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     

Thermal and mechanical properties of the polymers synthesized by the sequential polymerization of propylene and 1‐hexadecene

The block copolymer of poly(1‐hexadecene) (PHD) and polypropylene (PP) was effectively synthesized by the sequential polymerization of propylene and 1‐hexadecene by using highly isospecific TiCl₃/Cp₂Ti(CH₃)₂ (Cp = cyclopentadienyl). The block copolymers had two separate melting temperatures of constituent blocks. The modulus of PHD–PP block copolymer was enhanced as the content of sequentially polymerized PP block was increased. The elongation at break showed positive deviation at the intermediate compositions from the simple additive values of constituent homopolymers. Shape memory effect which utilizes the crystalline PHD block as a reversible phase and the crystalline PP block as a fixed structure was examined. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1709–1715, 2002; DOI 10.1002/app.10551     

Preparation of water‐soluble syndiotacticity‐rich high molecular weight poly(vinyl alcohol) microfibrillar fibers using copolymerization of vinyl pivalate and vinyl acetate and saponification

Water‐soluble high molecular weight (HMW) syndiotactic poly(vinyl alcohol) (s‐PVA) microfibrillar fibers were prepared by the saponification with various conditions such as amount of alkali solution, saponification temperature, and saponification concentration from copoly(vinyl pivalate (VPi)/vinyl acetate (VAc)) copolymerized using various VPi/VAc feed ratios. To produce s‐PVA microbrillar fibers having various water‐soluble temperatures for many industrial applications, the intrinsic viscosities, syndiotactic diad (S‐diad) contents, and degrees of saponification (DS)s of PVAs were finely controlled to 1.2–3.6 dL/g, 56.3–58.3%, and 91.4–98.3%, respectively. Through a series of experiments, it was found that the amount of alkali may alter the structure of the saponified polymers, primarily the DS, and the structural variation changes viscosity. That is, intrinsic viscosity was sharply decreased as the amount of alkali solution was increased. DS was increased with an increase in the amount of alkali solution. S‐diad content was increased with an increase in the VPi content. HMW s‐PVA microfibrillar fibers having S‐diad content of 56.3–58.3% prepared by the saponification of copoly(VPi/VAc) were completely soluble in water at 100°C. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1482–1487, 2003     

Preparation and characterizations of interpenetrating polymer network hydrogels of poly(ethylene oxide) and poly(methyl methacrylate)

Interpenetrating polymer network (IPN) hydrogels based on poly(ethylene oxide) and poly(methyl methacrylate) were prepared by radical polymerization using 2,2‐dimethyl‐2‐phenylacetophenone and ethylene glycol dimethacrylate as initiators and crosslinkers, respectively. The IPN hydrogels were analyzed for sorption behavior at 25°C and at a relative humidity of 95% using dynamic vapor sorption. The IPN hydrogels exhibited a relatively high equilibrium water content in the range of 13–68%. The state of water in the swollen IPN hydrogels was investigated using differential scanning calorimetry. The free water in the hydrogels increased as the hydrophilic content increased. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 258–262, 2003     

Synthesis and applications of unsaturated polyester resins based on PET waste

Three types of unsaturated polyester resins were synthesized from the glycolysis of polyethylene terephthalate (PET) plastic waste, considering environment, cost and properties for their applications. These synthesized unsaturated polyester resins could be used for various construction processes and materials such as no dig pipelining (NDR-1), pultrusion (PLR-1) and polymer concrete (PCR-1). PET was taken from common soft-drink bottles, and ethylene glycol (EG), diethylene glycol (DEG) and MPdiol glycol mixtures were used for the depolymerization at molar ratios. The glycolyzed PET 1 ^st products (oligomers) were reacted with maleic anhydride, phthalic anhydride and dicyclopentadiene (DCPD) (especially for polymer concrete) to form unsaturated polyester resins with mixed styrene. The lab scale (1–5 kg) and pilot plant scale-up tests (200 kg) were experimented to evaluate the processing characteristics, viscosity, acid number and curing behaviors. The main properties such as hardness, flexural strength, tensile strength, heat distortion temperature, elongation, and chemical resistance were determined based on the various uses of the three resins. Furthermore, the applicability and the properties of these developed resins were verified through many real application tests.     

