A kinetic model for polystyrene (PS) pyrolysis reaction

A mathematical model for the pyrolysis reaction of polystyrene (PS) in a semi-batch reactor has been presented. The thermal degradation of PS was flexibly modeled by a combination of random and specific chain-end scissions. Numerical simulation was used to investigate the effect of operating conditions on the PS products spectrum, the results of which were validated by the experimental data. It was found that as the reaction temperature increased (decreased), the monomer fraction in the products became lower (higher) while the trimer higher (lower). No significant variation in the product composition was, however, observed while constant temperature was maintained. These results indicate the reaction temperature is an effective manipulated variable for the control of products composition of PS pyrolysis. The calculation of the optimum temperature trajectories through the optimization study can thus be of interest for achieving productivity enhancement in plastics pyrolysis processes. This paper is dedicated to Professor Dong Sup Doh on the occasion of his retirement from Korea University.     

Relationship between chemical degradation and thickness loss of an amine-cured epoxy coating exposed to different UV environments

The relationship between chemical degradation and thickness loss of an unpigmented, non UV-stabilized, crosslinked amine-cured epoxy coating exposed to three UV conditions was investigated. Spin-coated samples having a thickness of approximately 7 μm on an Si substrate were prepared from a stochiometric mixture of a bisphenol A epoxy resin and a tetra-functional amine curing agent. Samples were exposed outdoors and to two accelerated laboratory UV environments. Chemical degradation and thickness loss were measured by transmission Fourier transform infrared spectroscopy (FTIRS) and laser scanning confocal microscopy (LSCM), respectively. In addition, surface roughness and morphological changes were measured by atomic forcemicrosocopy (AFM) and LSCM. Substantial chemical degradation, thickness loss, and morpholocal changes occurred in the exposed films, and the rate of chemical degradation was greater than that due to the thickness loss. This additional chemical loss was attributed to an inhomogeneous degradation process in which nanoscale localized depressions initiate at certain sites on the surface, which then enlarge and deepen with exposure time. The results of this study provide a better understanding of the degradation mechanism and should lead to the development of scientific-based models for predicting the service life of crosslinked amine-cured epoxy coatings. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, October 27–29, 2004, in Chicago, IL     

Preparation and electrical properties of metal sulfides–amidoximated PAN composite film

To improve the electrical conductivity of polyacrylonitrile (PAN) film, metallic sulfides and PAN composite film were prepared by the chelating method. Dense PAN film and porous PAN film were prepared by dry process and wet process, respectively. These PAN films were treated to NH₂OH solution to introduce the amidoxime group coordinated with metallic ion. Cu⁺² and Cd⁺² ions were adsorbed to amidoximated PAN films, the sulfur ion was treated with metal-adsorbed PAN films, and thus CuS—and CdS–PAN composite films were prepared. The adsorptive capacity of amidoximated PAN film for the Cu⁺² ion was independent of the morphology of the PAN film, but the adsorptive capacity of the Cd⁺² ion on amidoximated PAN film was dependent on porosity of the polymer. Adsorptive capacity of amidoximated porous PAN film for Cd⁺² was improved about four times than that of amidoximated dense PAN film. The electrical conductivities of CuS–dense and porous PAN composite film were both 10^?1 S/cm in optimum condition, but because of the difference in adsorptive capacity, the electrical conductivities of CdS–dense and CdS–porous PAN composite films were 10^?9 S/cm and 10^?4 S/cm, respectively. Additionally, because CdS was known as a photoconductive material, the photoconductive properties of CdS–porous PAN composite film were investigated.     

Rheological and electrical properties of polycarbonate/multi-walled carbon nanotube composites

Rheological and electrical properties of the polycarbonate (PC)/multi-walled carbon nanotube (MWNT) were studied. The MWNT was funtoinalized by treating with the hydrogen peroxide (H₂O₂). The H₂O₂ treated MWNT was dried by thermal and freeze drying methods. From the morphological studies, the degree of entanglement of the MWNT was decreased after treating with the H₂O₂. For the H₂O₂ treated MWNT (thermal drying), the length of the MWNT was shortened compared that of the H₂O₂ treated MWNT (freeze drying). The rheological and electrical properties of the PC/MWNT (H₂O₂ treated) composites increased compared that of the PC/MWNT (untreated) composites. Also, the electrical conductivity showed higher value for the PC/MWNT (H₂O₂ treated, freeze drying) composites compared that of the PC/MWNT (H₂O₂ treated, thermal drying) composites. From the results of the morphological, rheological, and electrical properties of the PC/MWNT composites, it is suggested that the electrical and rheological properties of the PC/MWNT composites are affected by the MWNT-MWNT network structure, which is related with the MWNT morphologies such as the degree of aggregation and aspect ratio of the MWNT.     

