Optimal reaction conditions for the minimization of energy consumption and by‐product formation in a poly(ethylene terephthalate) process

We determined the optimal reaction conditions to minimize the energy cost and the quantities of by‐products for a poly(ethylene terephthalate) process by using the iterative dynamic programming (IDP) algorithm. Here, we employed a sequence of three reactor models: the semibatch transesterification reactor model, the semibatch prepolymerization reactor model, and the rotating‐disc‐type polycondensation reactor model. We selectively chose or developed the reactor models by incorporating experimentally verified kinetic models reported in the literature. We established the model for the entire reactor system by connecting the three reactor models in series and by resolving some joint problems arising when different types of reactor models were interconnected. On the basis of the simulation results of the reactor system, we scrutinized the cause and effect between the reaction conditions and the final quality of the polymer product. Here, we set up the optimization strategy by using IDP on the basis of the integrated reactor model, and the process variables with significant influence on the properties of polymer were selected as control variables with the help of a simulation study. With this method, we could refine the reaction conditions at the end of each iteration step by contracting the spectra of control regions, and the iteration process finally stopped when the profile of the optimal trajectory converged. We also took the constraints on the control variables into account to guarantee polymer quality and to suppress side reactions. Constituting six different strategies by setting weighting vectors differently, we examined the differences in optimal trajectories, the trend of optimality, and the quality of the final polymer product. For each of the strategies, we conducted the optimization to examine whether the number‐average degree of polymerization approached the desired value. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 993–1008, 2002     

Fabrication of high surface area graphitic nanoflakes on carbon nanotubes templates

Graphitic nanoflakes were fabricated on the carbon nanotubes templates for increasing the surface area utilizing bias assisted microwave plasma enhanced chemical vapor deposition (MWPECVD). The analysis of morphologies and structures were achieved by means of scanning electron microscopy and transmission electron microscopy. The surface area of graphitic nanoflakes, carbon nanotubes (CNTs) and graphitic nanoflakes/CNTs were 57.44 m²/g, 90.31 m²/g and 130.96 m²/g from BET measurement, respectively. The cyclic voltammetry was used to calculate the active area of platinum catalysts in 1 M sulfuric acid from hydrogen adsorption peak. An enhancement of activity could be observed from the calculation of CV results. This may be attributed to the small particle size and high dispersion of platinum particles coated on graphitic nanoflakes/CNTs. These high surface area materials could be used as catalysts supports or electrode for fuel cell applications.     

Study of alinite cement hydration by impedance spectroscopy

Two types of alinite cements, Mg-alinite and Zn-alinite, were synthesized using the reagent grade chemicals. Their hydration behavior was compared with ordinary Portland cement (OPC) using impedance spectroscopy (IS) and ²⁹Si nuclear magnetic resonance (NMR) spectroscopy. The bulk resistance in the IS spectra and the intensity ratio of the hydrous (Q₁ and Q₂) to anhydrous (Q₀) phases in the NMR spectra were estimated as the extent of hydration. The results obtained from both techniques were consistent each other. Mg-alinite had a comparable hydration rate to OPC and Zn-alinite exhibited faster hydration kinetics than Mg-alinite.     

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.     

The effct of asymmetries of die exit geometry on extrudate swell and melt fracture

Experimental investigations were performed to see how the die exit geometry and the extrusion velocity influence on extrudate swell and melt fracture for several polymer melts [low-density polyethylene, styrene-butadiene rubber (SBR) and SBR/HAF (carbon black) compound]. Four different types of die exit geometry were considered; 0° (symmetric. usual capillary die), and 30°, 45° and 60° (asymmetric dies) were chosen for the die exit angle. Extrudate diameters were measured without draw-down under isothermal condition. Polymer melts were extruded into an oil that has the same density and temperature as those of the extrudate. Extrudate swells from dies with different diameters were correlated with volumetric flow rates. It was observed that the extrudate swell increases with increasing volumetric flow rate and exhibits through a minimum value at about 45° die exit angle. As to the fracture phenomena, it was observed that the critical shear for the onset of melt fracture increases with the increasing die exit angle up to 45°. However, for 60° die exit angle, the onset of melt fracture is again similar to that of 0° exit angle.     

