Associative properties of perfluorooctyl end‐functionalized polystyrene–poly(ethylene oxide) diblock copolymers

The synthesis of 2,2,3,3‐tetrahydro‐perfluoroundecanoyl end‐functionalized polystyrene–poly(ethylene oxide) block (PS‐block‐PEO‐R_F) copolymers and their matching PS‐block‐PEO diblock copolymers was carried out by sequential anionic polymerization. Viscometry and ¹⁹F NMR studies show that the PS‐block‐PEO copolymers, in contrast to their matching PS‐block‐PEO‐R_F copolymers, exhibit a micellar rather than the associative behavior seen for the latter. However, the presence of an excess of fluorinated acid, used for end‐functionalization, produces a reduction of the associative behavior above the overlap concentration, with the fluorinated acid acting like a surfactant. A competition may also occur between PS—and R_F—mediated micellization. Copyright © 2004 Society of Chemical Industry     

Methacryloxyethyl phosphate‐grafted expanded polytetrafluoroethylene membranes for biomedical applications

Expanded polytetrafluoroethylene (ePTFE) membranes were modified by graft copolymerization with methacryloxyethyl phosphate (MOEP) in methanol and 2‐butanone (methyl ethyl ketone (MEK)) at ambient temperature using gamma irradiation. The effect of dose rate (0.46 and 4.6 kGy h^?1), monomer concentration (1–40 %) and solvent were studied and the modified membranes were characterized by weight increase, X‐ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). XPS was used to determine the % degree of surface coverage using the C? F (ePTFE membrane) and the C? C (MOEP graft copolymer) peaks. Grafting yield, as well as surface coverage, were found to increase with increasing monomer concentration and were significantly higher for samples grafted in MEK than in methanol solution. SEM images showed distinctly different surface morphologies for the membranes grafted in methanol (smooth) and MEK (globular), hence indicating phase separation of the homopolymer in MEK. We propose that in our system, the non‐solvent properties of MEK for the homopolymer play a more important role than solvent chain transfer reactions in determining grafting outcomes. Copyright © 2005 Society of Chemical Industry     

Trenched‐Sinker LDMOSFET (TS‐LDMOS) Structure for 2 GHz Power Amplifiers

This paper proposes a new LDMOSFET structure with a trenched sinker for high‐power RF amplifiers. Using a low‐temperature, deep‐trench technology, we succeeded in drastically shrinking the sinker area to one‐third the size of the conventional diffusion‐type structure. The RF performance of the proposed device with a channel width of 5 mm showed a small signal gain of 16.5 dB and a maximum peak power of 32 dBm with a power‐added efficiency of 25% at 2 GHz. Furthermore, the trench sinker, which was applied to the guard ring to suppress coupling between inductors, showed an excellent blocking performance below ?40 dB at a frequency of up to 20 GHz. These results confirm that the proposed trenched sinker should be an effective technology both as a compact sinker for RF power devices and as a guard ring against coupling.     

Tensile fracture and failure behavior of technical flax fibers

The apparent tensile strength of technical flax fibers was determined in single‐fiber tests at various clamping lengths (20, 40, and 80 mm) and the outcome was compared with literature data. It was demonstrated that the strength of flax at each clamping length obeyed the two‐parameter Weibull model. The failure mode and sequence were studied in situ (i.e., during loading) by SEM and acoustic emission (AE). The failure sequence (axial splitting of the technical fiber along its elementary constituents, radial cracking of the elementary fibers, multiple fracture of the elementary fibers) concluded reflected the hierarchical build‐up of the flax bast fibers. To the above failure events AE amplitude ranges were assigned. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3638–3645, 2003     

Catalytic dehydrogenation of ethylbenzene with carbon dioxide: promotional effect of antimony in supported vanadium–antimony oxide catalyst

Alumina-supported vanadium oxide, VO_x/Al₂O₃, and binary vanadium–antimony oxides, VSbO_x/Al₂O₃, have been tested in the ethylbenzene dehydrogenation with carbon dioxide and characterized by S_BET, X-ray diffraction, X-ray photoelectron spectroscopy, hydrogen temperature-programmed reduction and CO₂ pulse methods. VSbO_x/Al₂O₃ exhibited enhanced catalytic activity and especially on-stream stability compared to VO_x/Al₂O₃ catalyst. Incorporation of antimony into VO_x/Al₂O₃ increased dispersion of active VO_x species, enhanced redox properties of the systems and formed a new mixed vanadium–antimony oxide phase in the most catalytically efficient V_0.43Sb_0.57O_x/Al₂O₃ system.     

