Syntheses and biological activities of polymers containing methacryloyl‐2‐oxy‐1,2,3‐propanetricarboxylic acid or 5‐fluorouracil

A series of novel copolymers, poly(methacryloyl‐2‐oxy‐1,2,3‐propanetricarboxylic acid‐co‐exo‐3,6‐epoxy‐1,2,3,6‐tetrahydrophthalic acid) [poly(MTCA‐co‐ETAc)], poly(methacryloyl‐2‐oxy‐1,2,3‐propanetricarboxylic acid‐co‐hydrogenethyl‐exo‐3,6‐epoxy‐1,2,3,6‐tetrahydrophthalate) [poly(MTCA‐co‐HEET)], and poly(methacryloyl‐2‐oxy‐1,2,3‐propanetricarboxylic acid‐co‐α‐ethoxy‐exo‐3,6‐epoxy‐1,2,3,6‐tetrahydrophthaloyl‐5‐fluorouracil) [poly(MTCA‐co‐EETFU)], were prepared from corresponding monomers by photopolymerizations at 25°C for 48 h. The polymers were identified by FTIR, ¹H‐NMR, and ¹³C‐NMR spectroscopies. The number‐average molecular weights of the fractionated polymers determined by GPC were in the range from 9400 to 14,900 and polydispersity indices were 1.2–1.4. The in vitro IC₅₀ values of polymers against mouse mammary carcinoma (FM3A), mouse leukemia (P388), and human histiocytic lymphoma (U937) as cancer cell lines and mouse liver cells (AC2F) as a normal cell line were much higher compared to that of 5‐fluorouracil (5‐FU). The in vivo antitumor activities of monomers and polymers against mice bearing sarcoma 180 tumor cell line were better than those of 5‐FU. The inhibition of DNA replication and antiangiogenesis activities of MTCA and copolymers were better compared to those of 5‐FU. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 57–64, 2004     

Synergistic Catalysis of Carbon Dioxide Hydrogenation into Methanol by Yttria-Doped Ceria/γ-Alumina-Supported Copper Oxide Catalysts: Effect of Support and Dopant

Methanol synthesis from carbon dioxide hydrogenation was studied over ceria/-alumina- and yttria-doped ceria (YDC)/-alumina-supported copper oxide catalysts to seek insight into the catalysis at metal–support interfaces. It was found that, in comparison with Cu/-Al₂O₃, the Cu/CeO₂/-Al₂O₃ and Cu/YDC/-Al₂O₃ catalysts exhibited substantial enhancement in activity and selectivity toward methanol formation. The extent of enhancement was augmented by increased ceria loading on -alumina and with increased yttria doping into ceria. The enhancement is inferred to result from the synergistic effect between copper oxide and surface oxygen vacancies of ceria.     

Selective CO oxidation in the presence of hydrogen over supported Pt catalysts promoted with transition metals

Selective CO oxidation in the presence of excess hydrogen was studied over supported Pt catalysts promoted with various transition metal compounds such as Cr, Mn, Fe, Co, Ni, Cu, Zn, and Zr. CO chemisorption, XRD, TPR, and TPO were conducted to characterize active catalysts. Among them, Pt-Ni/γ-Al₂O₃ showed high CO conversions over wide reaction temperatures. For supported Pt-Ni catalysts, Alumina was superior to TiO₂ and ZrO₂ as a support. The catalytic activity at low temperatures increased with increasing the molar ratio of Ni/Pt. This accompanied the TPR peak shift to lower temperatures. The optimum molar ratio between Ni and Pt was determined to be 5. This Pt-Ni/γ A1₂O₃ showed no decrease in CO conversion and CO₂ selectivity for the selective CO oxidation in the presence of 2 vol% H₂O and 20 vol% CO₂. The bimetallic phase of Pt-Ni seems to give rise to stable activity with high CO₂ selectivity in selective oxidation of CO in H₂-rich stream.     

Effects of melt‐extension and annealing on row‐nucleated lamellar crystalline structure of HDPE films

The row‐nucleated lamellar crystalline structure of high‐density polyethylene (HDPE) films was prepared by applying elongation stress to HDPE melt during T‐die cast film extrusion and subsequently annealing the extruded films. This unusual crystalline structure was analyzed in terms of lamellar crystalline orientation, long‐period lamellar spacing, crystallite size, and degree of crystallinity. The contribution of melt‐extension represented by draw‐down‐ratio (DDR) to the overall orientation was found to be most noticeable than other processing variables. Meanwhile, the long‐period lamellar spacing, the crystallite size, and the degree of crystallinity were influenced predominantly by the annealing temperature. Finally, the processing (melt extension and annealing temperature) – structure (lamellar crystalline structure) – property (hard elasticity) relationship of HDPE films was investigated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3326–3333, 2007     

The removal of hydrogen sulfide with manganic sorbent in a high-temperature fluidized-bed reactor

The removal of hydrogen sulfide (H₂S) from simulated gas was carried out in a batch type fluidized-bed reactor using natural manganese ore (NMO), which consists of several metal oxides (MnO_x: 51.85%, FeO_y: 3.86%, CaO: 0.11%). The H₂S breakthrough curves were obtained by changing temperature, gas velocity, initial H₂S concentration, and aspect ratio. Moreover, the effects of the particle size and the particle-mixing fraction on H₂S removal were investigated in a binary system of different particle size. From this study, H₂S removal efficiency increased with increasing temperature but decreased with increasing excess gas velocity. The breakthrough time for H₂S decreased as the gas velocity increased, which leads to reducing gas-solid contacting due to gas bypassing in a fluidized bed reactor. Improvement of H₂S removal efficiency in continuous process can be expected from the results of the binary particle system with different size in a batch experiment. The NMO could be considered as a potential sorbent in H₂S removal.     

