Autoxidation of ethyl eicosapentaenoate and docosahexaenoate

The extent of oxidation of ethyl esters of eicosapentaenoic (EPA) and docosahexaenoic acids (DHA) was compared quantitatively with that of ethyl linoleate (Lo) and ethyl linolenate (Ln) by oxygen uptake and formation of conjugated diene, hydroperoxide and secondary oxidation products. EPA and DHA esters were oxidized rapidly even at 5 C in the dark after an induction period of 3–4 days, while the induction periods of Ln and Lo esters were 20 days and more than 60 days, respectively. Oxygen uptake of EPA and DHA esters after the induction period was 5.2 and 8.5 times faster than that of ethyl Ln, respectively. Hydroperoxides of EPA and DHA esters are much less stable than those of ethyl Lo. The peroxide value is not necessarily a good indication of oxidation in these polyenoic acids because a considerable amount of secondary products is formed at the early stage of oxidation. Polymers were found to be major secondary products in these polyenoic esters.     

Oxidative coupling of methane over Na+-ZrO2-C1-/Al2O3 catalysts

Oxidative coupling of methane (OCM) was carried out over Na⁺-ZrO₂-Cl /A1[₂O₃ catalysts in a temperature range from 1023 to 1123 K. The catalysts were prepared by impregnating the α- or γ-Al₂O₃ supports with sodium carbonate and/or zirconyl chloride. The OCM activity was examined using the catalysts prepared by three different preparation procedures. The best catalyst was the one prepared by subsequent impregnation of sodium carbonate-preimpregnated γ-Al₂O₃ with a mixed solution of sodium carbonate and zirconyl chloride. It was found that preimpregnated sodium played an important role in reducing the combustion activity of the γ-Al₂O₃. The catalyst with an optimal composition showed the highest C₂ selectivity and yield of 40.8% and 15.1%, respectively. From the X-ray diffraction analysis it was found that tetragonal ZrO₂ was formed and that NaCl existed in the catalysts with relatively high sodium contents.     

Oil absorbents based on styrene–butadiene rubber

Four oil absorbents based on styrene–butadiene (SBR)—pure SBR (PS), 4‐tert‐butylstyrene–SBR (PBS), EPDM–SBR network (PES), and 4‐tert‐butylstyrene‐EPDM‐SBR (PBES)—were produced from crosslinking polymerization of uncured styrene–butadiene rubber (SBR), 4‐tert‐butylstyrene (tBS), and ethylene–propylene–diene terpolymer (EPDM). The reaction took place in toluene using benzoyl peroxide (BPO) as an initiator. Uncured SBR was used as both a prepolymer and a crosslink agent in this work, and the crosslinked polymer was identified by IR spectroscopy. The oil absorbency of the crosslinked polymer was evaluated with ASTM method F726‐81. The order of maximum oil absorbency was PBES > PBS > PES > PS. The maximum values of oil absorbency of PBES and PBS were 74.0 and 69.5 g/g, respectively. Gel fractions and swelling kinetic constants, however, had opposite sequences. The swelling kinetic constant of PS evaluated by an experimental equation was 49.97 × 10^?2 h^?1. The gel strength parameter, S, the relaxation exponent, n, and the fractal dimension, d_f, of the crosslinked polymer at the pseudo‐critical gel state were determined from oscillatory shear measurements by a dynamic rheometer. The morphologies and light resistance properties of the crosslinked polymers were observed, respectively, with a scanning electron microscope (SEM) and a color difference meter.     

Thermal runaway prevention in catalytic packed bed reactor by solid temperature measurement and Control

Magnetic crystallite thermometry has been used to measure the average nickel crystallite temperature in packed bed reactors during ethane hydrogenolysis, an exothermic reaction. The technique is based on the temperature dependence of the magnetic moment of dispersed nickel catalysts. Measurement of the average catalyst temperature is very useful for reactor control because of its shorter time constant compared with exit fluid temperature. Bed temperature control based on the exit fluid temperature, which has often been used as a control variable, is too slow to protect thermal runaway of the bed. The advantage of short time constant by measuring the average catalyst temperature has been incorporated with enhanced feedback control system to control the bed temperature and prevent the thermal runaway of the catalyst bed. An enhanced feedback control structure with supervisory action performed better than the classical proportional-integral control in runaway prevention when the two control schemes were compared with each other on the basis of the trippoint (incipient thermal runaway).     

Fabrication of a gradient refractive index preform using laminar shear mixing

A gradient refractive index rod was successfully prepared by a new fabrication method using laminar shear mixing, and a graded index polymer optical fiber that satisfied IEEE1394b was obtained from the method. To fabricate the gradient refractive index rod, a liquid monomer mixture with a relatively low refractive index was placed in a prepared cylindrical glass reactor and a transparent polymer rod with a higher refractive index was introduced at the center of the reactor. The reactor and the polymer rod were then rotated concurrently with a small rotating speed difference to generate a Couette flow in the liquid phase. The centrifugal force generated by rotation and the polymer diffusion into the liquid monomer mixture developed a graded concentration profile in a radial direction. The Couette flow could reduce the concentration fluctuation in a tangential direction. In addition, the graded index profile could be controlled by the copolymer composition of the rod and its diameter. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1100–1104, 2005     

Electromechanical behavior of hybrid carbon/glass fiber composites with tension and bending