Highly Efficient Overall Water Splitting Through Optimization of Preparation and Operation Conditions of Layered Perovskite Photocatalysts

The layered perovskite materials were found to give the high photocatalytic activity in water splitting reaction under UV irradiation, where the electronic structure of perovskite slab constructing the layered structure (the total cation valency) was the most crucial factor to the high photocatalytic activity. Both the excessive cation valency and the layered structure were required for active photocatalysts, while the slab thickness of layered perovskites had an insignificant effect on water-splitting activity. In order to identify key variables that affected photocatalytic activity and to optimize the performance of (110) layered perovskite, La₂Ti₂O₇ was modified by various methods. The optimum amount of loaded nickel had a great effect and the amount depended on the surface area of the perovskite phase. When an alkaline-earth element such as Ba, Sr, and Ca was doped on La₂Ti₂O₇, the photocatalytic activity was enhanced markedly. Introduction of an alkaline hydroxide into the reaction system as an external additive enhanced the activity further showing extremely high quantum yields close to 50%.     

Mechanical and thermal properties of ceramic‐modified poly(amide imide)

Poly(amide imide)–epoxysilane (coupling agent) composites were reacted with silica, a condensation product of tetraethylorthosilicate (TEOS), by a sol–gel process and were then cast into films. After this procedure, the chemical characteristics and mechanical and thermal properties were measured. Fourier transform infrared showed that silica existed in the poly(amide imide) matrix. When a proper amount of silica was added to the poly(amide imide) matrix, the tensile strength, elongation, and toughness increased greatly. A poly(amide imide)/30 wt % epoxysilane composite with 20 wt % TEOS had the best mechanical properties. Thermogravimetric analysis under nitrogen and oxygen atmospheres indicated that the char contents increased with the amount of silica. The glass‐transition temperatures of the poly(amide imide)–silica nanocomposites were observed around 170–180°C with differential scanning calorimetry. This approach may be a new method for the low‐temperature thermal curing of poly(amide imide). © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1780–1788, 2004     

Fabrication of SiO2-ZrO2 composite fiber mats via electrospinning

(1 − x)SiO₂-(x)ZrO₂ (x = 0.1, 0.2) composite fiber mats were prepared by electrospinning their sol-gel precursors of zirconium acetate and tetraethyl orthosilicate (TEOS) without using a polymer binder. The electrospun composite fibers were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), fourier transform infrared spectroscopy (FT-IR) and mercury porosimetry. The composite fibers having a tetragonal crystalline ZrO₂ were obtained by calcining the electrospun composite fibers at high temperatures. The results show that the structure and crystallization of ZrO₂ in the composite fibers can be controlled by sintering temperature, while the porosity and morphology of the fiber mats did not depend on the sintering temperature.     

Efficient verifiably encrypted signatures from lattices

Verifiably encrypted signature schemes can convince a verifier that a given ciphertext is an encryption of an ordinary signature on a given message and the ordinary signature can be recovered by the third party, called adjudicator. In 2010, Rückert et al. proposed a general construction for the verifiably encrypted signatures, and then, they also showed that there exist the lattice-based verifiably encrypted signature schemes. Their constructions are very insightful, but their schemes need an extra adjudication setup phase and Merkle trees, so they have large parameters and keys, that is, they are inefficient. Also, their schemes provide only the limited signature capacity because the signing keys should be reissued after generating \(k\) th verifiably encrypted signatures. To overcome the weaknesses of Rückert et al.’s scheme, we construct a verifiably encrypted signature scheme based on the hard lattice problems. Our scheme provides the full functionality, i.e., the signatures can be generated without any limitations and does not need any extra adjudication setup phases. Moreover, the size of the secret keys in our scheme is constant. Our scheme provides unforgeability, opacity, extractability, and abuse-freeness in the random oracle model.     

The effects of Ni and Li doping on the performance of lithium manganese oxide material for lithium secondary batteries

Layered Li_0.7[M_1/6Mn_5/6]O₂ (M=Li, Ni) was synthesized using a sol-gel method. P2-Na_0.7[M_1/6Mn_5/6]O₂ precursor was first synthesized by a sol-gel method, and then O2-Li_0.7[M_1/6Mn_5/6]O₂ was prepared by an ion exchange of Li for Na in P2-Na_0.7[M_1/6Mn_5/6]O₂ precursor. From charge/discharge curves, it was seen that Li_0.7[Li_1/6Mn_5/6]O₂ has two plateaus similar to those observed from a spinel structure, but Li_0.7[Ni_1/6Mn_5/6]O₂ holds a single plateau as observed from a typical layered structure. It was considered that Li_0.7[Li_1/6Mn_5/6]O₂ undergoes a phase transformation from layered to spinel structure during the charge/discharge cycle, but Li_0.7[Ni_1/6Mn_5/6]O₂ maintains O2-layered structure after the cycles. Li_0.7[Ni_1/6Mn_5/6]O₂ was higher in discharge capacity and retention rate than Li_0.7[Li_1/6Mn_5/6]O₂.