Dissipative structures of autocatalytic reactions in tubular flow reactors

Dissipative structures of autocatalytic reactions with initially uniform concentrations are studied in tubular flow reactors. A unique steady state exists in a continuous stirred tank reactor. Linear stability analysis predicts either a stable node, a focus or an unstable saddle-focus. Sustained oscillations around the unstable focus can occur for high values of Damköhler number. In distributed parameter systems, travelling, standing or complex oscillatory waves are detected. For low values of Damköhler number, travelling waves with pseudo-constant patterns are observed. With intermediate values of Damköhler number, single or multiple standing waves are obtained. The temporal behavior indicates also the appearance of retriggering or echo waves. For high values of Damköhler number, both single peak and complex multipeak oscillations are found. In the cell model, both regular oscillations near the inlet and chaotic behavior downstream are observed. In the dispersion model, higher Peclet numbers eliminate the oscillations. The spatial profile shows a train of pulsating waves for the discret model and a single pulsating or solitary wave for the continuous model.     

Effect of Processing Parameters on the Mechanical and Microstructural Behavior of Ultra-Fine Al2O3– (ZrO2+8%Mol Y2O3) Bioceramic, Densified By High-Frequency Induction Heat Sintering

High-frequency induction heat sintering (HFIHS) is a comparatively new technique that consolidates metals and ceramics very rapidly to full density. In this work, superfast densification behavior and the attendant microstructural features of Al₂O₃–(ZrO₂+8% mol Y₂O₃) composites processed by HFIHS were investigated. The effects of processing parameters such as sintering temperatures, pressures, and heating rate, on the mechanical and microstructural properties were studied. The results indicated that HFIHS was effective in the preparation of fine-grained, nearly fully dense Al₂O₃–8YSZ ceramics from the powder with a smaller particle size by optimizing the overall processing parameters.     

Swelling and mechanical properties of superporous hydrogels of poly(acrylamide-co-acrylic acid)/polyethylenimine interpenetrating polymer networks

Swelling and mechanical properties were investigated for superporous hydrogels (SPHs) of poly(acrylamide-co-acrylic acid)/polyethylenimine (P(AM-co-AA)/PEI) interpenetrating polymer networks (IPNs). Gelation kinetics of SPHs changed significantly according to the acidic condition of reactant. The compressive strength of neutralized SPHs decreased monotonically with AA concentration, while the maximum swelling was observed around the AA weight fraction of 0.4 for all PEI concentrations. The SPH samples composed of high concentrations of AA and PEI were easily cracked in water due to the swelling stress developed during water uptake. The swelling kinetics decreased with increasing PEI and PAA concentrations because of the high molecular entanglement and network density associated with ionic interaction between PAA and PEI molecules. For non-neutralized SPHs, the equilibrium water uptake decreased but the compressive strength increased with PEI and PAA concentrations by simple plasticization effect.     

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.     

Continuous polymerization of lactam–lactone block copolymers in a twin‐screw extruder

Continuous copolymerizations of ?‐caprolactone with ?‐caprolactam and ω‐lauryl lactam were carried out in a modular intermeshing corotating twin‐screw extruder. Sodium hydride (initiator) and N‐acetyl caprolactam (coinitiator) were used to synthesize lactam–lactone copolymers in a twin‐screw extruder. We consider the variables of feeding order and feed rate of comonomers on the reactive extrusion of lactam–lactone copolymers. It was observed that simultaneous feeding of both monomers with initiator and coinitiator in the first hopper produced a mixture of homopolymers. When we fed the lactam into the first hopper and caprolactone sequentially into the second hopper, we obtained the lactam–caprolactone block copolymers. However, when we fed caprolactone first into the first hopper and the lactam into the second hopper, the extruded product was a mixture of poly(?‐caprolactone) and lactam monomer. We synthesized high molecular weight copolymers of poly(caprolactam‐b‐caprolactone) and poly(lauryl lactam‐b‐caprolactone) with different block lengths by sequential feeding of monomers. The block length of the block copolymer could be adjusted by controlling the feed rate of each monomer during reactive extrusion. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1429–1437, 2003     

Continuous ethanol production from wood hydrolysate by chemostat and total cell retention culture