Positively Thermo‐Sensitive Monodisperse Core–Shell Microspheres

In this paper, we report on a novel family of monodisperse thermo‐sensitive core–shell hydrogel microspheres that is featured with high monodispersity and positively thermo‐responsive volume phase transition characteristics with tunable swelling kinetics, i.e., the particle swelling is induced by an increase rather than a decrease in temperature. The microspheres were fabricated in a three‐step process. In the first step, monodisperse poly(acrylamide‐co‐styrene) seeds were prepared by emulsifier‐free emulsion polymerization. In the second step, poly(acrylamide) or poly[acrylamide‐co‐(butyl methacrylate)] shells were fabricated on the microsphere seeds by free radical polymerization. In the third step, the core–shell microspheres with poly‐ (acrylamide)/poly(acrylic acid) based interpenetrating polymer network (IPN) shells were finished by a method of sequential IPN synthesis. The proposed monodisperse core–shell microspheres provide a new mode of the phase transition behavior for thermo‐sensitive “smart” or “intelligent” monodisperse micro‐actuators that is highly attractive for targeting drug delivery systems, chemical separations, sensors, and so on.     

High‐Performance,Monolithic Polyaniline Electrochemical Actuators

New polyaniline (PANI) asymmetric membranes were fabricated using a phase‐inversion technique with hexane as the coagulation bath. These membranes exhibit a dense structure with macrovoids distributed asymmetrically throughout the cross‐section. A stress–strain study demonstrated that the Young's modulus (1.421 GPa) and strain at break (7.6 %) of the new PANI asymmetric membranes prepared from hexane are approximately 12 and 4 times higher, respectively, than the values reported previously for the PANI integrally skinned asymmetric membranes (ISAMs) (123 MPa Young's modulus and 1.8 % strain at break). Furthermore, monolithic electrochemical actuators based on a single PANI asymmetric membrane were constructed, and a bending movement of up to 20 Hz was experimentally recorded in a hydrochloric acid aqueous solution. A lifetime of over 329 500 cycles was determined for these actuators at a ± 2° angular displacement (5 Hz). The lifetime is limited by a bending fatigue that creates a transversal crack on the PANI membrane at the air–water interface. Control over the actuator movement is also manifested by the linear dependences of the bending angle on the charge and of the angular velocity on the current. These relationships are independent of both the kind of applied electric signal and the frequency used.     

Possibilities and extension of XRD material response analysis in failure research for the advanced evaluation of the damage level of Hertzian loaded components

Due to clearly distinguishable damage symptoms, it is differentiated between the surface and sub‐surface failure mode of rolling bearings. Material states red out by X‐ray diffraction (XRD) residual stress measurements point to a variety of loading conditions especially at raceway surfaces that are associated with several competing failure mechanisms. The corresponding lifetime reduction can range from the lower fatigue strength region to material ratcheting in extreme cases. Relevant position of the microstructural changes and nature of the failure mechanisms are characterized. The time alteration of the XRD material parameters measured at or near the surface and at the depth of the maximum equivalent stress correlates, in a different manner, with the statistical parameter of the 10 % bearing life. Both failure modes are illustrated by concrete examples. Contaminated lubricant and boundary lubrication, which represent practically important surface‐induced failures, are discussed in more detail. Gray staining, i.e. shallow pitting, often occurs without distinct indication of global material aging by means of XRD characteristics. Here, scanning electron microscopy observations and electron microprobe analyses point to corrosion fatigue as acting surface failure mechanism. The interaction between material and lubricant under complex loading regimes particularly of mixed friction and corrosion opens further failure research areas in the field of tribology.     

Lipase‐catalyzed dynamic kinetic resolution of (R,S)‐fenoprofen thioester in isooctane

A lipase‐catalyzed enantioselective hydrolysis process under in situ racemization of the remaining (R)‐thioetser substrate with trioctylamine as the catalyst was developed for the production of (S)‐fenoprofen from (R,S)‐fenoprofen 2,2,2‐trifluoroethyl thioester in isooctane. Detailed investigations of trioctylamine concentration on the enzyme activation and the kinetic behavior of the thioester in racemization and enzymatic reactions were conducted, in which good agreement between the experimental data and theoretical results was observed. © 2002 Society of Chemical Industry