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.     

Copolymerization of bromophenylmaleimide with ethyl or butyl methacrylate

N‐p‐Bromophenylmaleimide (BrPMI) does not polymerize in solution by conventional free radical mechanism. However, it readily polymerized in bulk when mixed with a free radical initiator and heated in a microwave oven for 7–8 min. Copolymerization of ethyl methacrylate or butyl methacrylate with BrPMI was conducted in dioxane. The copolymers were characterized by IR and ¹H NMR spectroscopy and gel permeation chromatography. The monomer reactivity ratios were calculated by a non‐linear least‐square analysis. Thermal analysis indicated a great improvement in thermal stability of the copolymers compared with the methacrylate homopolymers. BrPMI was also polymerized in bulk in the DSC pan, which allowed the calculation of the activation energy of its polymerization. Copyright © 2003 Society of Chemical Industry     

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.     

Prediction of evaporation heat transfer coefficient and pressure drop of refrigerant mixtures

A study on the prediction of heat transfer coefficient (HTC) and pressure drop of refrigerant mixtures is reported. HTCs and pressure drops of prospective mixtures to replace R12 and R22 are predicted on the same cooling capacity basis. Results indicate that nucleate boiling is suppressed at qualities greater than 20.0% for all mixtures and evaporation becomes the main heat transfer mechanism. For the same capacity, some mixtures containing R32 and R152a show 8.0–10.0% increase in HTCs. Some mixtures with large volatility difference exhibit as much as 55.0% reduction compared with R12 and R22, caused by mass transfer resistance and property degradation due to mixing (32.0%) and reduced mass flow rates (23.0%). Other mixtures with moderate volatility difference exhibit 20.0–30.0% degradation due mainly to reduced mass flow rates. The overall impact of heat transfer degradation, however, is insignificant if major heat transfer resistance exists in the heat transfer fluid side (air system). If the resistance in the heat transfer fluid side is of the same order of magnitude as that on the refrigerant side (water system), considerable reduction in overall HTC of up to 20% is expected. A study of the effect of uncertainties in transport properties on heat transfer shows that transport properties of liquid affect heat transfer more than other properties. Uncertainty of 10.0% in transport properties causes a change of less than 6% in heat transfer prediction.     

Synthesis and characterization of chitosan/poly(acrylic acid) polyelectrolyte complex

Polyelectrolyte complex based on chitosan and acrylic acid monomer by photoinitiated free‐radical polymerization in the absence of crosslinker showed a large transition in swelling in response to changes in pH of surrounding medium. Their ability to swell arises from polyelectrolyte interactions and molecular structure of the complex. The main properties of interest that related to the molecular structure, swelling volumes, glass transition temperature, and elastic modulus of the complex were investigated. The effect of water content, the only variable in the sample component, played an important role in molecular structure of the complex and as a consequence, the extent of intermolecular linkage, especially amide bonds which in turn governed the degree of swelling of the polyelectrolyte complex in this study. The decreased degree of swelling and higher temperature shift of glass transition temperature was found with increased water content, whereas increased modulus of elasticity of dry complex was found in lower water content of synthesis component. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1025–1035, 2002     

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