Novel positive‐working aqueous‐base developable photosensitive polyimide precursors based on diazonaphthoquinone‐capped polyamic esters

Novel positive‐working aqueous‐base developable photosensitive polyimide (PSPI) precursors based on partially diazonaphthoquinone (DNQ)‐capped polyamic esters bearing phenolic hydroxyl groups and a DNQ photosensitive compound (PIC‐3) were developed. The partially DNQ capped polyamic esters were prepared from an esterification reaction of 1,2‐naphthoquinone diazide‐5‐sulfonyl chloride with the polyamic esters. The partially DNQ capped polyamic esters decreased the dark film loss effectively in the aqueous‐base developer and were able to make thicker film resists compared to the uncapped polyamic esters. The 25 mol % DNQ‐capped BisAPAF–PMDA polyamic ester and BisAPAF–ODPA polyamic ester containing 25 wt % PIC‐3 photosensitive compound showed a sensitivity of 176 and 185 mJ/cm², and a contrast of 1.68 and 1.02, respectively, in a 3‐μm film with 1.25 wt % tetramethylammonium hydroxide developer. A pattern with a resolution of 5 μm was obtained from both PSPI precursor compositions. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2293–2300, 2003     

On a Mixture GARCH Time‐Series Model

Abstract. Recently, there has been a lot of interest in modelling real data with a heavy‐tailed distribution. A popular candidate is the so‐called generalized autoregressive conditional heteroscedastic (GARCH) model. Unfortunately, the tails of GARCH models are not thick enough in some applications. In this paper, we propose a mixture generalized autoregressive conditional heteroscedastic (MGARCH) model. The stationarity conditions and the tail behaviour of the MGARCH model are studied. It is shown that MGARCH models have tails thicker than those of the associated GARCH models. Therefore, the MGARCH models are more capable of capturing the heavy‐tailed features in real data. Some real examples illustrate the results.     

Cement-based materials for stress sensing by dielectric measurement

The self-sensing of stress by measurement of the relative dielectric constant (κ) has been shown in cement pastes containing steel fibers of 8 μm diameter and carbon filaments of 0.1 μm diameter. The κ value increases nonlinearly and quite reversibly with compressive stress up to 6.4 MPa, although the reversibility is not complete. Inferior sensing performance was observed in cement paste with carbon fibers of 15 μm diameter, although the performance was still better than cement paste without admixture.     

Blends of chlorinated isotactic polypropylene with poly(ethylene-co-vinyl acetate) I. Effect of component polymers composition on the blend miscibility

Chlorinated isotactic polypropylenes (CPP) having various chlorine contents were blended with poly(ethylene-co-vinyl acetate)s (EVA) having various vinyl acetate (VA) contents. The blends were made by casting films from dilute THF solutions and miscibility of the blends was identified by single glass transition temperature, which was confirmed by DSC and dynamic mechanical measurements. Based on the miscibility data from a large number of CPP/EVA combinations, a miscibility map was depicted where CO equivalent weight (CO-EQW) of EVA was plotted against chlorine equivalent weight (Cl-EQW) of CPP. Though an attractive interaction between CPP and EVA could be detected in all the miscible and immiscible blend pairs, miscibility of the CPP/EVA blends could solely be observed in a relatively narrow range of Cl-EQW ca. 65–100 and CO-EQW ca. 170–230.     

Improved mechanical properties of shape‐memory polyurethane block copolymers through the control of the soft‐segment arrangement

High‐performance shape‐memory polyurethane block copolymers, prepared with two types of poly(tetramethylene glycol) (PTMG) used as soft segments, were investigated for their mechanical properties. Copolymers with a random or block soft‐segment arrangement had higher stresses at break and elongations at break than those with only one kind of PTMG. Random copolymers with fewer interchain interactions showed higher elongation than block copolymers. All the copolymers had shape‐recovery ratios higher than 80%. In dynamic mechanical testing, the glass‐transition behavior clearly depended on the soft‐segment arrangement: random copolymers had only one glass‐transition peak, whereas block copolymers showed two separate glass‐transition peaks. Overall, the control of the soft‐segment arrangement plays a vital role in the development of high‐performance shape‐memory polyurethane. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2410–2415, 2004     

The temporal evolution of thermal instability in fluid layers isothermally heated from below

The temporal development of thermal disturbances in the fluid layer heated isothermally from below is investigated, based on propagation theory. This theory is examined by using scaling. To examine the behavior of thermal instability the mean-field approximation is employed and resulting equations are solved by Galerkin method. The stability criteria to mark the onset of convective instability are newly suggested as the intersection point of the growth rate of averaged temperature with that of its fluctuation. The resulting critical time is close to that derived from propagation theory. By considering the nonlinear effects, the characteristic times to represent the detection time of manifest convection and also to exhibit the minimum Nusselt number are discussed.     

