. Teil 2: Charakterisierung der Gefügeausbildung mittels hochauflösender Durchstrahlungselektronenmikroskopie und Feinbereichsbeugung

Chemical Composition and Microstructure of Polymer‐Derived Glasses and Ceramics in the Si–C–O System. Part 2: Characterization of microstructure formation by means of high‐resolution transmission electron microscopy and selected area diffraction Liquid or solid silicone resins represent the economically most interesting class of organic precursors for the pyrolytic production of glass and ceramics materials on silicon basis. As dense, dimensionally stable components can be cost‐effectively achieved by admixing reactive filler powders, chemical composition and microstructure development of the polymer‐derived residues must be exactly known during thermal decomposition. Thus, in the present work, glasses and ceramics produced by pyrolysis of the model precursor polymethylsiloxane at temperatures from 525 to 1550 °C are investigated. In part 1, by means of analytical electron microscopy, the bonding state of silicon was determined on a nanometre scale and the phase separation of the metastable Si–C–O matrix into SiO₂, C and SiC was proved. The in‐situ crystallization could be considerably accelerated by adding fine‐grained powder of inert fillers, such as Al₂O₃ or SiC, which permits effective process control. In part 2, the microstructure is characterized by high‐resolution transmission electron microscopy and selected area diffraction. Turbostratic carbon and cubic β‐SiC precipitate as crystallization products. Theses phases are embedded in an amorphous matrix. Inert fillers reduce the crystallization temperature by several hundred °C. In this case, the polymer‐derived Si–C–O material acts as a binding agent between the powder particles. Reaction layer formation does not occur. On the investigated pyrolysis conditions, no crystallization of SiO₂ was observed.     

Development of geometrically exact new shell elements based on general curvilinear co‐ordinates

In the present study first‐order shear deformable shell finite elements based on general curvilinear co‐ordinates are proposed. For the development of the present shell elements, a partial mixed variational functional with independently assumed strains is provided in order to avoid the severe locking troubles known as transverse shear and membrane lockings. Bubble functions are included in the shape function of displacement to improve the performance of the developed element. The proposed assumed strain four‐ and nine‐node elements based on the general tensor shell theory provide an efficient linkage framework for shell surface modelling and finite element analysis. In the several benchmark problems, the present shell elements with exact geometric representations demonstrate their performance compared to previously reported results. Copyright © 2002 John Wiley & Sons, Ltd.     

The Cooperative Molecular Field Effect

Two‐dimensional arrangements of molecules can show remarkable cooperative electronic effects. Such effects can serve to achieve direct electronic sensing of chemical and physical processes via electrostatic effects, i.e., without transfer of charge or matter between the locus of sensing and that of detection.     

Energy use in controlled temperature marine aquaculture

Temperature control offers benefits in land‐based marine aquaculture: stock growth rates may be enhanced by heating in winter; mortality rates in summer may be reduced by cooling. However, if the plant is not well designed, temperature control may create very large energy demands. This paper describes the application of temperature control in abalone aquaculture in New Zealand, with a focus on energy considerations in plant design. An abalone farm using a semi‐closed water conditioning system is used as a case study for which an energy model, based on a heat pump system, is developed. The model is used to determine the impact of plant design and tank conditions on the economics of the operation. Copyright © 2002 John Wiley & Sons, Ltd.     

CD++: a toolkit to develop DEVS models

The features of a toolkit for modeling and simulation based on the DEVS formalism are presented. The tool is built as a set of independent software pieces running on different platforms. Not only are the main characteristics of the environment presented, a focus on its use is also considered by inclusion of application examples for a variety of problems. Many models can be defined in an automated fashion, simplifying the construction of new models and easing their verification. The use of this formal approach has allowed the development of safe and cost‐effective simulations, significantly reducing development time. Copyright © 2002 John Wiley & Sons, Ltd.     

Breakdown characteristics of oil and paper insulation for a very fast transient voltage

This paper describes the dielectric breakdown characteristics of oil and oil‐impregnated paper for very fast transient (VFT) voltages. Blumlein circuits generate VFT voltages of 60 and 300 ns in a pulse width that simulates disconnecting switching surges in gas‐insulated switch gears. We measured the breakdown voltages of needle‐to‐plane, plane‐to‐plane oil gaps and several pieces of paper between plane electrodes for VFT and lightning impulse voltages. The measured data were formulated in V‐t characteristics and Weibull probability distributions. The inclination n of V‐t characteristics of insulating paper is 150, which is less than n = 13.7 of the plane‐to‐plane oil gap in the VFT time range. The shape parameters of Weibull distribution obtained in this study show that the scattering of breakdown voltages of paper is much less than that of oil. © 2002 Wiley Periodicals, Inc. Electr Eng Jpn, 141(4): 16–24, 2002; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/eej.10043     

A robust adaptive pole‐placement controller without strictly positive real condition

This paper considers the adaptive pole‐placement control problem for system (1) with unmodelled dynamics η_n dominated by a small constant ε multiplied by a quantity independent of ε but tending to infinity as the past input, output, and noise grow. Using bounded external excitation and randomly varying truncation techniques, we give a design method of adaptive pole‐placement controller. It is shown that the closed‐loop system is globally stable, the estimation error for the parameter contained in the modelled part is of order ε, and the closed‐loop system under the adaptive pole‐placement control law is suboptimal in the sense of $$\mathop{\lim\sup}\limits_{{n\to\infty }}{1\over n}\mathop{\sum}\limits_{i=0}^n{\left({A^{*}(z)y_{n}‐L(z)C(z)w_{n}‐B(z)R(z)y_{n}^{*}}\right)^{2}{\leq}O({\varepsilon}^{2})+\gamma^{2}\mathop{\sum}\limits_{j=1}^q{b_{j}^{2}}}$$\nopagenumbers\end while the SPR condition used usually in other papers is replaced by a stability condition. Copyright © 2001 John Wiley & Sons, Ltd.     

Monoacylglycerols derived from butter oil by Penicillium roquefortii in suspension cultures

Structural isomers of monoacylglycerols (monoglycerides, MAGs) were identified and compared after degradation of butter oil by two strains of Penicillium roquefortii and a commercial lipase from P roquefortii (EC 3.1.1.3) at pH 7.0 and 10 °C. The conditions were selected as they were comparable with those used in the manufacture of blue mould‐ripened cheese. The commercial lipase was selected to compare with the fungal strains in terms of acyl migration. Results showed that the main isomers formed by lipolysis with the commercial lipase were sn‐2 MAGs (64 mol%), whilst spores and emerging mycelia of P roquefortii produced mainly sn‐1(3) MAGs (83–90 mol%). The work reported here may lead to further assessment of different MAG structural isomers as natural preservatives in foods and dairy products. © 2002 Society of Chemical Industry