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     

Fractional composition of partly hydrolysed polyvinyl acetate and its compatibility with hydroxypropyl methylcellulose in aqueous solutions

Fractionation of partly hydrolysed polyvinyl acetate (PVA) was performed by warming of its aqueous solutions. The following properties of the obtained fractions were determined: viscosity, molecular weight and molecular weight distribution, surface tension, and absorbance in the IR range. The blockiness of the polymer molecules, characterized by their behaviour towards iodine-containing systems such as I₂,-H₃BO₃ and I₂,-KI, was estimated. Fractionation of the aqueous solutions of PVA by warming is based mainly on the different internal molecular structure of the separated products, i.e. on the length of the vinyl acetate blocks in the PVA molecules and, to a lesser extent, on the degree of hydrolysis and the degree of polymerization. The more blocklike are the PVA molecules, the less compatible are the polymers in the PVA-hydroxypropyl methylcellulose (HPMC)-water system. At phase separation in this sytem the PVA molecules which are not compatible with HPMC are, in the first place, those of the highest blockiness.     

Accurate estimation of environment parameters from ultrasonic data

This paper describes a robust and accurate ultrasonic sensing system for a mobile robot. The system continuously updates a local map of the environment in which obstacles are represented by straight lines or points in a robot centered coordinate frame. The presented algorithms use a Kalman filter for the reduction of the noise in the ultrasonic data and use a systematical error correction (‘bundle correction’) to reduce the uncertainty in obstacle direction. Experiments are carried out in simulation and with a real mobile robot system. Results show that the accuracy with which line parameters can be estimated is in the order of 1 degree for the orientation and about 2 cm for the position. The effect of the bundle correction is significant and maximal when the robot approaches walls under a small angle.     

Influences of artificial pre-stressing on ply stresses and tensile properties of Vinylon fibre-reinforced aluminium laminates (VIRALL)

A simple micromechanical model based primarily upon the rule-of-mixtures is developed which allows prediction of the effects of fibre preload on the ply stresses (i.e., the initial residual stresses of fibre, adhesive and matrix) induced within VIRALL laminates, and the tensile stress-strain curves and mechanical properties of VIRALL laminates. The analysis of the ply stresses of VIRALL laminates indicates that pre-stressing will dramatically influence the ply stresses. The predicted tensile stress-strain curves of VIRALL laminates are in good agreement with the experimental curves and the results show that the stress-strain curves of VIRALL laminates move upwards when the prestress increases. The predicted tensile mechanical properties of VIRALL laminates at room temperature show good agreement with those obtained experimentally; both show that prestress can improve the tensile properties (i.e., elastic limit strength, 0.2% yield strength and failure strength) of VIRALL laminates.     

Effect of degumming on the tensile properties of silkworm (Bombyx mori) silk fiber

Forcibly reeled silkworm (Bombyx mori) silk was used to study how exposure to a degumming treatment (boiling in distilled water for 30 min) affects tensile properties. Because forcibly reeled and naturally spun fibers exhibit comparable mechanical behavior, the results can be generalized to material obtained conventionally from cocoons. The effects of degumming include: a decrease in the initial elastic modulus, a decrease in the stress at the proportional limit (yield strength), a change in the qualitative shape of force‐displacement curves, and significant qualitative and quantitative variability in force‐displacement data from samples subjected to nominally identical degumming histories. Immersion in water at room temperature or heating in air at 100°C for 30 min are both qualitatively equivalent to a 30‐min degumming treatment in boiling water, in terms of the effect on silk tensile properties. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1431–1437, 2002; DOI 10.1002/app.10366     

Synthesis and characterization of novel copolymers with the trimethylsilyl group for deep‐UV photoresists

N‐(4‐Acetoxyphenyl) maleimide (APMI) and three kinds of comonomers bearing a trimethylsilyl group were copolymerized at 60°C in the presence of azobisisobutyronitrile (AIBN) as an initiator in 1,4‐dioxane to obtain the three IP, IIP, and IIIP copolymers. These copolymers were removed from the acetoxy group in a transesterification process into new IVP, VP, and VIP copolymers with a pendant hydroxyl group. Two modified processes were adopted to prepare photoresists using these copolymers. The first process involved mixing the dissolution inhibitor, o‐nitrobenzyl cholate, with the new copolymers. Second, o‐nitrobenzyl cholate was introduced into the copolymers using 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) in dimethylformamide (DMF). The cyclic maleimide structure is responsible for the high thermal stability of these copolymers. After irradiation using deep–UV light and development with aqueous Na₂CO₃ (0.01 wt %), the developed patterns showed positive images and exhibited good adhesion to the silicon wafer without using any adhesion promoter. The resolution of these resists was at least 0.8 μm and an oxygen‐plasma etching rate was 1/5.3 to that of hard‐baked HPR‐204. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2791–2798, 2002; DOI 10.1002/app.10255