Chemostat and total cell retention cultures with internal filter system ofSaecharomyc.es cerevisiae H1-7 were carried out to produce ethanol from wood hydrolysate. Maximum ethanol productivity obtained in a chemostat with the aeration rate of 1 vvm was 3.79 g/(L·h). This was 20% higher than that in a chemostat without aeration. However, the substrate was not completely consumed at the dilution rate with the maximum productivity. The realistic productivity, which has higher than 99% conversion rate of substrate, was. 2.95 g/(L·h). The maximum productivity in the total cell retention culture was 6.65 g/(L·h) at the dilution rate of 0.19 h¹ and the residual glucose concentration was negligible.     

Cure kinetics and mechanical properties of the blend system of epoxy/diaminodiphenyl sulfone and amine terminated polyetherimide-carboxyl terminated poly(butadiene-co-acrylonitrile) block copolymer

The cure kinetics of blends of epoxy resin (4,4’-tetraglycidyl diaminodiphenyl methane; TGDDM)/curing agent (diaminodiphenyl sulfone; DDS) with ATPEI (amine terminated poly-etherimide) -CTBN (carboxyl terminated poly (butadiene-co-acrylonitrile)) block copolymer (AB type) were studied using differential scanning calorimetry under isothermal conditions to determine the reaction kinetic parameters such as activation energy and reaction constants. Final cure conversion decreased with increasing amount of AB in the blends. A diffusion controlled reaction was observed as the cure conversion increased, and the curing reaction was successfully analyzed by incorporating the diffusion control term in the rate equation for the epoxy/DDS/AB blends. The fracture toughness was improved to about 350% compared to that of the unmodified resin at 30% of AB block copolymer. This is attributed to the formation of co-continuous morphology between the epoxy phase and AB block copolymer phase. By increasing the amount of AB, the modulus of the cured blends decreased, which was due to the presence of CTBN rubbery phases.     

The effect of various anti-setting systems in wool dyeing. Part 3; Sodium thiocyanate based systems

Wool fabrics undergo setting during dyeing. The degree of set can be controlled by careful selection of dyebath conditions and also by the addition to the dyebath of chemicals termed anti-setting agents. The anti-setting effect of sodium thiocyanate has been evaluated according to its concentration in the dyebath and the dyebath pH. The fabric crease-angle method was adopted to estimate the degree of anti-setting. In the case of wool fabric boiled in the presence of sodium thiocyanate, good anti-setting effects resulted from the pH 3 and pH 5 treatment baths. Chemical changes in the wool were detected using FTIR analysis.     

Compatibility and thermal properties of poly(acrylonitrile–butadiene–styrene) copolymer blends with poly(methyl methacrylate) and poly(styrene‐co‐acrylonitrile)

The mechanical and heat‐resistant properties of acrylonitrile–butadiene–styrene (ABS) binary and ternary blends were investigated. The relationship of compatibility and properties was discussed. The results show that poly(methyl methacrylate) (PMMA) and styrene–maleic anhydride (SMA) can improve the thermal properties of conventional ABS. The Izod impact property of ABS/PMMA blends increases significantly with the addition of PMMA, whereas that of ABS/SMA blends decreases significantly with the addition of SMA. Blends mixed with high‐viscosity PMMA are characterized by higher heat‐distortion temperature (HDT), and their heat resistance is similar to that of blends mixed with SMA. For high‐viscosity PMMA, from 10 to 20%, it is clear that blends appear at the brittle–ductile transition, which is related to the compatibility of the two phases. TEM micrographs show low‐content and high‐viscosity PMMA in large, abnormally shaped forms in the matrix. Compatibility between PMMA and ABS is dependent on both the amount and the viscosity of PMMA. When the amount of high‐viscosity PMMA varied from 10 to 20 wt %, the morphology of the ABS binary blends varied from poor to satisfactory compatibility. As the viscosity of PMMA decreases, the critical amount of PMMA needed for the compatibility of the two phases also decreases. SMA, as a compatibilizer, improved the interfacial adhesiveness of ABS and PMMA, which results in PMMA having good dispersion in the matrix. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2652–2660, 2002     

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.