Chemical Stability of the Fiber Coating Matrix Interface in Silicon-Based Ceramic Matrix Composites

Carbon and boron nitride are used as fiber coatings in silicon-based composites. In order to assess the long-term stability of these materials, reactions of carbon/Si₃N₄ and BN/SiC were studied at high temperatures with Knudsen effusion, coupon tests, and by microstructural examination. In the carbon/Si₃N₄ system, carbon reacted with Si₃N₄ to form gaseous N₂ and SiC. The formation of SiC limited further reaction by physically separating the carbon and Si₃N₄. Consequently, the development of high p (N₂) at the interface, predicted from thermochemical calculations, did not occur, thus limiting the potential deleterious effects of the reaction on the composite. Strong indications of a reaction between BN and SiC were shown by TEM and SIMS analysis of the BN/SiC interface. In long-term exposures, this reaction can lead to a depletion of a BN coating and/or an unfavorable change of the interfacial properties, limiting the beneficial effects of the coating.     

Advanced underfill for high thermal reliability

The key to the success of flip‐chip technology lies in the availability of sucessful underfill materials. However, the reliability of flip‐chip technology using current underfill materials is generally found to be lower than that of conventional wire‐bond connection packaging materials such as epoxy molding compound (EMC) because of the high coefficients of thermal expansion (CTE) and moisture absorption of cured underfill material. In this study desbimide (DBMI), which has a low melting point (about 80°C), was used in the underfill materials as a cohardener. As a result, DBMI‐added underfill can show excellent thermal reliability, which is due to the superior properties of the CTE, the elastic modulus, and water resistance. When the properties of a 2 wt % DBMI‐added underfill were compared with those of a typical underfill (epoxy/anhydride), the CTE value was reduced to less than one‐half at the solder reflow temperature (about 200°C), the elastic modulus was reduced to less than one‐half in the temperature region below the glass‐transition temperature, and the water resistance was improved twofold. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2617–2624, 2002     

Dependence of the Microstructure and the Electrical Properties of Lanthanum-Substituted (Na1/2Bi1/2)TiO3 on Cation Vacancies

The sintering and electrical characteristics of La-modified Na_1/2Bi_1/2TiO₃ (NBT) was investigated from a defect structure viewpoint. To reveal the role of cation vacancies, two series of ceramics, with different cation vacancies, were processed to compensate the excess positive charge of lanthanum ions. In a region of complete solid solution, the grain size of NBLT-B {[(Na_0.5Bi_0.5)_{1− x} La _x ]Ti_{1−0.25 x} O₃} was smaller than that of NBLT-A {[(Na_0.5Bi_0.5)_{1−1.5 x} La _x ]TiO₃} and densification was enhanced more effectively in NBLT-B. With the aid of thermoelectric power, electric conductivity, and electrotransport measurements, it was found that different sintering behaviors between NBLT-A and NBLT-B specimens were related to the change in the type of cation vacancies present and that lanthanum ion–cation vacancy pairs played an important role in reducing the grain growth and enhancing the densification process.     

Synthesis and luminescence properties of new blue‐light‐emitting polyconjugated poly{1,1′‐biphenyl‐4,4′‐diyl‐[1‐(4‐t‐butylphenyl)]vinylene} polymers and copolymers

Three new soluble polyconjugated polymers, all of which emitted blue light in photoluminescence and electroluminescence, were synthesized, and their luminescence properties were studied. The polymers were poly{1,1′‐biphenyl‐4,4′‐diyl‐[1‐(4‐t‐butylphenyl)]vinylene}, poly((9,9‐dioctylfluorene‐2,7‐diyl)‐alt‐{1,4‐phenylene‐[1‐(4‐t‐butylphenyl)vinylene‐1,4‐phenylene]}) [P(DOF‐PVP)], and poly([N‐(2‐ethyl) hexylcarbazole‐3,6‐diyl]‐alt‐{1,4‐phenylene‐[1‐(4‐t‐butylphenyl)]vinylene‐1,4‐phenylene}). The last two polymers had alternating sequences of the two structural units. Among the three polymers, P(DOF‐PVP) performed best in the light‐emitting diode devices of indium–tin oxide/poly(ethylenedioxythiophene) doped with poly(styrene sulfonate) (30 nm)/polymer (150 nm)/Li:Al (100 nm). This might have been correlated with the balance in and magnitude of the mobility of the charge carriers, that is, positive holes and electrons, and also the electronic structure, that is, highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) levels, of the polymers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 307–317, 2006     

Dynamics of single-walled carbon nanotube (SWNT)/polyisoprene (PI) nanocomposites in electric and mechanical fields

Relaxation dynamics of single-walled carbon nanotube (SWNT)/polyisoprene (PI) nanocomposites were examined by dielectric relaxation spectroscopy (DRS) and dynamic mechanical spectroscopy (DMS) over a wide range of frequency and temperature. Both functionalized (SWNT-f) and pristine (SWNT-p) nanotubes were used and their effect on dynamics compared. Functionalized (PISF) nanocomposites were characterized by an increase in the time scale of the normal mode process as a consequence of the strong surface interactions between the polymer matrix and the nanotubes. The exact opposite is seen in pristine (PISP) nanocomposites where a decrease in the time scale of the normal mode relaxation is observed and attributed to weaker surface interactions and the effect of confinement on dynamics. The segmental process in PISF or PISP is not affected by the presence of nanotubes. The temperature dependence of the average relaxation time for normal and segmental modes is of the Vogel-Fulcher-Tammann (VFT) type. A good agreement is observed in the time scale of processes measured by DRS and DMS in PISF nanocomposites. In PISP nanocomposites, however, the time scales obtained from DRS and DMS measurements are not in consistently good agreement and an explanation is offered in terms of confinement.