To understand the smart (i.e., good memory) characteristics of hybrid composites of carbon fibers (CFs) and glass fibers (GFs) with epoxy resin as a matrix, the changes in the electrical resistance of composites with tension and on bending were investigated. The electrical resistance behavior of composites under tension changed with the composition of the CF/GF, as well as with the applied strain. The fractional electrical resistance increased slowly with increasing strain within a relatively low strain region. However, with further loading it increased stepwise with the strain according to the fracture of the CF layers. The strain sensitivity of the samples increased with increasing CF weight percentage, and the samples incorporating more than 40 wt % CF showed a strain sensitivity higher than 1.54 for a single CF. The changes in the fractional electrical resistance with bending were not so dominant as those with tension. This difference was attributed to the action of two cancelling effects, which are the increasing and decreasing fractional electrical resistance due to tension and compression with bending, respectively. On recovery from a large applied bending, the fractional electrical resistance decreased slowly with unloading because of the increase of contacts between the fibers that resulted from the reorganization of ruptured CFs during the recovery. Even the composites incorporating a relatively small CF content showed an irreversible electrical resistance with both tension and bending. However, the strain sensitivity being larger with tension than with bending is ascribed to the difference in their mechanical behaviors. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2447–2453, 2002     

Effects of chemical additives on high-field electromechanical properties of PMN–PT–BT ceramics

A chemical additive method using sol–gel reactions was used to modify the composition and resultant properties of a commercially available 0.96(0.91Pb(Mg_1/3Nb_2/3)O₃–0.09PbTiO₃)–0.04 BaTiO₃ (PMN–PT–BT) ceramic. Without an additional ball-mixing process, several combinations of minor additives such as Fe, Ba, Sr, Zn, and Ti were incorporated by the chemical method. Weak- and high-field characteristics including dielectric properties, induced strain and polarization, and associated hystereses were evaluated for the samples sintered at 1200 °C for 4 h. All properties were found to depend on the chemical additives and temperature. Especially, the temperature dependence of high-field characteristics revealed different behavior from that reported for conventionally prepared samples. For example, the samples containing 0.5 wt.% SrO, 0.5 wt.% ZnO, and 0.5 wt.% TiO₂ did not exhibit a transition to piezoelectric behavior at the temperature expected from the dielectric measurements. Overall, the coating process has been successfully used to modify, and in some cases, enhance the high-field characteristics of PMN-based ceramics for electromechanical uses.     

Preparation of porous thin films of a partially aliphatic polyimide

A thermally labile polymer, poly(propylene glycol), was modified to obtain PPG having an amino end group. PPG was incorporated into a partially aliphatic polyimide based on an alicyclic dianhydride, and this afforded triblock copolymers containing various amounts of PPG blocks. The thermal properties of the copolymers were investigated by thermogravimetric analysis and differential scanning calorimetry. The thermal decomposition of the PPG block in the copolymers was carried out at 240°C under various pressures to obtain porous polyimide films. The pores remained during the thermolysis under a reduced pressure of 710 mmHg, whereas they collapsed under (near) atmospheric pressure. The pore size increased as the amount of the PPG block in the copolymers increased. The dielectric constants of the porous polyimides varied from 2.60 to 2.42 with the original copolymer composition. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 532–538, 2006     

Comparison of liquid-phase and methanol-swelling crosslinking processes of polyimide dense membrane for CO2/CH4 separation

To overcome the plasticization effect in polyimide membranes, many researchers have proposed crosslinking method. This can reduce an inter-segmental mobility by tightening and rigidifying the polymer chains. However, it is difficult to modify the whole polymer chains throughout the membrane because the reaction can be hindered by the diffusion rate of the crosslinker. In particular, it is hard for bulky crosslinker to penetrate a dense membrane with a small d-spacing. This study investigated the effect of crosslinking a dense Matrimid membrane with p-phenylenediamine (p-PDA) via two different crosslinking methods (i.e., methanol-swelling crosslinking process [M-SCP] and liquid-phase crosslinking process [L-PCP]). Most of the crosslinking reaction in M-SCP occurs on the membrane surface due to difficulty in penetration of the bulky p-PDA into the Matrimid dense membrane. In contrast, the L-PCP allows uniform crosslinking across the membrane. The membranes crosslinked using L-PCP showed excellent chemical resistance. Furthermore, the plasticization phenomenon was not observed in the membranes crosslinked using L-PCP with p-PDA more than 15%. Meanwhile, the membrane crosslinked using M-SCP exhibited poor plasticization and chemical resistance properties. These results showed that the L-PCP method can be more effective for the crosslinking of dense membrane to deliver both high plasticization and chemical resistance.     

Nitrogen removal using recycled polystyrene bottles as biofilm media

The performance of an attached growth wastewater treatment process was investigated in an effort to improve nitrogen removal efficiency. Recycled Yakult (lactic acid fermentation drink) bottles made of polystyrene were used as a biofilm media. The use of Yakult bottles as a biofilm media has been attempted by numerous researchers in Japan for the removal of solids and organics. However, these studies focused only on the removal of solids and organics. This study extended their application to the removal of nitrogen for domestic sewage treatment. Yakult media was placed in a reactor with 70% apparent reactor volume in a conventional A/O process. The bottom of the Yakult media was removed, and randomly filled Yakult media were effectively able to reduce the flow in tanks, resulting in an increase in the contact time between pollutants and microorganisms. With higher HRT, the nitrogen removal efficiency was increased by up to 83% with 12 hr of HRT. Nitrification appeared to be the limiting factor of nitrogen removal at an HRT that is less than 12 hr, indicating that the Yakult process requires more retention time to achieve nitrification compared to other biofilm processes. The removal efficiencies of organics and solids were high regardless of the change of operational parameters. This article is based on a presentation in “The 7th Korea-China Workshop On Advanced Materials” organized by the Korea-China Advanced Materials Cooperation Center and the China-Korea Advanced Materials Cooperation Center, held at Ramada Plaza Jeju Hotel, Jeju Island, Korea on August 24–27, 2003.