Electrochemical cell current requirements for toxic organic waste destruction in Ce(IV)-mediated electrochemical oxidation process

The electrochemical cell for cerium oxidation and reactor for organic destruction are the most important operation units for the successful working mediated electrochemical oxidation (MEO) process. In this study, electrochemical cells with DSA electrodes of two types, single stack and double stack connected in series, were used. The performances towards the electrochemical generation of Ce(IV) in nitric acid media at 80 °C were studied. The current-voltage curves and cerium electrolysis kinetics showed the dependence on number of cell stacks needed to be connected in series for the destruction of a given quantity of organic pollutant. The presence of an optimum region for Ce(III) oxidation with a contribution of oxygen evolution, especially at low Ce(III) concentration (high conversion ratios), was found. The cells were applied for the Ce(IV) regeneration during the organic destruction. The cell and reactor processes were fitted in a simple model proposed and used to calculate the current needed in terms of Ce(III) oxidation rate and the number of cell stacks required for maintaining Ce(IV)/Ce(III) ratio at the same level during the organic destruction. This consideration was based on the kinetic model previously developed by us for the organic destruction in the MEO process.     

Constraint release effects on the dynamics of polymer melts

The dynamical behavior of polymers with molecular weight distribution is analyzed from the standpoint of reptation and tube renewal. In a binary blend where the entanglements between longer chains are prominent, the shorter chain relaxes only by reptation, whereas the longer chain shows more complex behavior, i.e., reptation in the original tube, short-range tube renewal causing the tube enlargement, and thereafter reptation again in the expanded tube. Dynamic moduli data from literature are used for determining the compositional dependence of the relaxation times. Also on the basis of the relaxation mechanism considered here, the critical composition due to the onset of entanglements between different longer chains is proposed as a function of their component molecular weighl ratio.     

Rotational diffusion coefficient of rod-like polymer with a slight flexibility in semidilute and concentrated solutions

Summary A confined stiff chain model is suggested for the prediction of the rotational diffusion coefficient of a rigid rodlike polymer with a slight flexibility above the region of dilute solution (c1/L³). It shows a fairly good agreement with the experimental data of various polymers. Among them, PBLG and PBT with more rigidity are more consistent with the model when the log-jamming effect is considered. The predicted rotational diffusivity shows approximately the inverse seventh-power of length, which is less than 9 of Doi-Edwards tube model, but larger than the experimental value 5.7 of M-virus, while it shows the inverse power of concentration is a little larger than the value 2 of tube model except for the rodlike virus M-13.     

Preparation and characterization of eugenol‐grafted chitosan hydrogels and their antioxidant activities

The hydrogels composed of chitosan and eugenol were prepared to enhance and sustain antioxidant activities. The vinyl groups of eugenol monomer were directly grafted on the amino groups of chitosan, using ceric ammonium nitrate. The graft of eugenol onto chitosan was confirmed by using Fourier‐transform infrared and proton nuclear magnetic resonance spectroscopies. Results from the swelling behavior, thermal stability, and wide‐angle X‐ray diffraction revealed that the equilibrium water content decreased with increase of graft yields, because of the hydrophobicity of eugenol, although the introduction of eugenol as a side chain disturbed the ordered arrangement of chitosan's crystalline structure. The eugenol‐grafted chitosan hydrogels showed lower pH sensitivity in comparison with chitosan alone, because the amino groups, which were pH sensitive, of chitosan were grafted with eugenol. The scavenging activity of the tested hydrogels increased with graft yield of eugenol, because phenolic groups in the eugenol could play a major role as potent free‐radical terminators, in the results of improved antioxidant activity in eugenol‐grafted chitosan hydrogel in comparison with chitosan alone. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99:3500–3506, 2006