Manufacturing and foaming of high melt viscosity of polypropylene by using electron beam radiation technology

The high melt viscosity of polypropylene was studied by grafting bifunctional monomers, 1,6‐hexanediol diacrylate (HDDA) and tripropylene glycol diacrylate (TPGDA), onto homopolypropylene (HPP) and random ter‐polypropylene (RTPP) under electron‐beam irradiation. Creation of the high‐melt‐viscosity polypropylene was possible at low radiation dosage and low monomer content, under a prohibition of both radiation degradation and homopolymerization. TPGDA monomer was more effective in increasing the melt viscosity of HPP compared with RTPP, whereas HDDA monomer was more effective for enhancing the melt viscosity of RTPP. Such different effects of monomers on melt viscosity may arise from different monomer structures, namely, TPGDA has additional three methyl groups, but HDDA has no methyl groups. Electron‐beam radiation technology, on an increase of the melt viscosity, was much more effective in HPP than RTPP, when compared with virgin polymers. Modified RTPP and HPP with high melt viscosity were capable of foaming with numerous fine cells, of which the modified HPP with 1.5 mmol TPGDA and 0.5 kGy could create more spherical foam cells and its bending strength was 1.5 times more than that of the foamed RTPP. POLYM. ENG. SCI., 46:431–437, 2006. © 2006 Society of Plastics Engineers.     

Design and control of reactive distillation for ethyl and isopropyl acetates production with azeotropic feeds

Reactive distillations for the production of ethyl acetate (EtAc) and isopropyl acetate (IPAc) are classified as the type-II process where the first column consists of a reactive zone and a rectifying section followed by a stripper [Tang et al., 2005. Design of reactive distillations for acetic acid esterification with different alcohols. A.I.Ch.E. Journal 51, 1683-1699]. Instead of using pure alcohols and acetic acid as reactants, this paper studies the effects of reactant purity on the design and control of reactive distillation. This offers significant economical incentives (by reducing raw materials costs), because ethanol forms an azeotrope with water at 90 mol% and isopropanol/water has an azeotrope at 68%. The purities of the acid is set to 95% for acetic acid (industrial grade), 87% for ethanol, and 65% for isopropanol. The results show that the total annual costs (TAC) increase by a factor of 5% for EtAc and 8% for IPAc production using reactive distillation. Next, the operability of the reactive distillations with azeotrope feeds is explored. Three disturbances, feed flow, acid feed purity, and alcohol feed composition, are introduced to assess control performance using dual-temperature control and one-temperature-one-composition control. Simulation results indicate good control performance can be achieved for reactive distillation with azeotropic feeds.     

Synthesis and characterization of novel copolymers with acid‐labile ketal moieties derived from camphor

Novel diastereomeric acrylic ketal monomers derived from (+)‐camphor and (±)‐camphor were synthesized. To investigate the applications of the camphor derivatives on positive‐tone photoresists, the acrylic ketal monomers were copolymerized with methyl methacrylate, methacrylic acid, and n‐butyl methacrylate. The optical activities of the chiral monomers and polymers were all evaluated. After UV irradiation and postexposure baking, the optical activity of the polymers decreased because of the decomposition of the acid‐labile pendant chiral groups. The existence of alicyclic camphyl groups increased the etching resistance of the photoresists. The thermogravimetric properties of the copolymers, the exposure curves, the lithographic evaluation of the positive‐tone photoresists, and the effects of alicyclic groups on the plasma etching resistance of the copolymers were all investigated. A resolution of a line‐and‐space pattern of 0.3 μm was achieved. Acid‐catalyzed dehydration crosslinking was also found in this system. Sufficient UV irradiation and heat treatment could cause the acid‐catalyzed dehydration crosslinking of pendant carboxyl groups and thereby increase the efficiency of the thermal resistance of the polymers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2969–2978, 2003     

An improved technique for exfoliating and dispersing nanoclay particles into polymer matrices using supercritical carbon dioxide

An environmentally benign process, which uses supercritical carbon dioxide (sc-CO₂) as a processing aid, is developed in this work to help exfoliate and disperse nanoclay into the polymer matrices. The process relies on rapid expansion of the clay followed by direct injection into the extruder where the mixture is dispersed into the polymer melt. Results from the mechanical properties, rheological studies, and X-ray diffraction (XRD) show that this method represents a significant improvement relative to direct melt blending in single or twin-screw extruders or other methods using sc-CO₂. The greatest mechanical property response was a result of directly injecting pre-mixed sc-CO₂ and nanoclay into the polypropylene melt during extrusion. It was observed that for concentrations as high as 6.6 wt% (limited only by present process capabilities), XRD peaks were eliminated, suggesting a high degree of exfoliation. Mechanical properties such as modulus increased by as much as 54%. The terminal region of the dynamic mechanical spectrum was similar to that of the base polymer, contrary to what is frequently reported in the literature.     

Illumination invariant object tracking with adaptive sparse representation

Since the introduction of the sparse representation-based tracking method named ?₁ tracker, there have been further studies into this tracking framework with promised results in challenging video sequences. However, in the situation of large illumination changes and shadow casting, the tracked object cannot be modeled efficiently by sparse representation templates. To overcome this problem, we propose a new illumination invariant tracker based on photometric normalization techniques and the sparse representation framework. With photometric normalization methods, we designed a new illumination invariant template presentation for tracking that eliminates the illumination influences, such as brightness variation and shadow casting. For a higher tracking accuracy, we introduced a strategy that adaptively selects the optimum template presentation at the update step of the tracking process. The experiments show that our approach outperforms the previous ?₁ and some state-of-the-art algorithms in tracking sequences with severe illumination effects.     