Polyurethane–poly(methyl methacrylate) block copolymer dispersions through polyurethane macroiniferters

Polyurethane macroiniferter/poly(methyl methacrylate) block copolymer dispersions with inverse core‐shell morphologies were obtained from 1,1,2,2,‐tetraphenylethane‐1,2‐diol, dimethylol propionic acid, 4,4′‐diphenylmethane diisocyanate, and poly(propylene glycol) via a living radical mechanism. Molecular weight, particle size and dispersion viscosity, and thermal, mechanical, and dynamic mechanical properties of the dispersion cast films are reported as a function of copolymerization time. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1971–1975, 2003     

Analysis of microbial adaptation at enzyme level for enhancing biodegradation rate of BTX

Catechol was found to be a common intermediate in the degradation of benzene and toluene byAlcaligenes xyhsoxidans Y234, and the ring cleavage of the catechol mediated by catechol 1,2-dioxygenase was a rate-determining step. Since benzene induced higher level of catechol 1,2-dioxygenase than toluene, the cells pre-adapted to benzene showed higher degradation rate of benzene and toluene. The degradation rate ofm-xylene was also increased significantly when benzene-adapted cells were inoculated.m-Xylene was metabolized via 3-methyl catechol which was effectively cleaved by catechol 1,2-dioxygenase.     

Catalytic reduction of no over perovskite-type catalysts

In the present work, we have investigated the reduction of NO by propane over perovskite-type oxides prepared by malic acid method. The catalysts were modified to enhance the activity by substitution of metal into A or B site of perovskite oxides. In addition, the reaction conditions, such as temperature, O₂ concentration, and space velocity have been varied to understand their effects on the catalytic performance. In the LaCoO₃ type catalyst, the partial substitution of Ba and Sr into A site enhanced the catalytic activity in the reduction of NO. For the La_0.6Ba (Sr)_o.4 Co_1−x Fe_xO₃ (x=0-1.0) catalyst, the partial substitution of Fe into B site enhanced the conversion of NO, but excess amount of Fe decreased the conversion of NO. The surface area and catalytic activity of perovskite catalysts prepared by malic acid method showed higher values than those of solid reaction method. The conversion of NO increased with increasing O₂ concentration and contact time. The introduction of water into reactant feed decreased the catalytic activity but the deactivation was shown to be reversible over La_0.6Ba_0.4Co_1−x ,Fe_xO₃ catalyst.     

Effect of clinoptilolite addition and solids retention time on the extracellular polymeric substances composition and soluble chemical oxygen demands in activated sludge

This study was carried out to compare EPS (Extracellular Polymeric Substances) composition between conventional activated sludge (AS) and activated sludge dosed with clinoptilolite (CAS). Additionally, those were compared with organic removal efficiency in the effluent in conjunction with EPS concentrations. The experiments were conducted at SRT (Solids Retention Time) ranging from 5 to 100 d. For the CAS, proteins were more readily observed for SRT 20 and 100 d compared to that of the AS. Polysaccharide concentration in the sludge was greatly increased for the CAS, but it was significantly diminished when the SRT was extended. The level of EPS concentration observed from the effluent had the same pattern of variation for the two different types of systems. Regardless of type of reactor, the ratio of proteins for sludge versus effluent was independent of SRT, but the ratio of polysaccharides diminished as SRT increased. In the long run, the degree of protein synthesis directly ascribed to concurrent enhancement of SCOD removal efficiency was slightly more in the CAS. It was decided that clinoptilolite added system could be more reliably retrofitted to a conventional activated sludge process.     

Electrosteric stabilization of concentrated cement suspensions imparted by a strong anionic polyelectrolyte and a non-ionic polymer

Strong polyelectrolytes, known as superplasticizers, improve the initial fluidity of concentrated cement suspensions through electrostatic stabilization. These polyelectrolytes do not maintain the initial fluidity, however, primarily due to an increase in the ionic strength of the cementitious suspension. Consequently, non-ionic polymers are often used in conjunction with polyelectrolytes to provide steric stabilization and hence to sustain the desired fluidity over a longer time, and this has lead to the development of copolymers with both electrostatic and steric (electrosteric) functionalities. To design such polymers, it is necessary to optimize the balance between electrostatic and steric stabilization to maximize suspension fluidity. We have quantified the effects of a strong anionic polyelectrolyte, melamine formaldehyde sulfonate (MFS), and a non-ionic polymer, hydroxypropylmethylcellulose (HPMC), on the zeta potential of cement particles and the steady shear and low-amplitude rheological properties of concentrated cement suspensions. While the adsorption of MFS onto the cement particle surfaces leads to a sign inversion in the zeta potential, the adsorption of the non-ionic HPMC has no significant effect on the potential. The addition of HPMC to the suspensions substantially reduces the steady shear viscosity and the storage modulus at constant MFS concentration; in addition, there exists an intermediate HPMC concentration that minimizes fluidity. The resulting suspension fluidity is also maintained over a longer time than in the absence of HPMC. This improvement in the stability and fluidity of cement suspensions is attributed to “complementary electrosteric dispersion/stabilization”, and provides insight to the design of polymers with electrosteric functionality.