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.     

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.     

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.     

A new efficient method for one‐pot conversions of aryl carboxylic acids into nitriles without solvent

A new efficient method for synthesising nitriles, important organic reagents, is reported in this paper. In an environmentally benign solvent‐free system, aryl carboxylic acids were converted into the corresponding nitriles via one‐pot reactions, by amidation with ethyl carbamate followed by dehydration with thionyl chloride, in excellent yields. The results showed that the method has the advantages of lower cost, higher yield, less pollution and greater ease of work‐up. Copyright © 2008 Society of Chemical Industry     

Clarification of a wheat straw‐derived medium with ion‐exchange resins for xylitol crystallization

BACKGROUND: Xylitol bioproduction from lignocellulosic residues comprises hydrolysis of the hemicellulose, detoxification of the hydrolysate, bioconversion of the xylose, and recovery of xylitol from the fermented hydrolysate. There are relatively few reports on xylitol recovery from fermented media. In the present study, ion‐exchange resins were used to clarify a fermented wheat straw hemicellulosic hydrolysate, which was then vacuum‐concentrated and submitted to cooling in the presence of ethanol for xylitol crystallization. RESULTS: Sequential adsorption into two anion‐exchange resins (A‐860S and A‐500PS) promoted considerable reductions in the content of soluble by‐products (up to 97.5%) and in medium coloration (99.5%). Vacuum concentration led to a dark‐colored viscous solution that inhibited xylitol crystallization. This inhibition could be overcome by mixing the concentrated medium with a commercial xylitol solution. Such a strategy led to xylitol crystals with up to 95.9% purity. The crystallization yield (43.5%) was close to that observed when using commercial xylitol solution (51.4%). CONCLUSION: The experimental data demonstrate the feasibility of using ion‐exchange resins followed by cooling in the presence of ethanol as a strategy to promote the fast recovery and purification of xylitol from hemicellulose‐derived fermentation media. Copyright © 2008 Society of Chemical Industry     

Poly(butylene terephthalate)–clay nanocomposites prepared by melt intercalation: morphology and thermomechanical properties

Nanocomposites based on poly(butylene terephthalate) (PBT) and an organoclay (Cloisite 30B) were prepared by melt blending using a twin‐screw extruder. Two kinds of PBTs, ie PBT‐A and PBT‐B, with different inherent viscosities (η_inh), were used for this study (η_inh of PBT‐A and PBT‐B were 0.74 and 1.48, respectively). Dispersion of the clay layers in the PBT nanocomposites was characterized by using X‐ray diffraction (XRD) and transmission electron microscopy (TEM). Tensile and dynamic mechanical properties and non‐isothermal crystallization temperatures of the nanocomposites were also examined. Nanocomposites based on the higher‐viscosity PBT (PBT‐B) showed a higher degree of exfoliation of the clay and a higher reinforcing effect when compared to the composites based on the lower‐viscosity PBT (PBT‐A). The clay nanolayers dispersed in PBT matrices lead to increases in the non‐isothermal crystallization temperatures of the PBTs, with such increases being more significant for the PBT‐B nanocomposites than for the PBT‐A nanoocomposites. Copyright © 2004 Society of Chemical Industry