Analysis of cell aggregation in the culturing of cerebellar granule neurons

We have proposed previously that an increased concentration of growth factor secreted by neurons themselves has a direct effect on survival of the neurons, and thereby cell density serves as a regulator of survival of neurons. In this study, the same idea was used to analyze the aggregation of cerebellar granule neurons in culture experimentally and theoretically. Assuming the transport of growth factor and substrate within an aggregate is by molecular diffusion, the metabolic efficiency of neurons, on the basis of an autocatalytic phenomenon, was increased within an aggregate compared to an identical quantity of dispersed cells. A good agreement in the size of neuronal aggregate between the theoretical prediction and the experimental result was found. This illustrates that growth factors produced by neurons acting in either an autocrine or paracrine manner play an important role during the development of cultured neurons.     

Effect of imidization temperature on properties of polymide films

Some mechanical and electrical properties of the BPDA/ODA/PDA polyimide film prepared on mylar followed by various cure schedules have been studied. It has been found by FTIR that the imidization reaches its maximum after a 200°C cure schedule for this polyimide. However, the optimum condition of curing is a 350°C cure schedule. Following this cure schedule, one can obtained a polymide film with good mechanical and electrical properties. © 1993 John Wiley & Sons, Inc.     

Corrosion-resistant lightweight metallic bipolar plates for PEM fuel cells

Corrosion resistant treated metal bipolar plates with higher rigidity and electrical conductivity than graphite were developed and tested for PEM fuel cell applications. Six replicas of single cells were used three of which were made of graphite composites bipolar plates and the other three of the treated metallic plates. A Membrane Electrode Assembly (MEA) with 5.55 cm² active electrode areas, 0.3 mg cm^–2 Pt loading and Nafion membrane 115 was fitted to each cell and operated under identical conditions. The experimental testing was conducted at room temperature (20 °C). The average value of the data obtained for the three graphite cells was plotted. Similarly, the average value of the data obtained for the three treated metal cells was plotted on the same graph for comparison. Generally, the treated metal bipolar plate provided at least 12% saving in hydrogen consumption in comparison to graphite. This is attributed to the lower bulk and surface contact resistance of the metal used in this study in relation to graphite. The results of lifetime testing, conducted at room temperature under variable loading showed no indication of power degradation due to metal corrosion for at least 1500 hours.     

Synthesis and properties of poly(amide–imide)s based on N,N′‐bis(4‐carboxyphenyl)‐4,4′‐oxydiphthalimide,p‐aminobenzoic acid and various aromatic diamines

A new diimide–diacid monomer, N,N′‐bis(4‐carboxyphenyl)‐4,4′‐oxydiphthalimide (I), was prepared by azeotropic condensation of 4,4′‐oxydiphthalic anhydride (ODPA) and p‐aminobenzoic acid (p‐ABA) at a 1:2 molar ratio in a polar solvent mixed with toluene. A series of poly(amide–imide)s (PAI, III_a–m) was synthesized from the diimide–diacid I (or I′, diacid chloride of I) and various aromatic diamines by direct polycondensation (or low temperature polycondensation) using triphenyl phosphite and pyridine as condensing agents. It was found that only III_k–m having a meta‐structure at two terminals of the diamine could afford good quality, creasable films by solution‐casting; other PAIs III using diamine with para‐linkage at terminals were insoluble and crystalline; though III_g–i contained the soluble group of the diamine moieties, their solvent‐cast films were brittle. In order to improve their to solubility and film quality, copoly(amide–imide)s (Co‐PAIs) based on I and mixtures of p‐ABA and aromatic diamines were synthesized. When on equimolar of p‐ABA (m = 1) was mixed, most of Co‐PAIs IV had improved solubility and high inherent viscosities in the range 0.9–1.5 dl g^?1; however, their films were still brittle. With m = 3, series V was obtained, and all members exhibited high toughness. The solubility, film‐forming ability, crystallinity, and thermal properties of the resultant poly(amide–imide)s were investigated. © 2002 Society of Chemical Industry     

Equilibrium and kinetic studies of the extraction of chelated copper(II) anions with Aliquat 336

The equilibrium and kinetics of solvent extraction of Cu²⁺ from aqueous solutions containing equimolar EDTA with Aliquat 336 in n‐decanol and kerosene at 298 K were investigated. The concentrations of Cu²⁺ (8–50 mol m^?3), Cl^? (5–60 mol m^?3), and Aliquat 336 (20–100 mol m^?3) were varied. A semi‐empirical model with three parameters was proposed to describe the equilibrium behavior, in which the non‐idealities in both aqueous and organic phases were considered. Over the ranges studied, the model agreed reasonably well with the experimental data (standard deviation, 15%). The forward and backward reaction rate constants were determined as (5.31 ± 0.16)×10^?6 m^9/4 mol^?3/4 s^?1 and (2.62 ± 0.09)×10^?7 s^?1, respectively, at 298 K. An interfacial reaction mechanism was proposed, which revealed that the reaction between the chelated anions and trimeric amine molecules at the interface was rate limiting. The derived rate laws were consistent with the experimental results. © 2002 Society of Chemical Industry