Development of density distributions in injection molded amorphous engineering plastics. Part I

The gapwise density distributions of the injection molded specimens of two engineering thermoplastics, i.e., poly(phenylene ether) and poly(ether imide), were characterized employing the density gradient column technique. The samples were molded using a 40t Van Dorn injection molding machine. The effects of the thermal history on the density distribution of unconstrained quenched specimens were also investigated. In addition, various material properties, such as pressure-volume-temperature, isothermal contraction, and pressure induced densification behavior were characterized, for the two resins employed in this study. The moldings of the two resins exhibited different trends in their density distributions. These findings were explained in terms of the competing effects of cooling rate and the pressure history experienced by the engineering plastic resins during the molding cycle. The data collected were also used as input to mathematical modeling of density distributions in injection molded articles, which is reported in Part II of this article.     

Modeling and economic analysis of CO<Subscript>2</Subscript> separation process with hollow fiber membrane modules

The main purpose of the study was to develop a model using ASPEN and Excel simulation method to establish optimum CO₂ separation process utilizing hollow fiber membrane modules to treat exhaust gas from LNG combustion. During the simulation, optimum conditions of each CO₂ separation scenario were determined while operating parameters of CO₂ separation process were varied. The characteristics of hollow fibers membrane were assigned as 60 GPU of permeability and 25 of selectivity for the simulation. The simulation results illustrated that 4 stage connection of membrane module is required in order to achieve over 99% of CO₂ purity and 90% of recovery rate. The resulted optimum design and operation parameters throughout the simulation were also correlated with the experimental data from the actual CO₂ separation facility which has a capacity of 1,000 Nm³/day located in the Korea Research Institute of Chemical Technology. Throughout the simulation, the operating parameters of minimum energy consumption were evaluated. Economic analysis of pilot scale of CO₂ separation plant was done with the comparison of energy cost of CO₂ recovery and equipment cost of the plant based on the simulation model. This work was presented at the 6 ^th Korea-China Workshop on Clean Energy Technology held at Busan, Korea, July 4–7, 2006.     

Ce3+/Tb3+-coactived NaMgBO3 phosphors toward versatile applications in white LED,FED, and optical anti-counterfeiting

Ce³⁺/Tb³⁺ co-doped NaMgBO₃ phosphors were successfully synthesized by solid-state method. Under 381 nm excitation, the cyan emission owing to the 5d → 4f of Ce³⁺ ions and green emissions arising from the ⁵D₄ → ⁷F_J (J = 6, 5, 4, and 3) transitions of Tb³⁺ ions were seen in all the phosphors. Through theoretical analysis, one knows that the energy transfer from Ce³⁺ to Tb³⁺ ions with high efficiency of 83.74% was contributed by dipole–dipole transition. Furthermore, the internal quantum efficiency of NaMgBO₃:0.01Ce³⁺,0.03Tb³⁺ phosphor was 54.28%. Compared with that of at 303 K, the emission intensity of the developed products at 423 K still kept 73%, revealing the splendid thermal stability of the studied phosphors. Through utilizing the resultant phosphors as cyan-green components, the fabricated white-LED device exhibited an excellent correlated color temperature of 2785 K, high color-rendering index of 85.73, suitable luminance efficiency of 25.00 lm/W, and appropriate color coordinate of (0.4279, 0.3617). Aside from the superior photoluminescence, the synthesized phosphors also exhibited excellent cathode-luminescence properties which were sensitive to the current and accelerating voltage. Furthermore, the NaMgBO₃:0.01Ce³⁺,0.03Tb³⁺ phosphors with multi-mode emissions were promising candidates for optical anti-counterfeiting. All the results indicated that the Ce³⁺/Tb³⁺ co-doped NaMgBO₃ phosphors were potential multi-platforms toward white-LED, field emission displays, and optical anti-counterfeiting applications.     

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.     

铝波导真空钎焊

试验证明,铝波导滤波器的理想钎焊方法是真空钎焊。基体材料为LF21铝合金。钎料为Al-11.5Si-1.5Mg 和Al-7Si-1.5Mg。部件的钎焊温度为605～615℃,其真空度为1×10~(-5)Tor,试验指出,在真空钎焊时,铝的氧化膜并不能去除,熔化钎料是沿着金属和氧化膜之间的界面铺展的,氧化膜被举起,熔化钎料沿铝表面流动。因此,毛细作用微弱,且不能很好地形成连续的钎缝。为了提高毛细作用和得到连续的圆角,部件表面进行了局部打磨,而在真空腔内放置了“工艺罩”,在罩内放置了适当量的镁块。试验证明这是有效的:钎料的润湿和铺展非常好;流动距离和填充间隙能力提高了两倍;而组合件一次可以满意地焊成,且不会产生腐蚀和明显变形,从而不需焊后清洗和修整.