钒在陶瓷工业中的应用

本文通过钒的应用，阐述了金光釉和凹釉的形成机理。并说明了其在陶瓷釉料生产中所扮演的重要角色。     

Effect of hydrophobic hexafluoroisopropylidene group on the water sorption behaviors of rigid poly(p‐phenylene pyromellitimide) polyimide thin films

We prepared poly(p‐phenylene pyromellitimide) (PMDA–PDA), poly(p‐phenylene 4,4′‐hexafluoroisopropylidene diphthalimide), and their copolyimides with various compositions to explore the relationship between the water sorption and structure. The water sorption behaviors were gravimetrically investigated as a function of composition and temperature and interpreted with a Fickian diffusion model in films. Overall, the water sorption behaviors were strongly dependent on the changes in morphological structure, which originated from the variations in composition. When the content of the bulky hexafluoroisopropylidene group (6FDA) was increased, the water uptake decreased from 5.80 to 3.18 wt %, whereas the diffusion coefficient increased from 3.6 × 10^?10 to 11.3 × 10^?10 cm²/s. The relatively high water uptake in the PMDA–PDA polyimide film was successfully healed by the incorporation of 6FDA, which may have resulted from the increases in the intermolecular packing order and hydrophobicity. The degree of orientation and crystallinity, which are in‐plane characteristics, were directly correlated to the diffusion coefficient and activation energy in the polyimide film. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3442–3446, 2003     

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.     

Preparation and properties of polyimide/silica hybrid composites based on polymer‐modified colloidal silica

A new type of polyimide/silica (PI/SiO₂) hybrid composite films was prepared by blending polymer‐modified colloidal silica with the semiflexible polyimide. Polyimide was solution‐imidized at higher temperature than the glass transition temperature (T_g) using 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA) and 4,4′‐diaminodiphenyl ether (ODA). The morphological observation on the prepared hybrid films by scanning electron microscopy (SEM) pointed to the existence of miscible organic–inorganic phase, which resulted in improved mechanical properties compared with pure PI. The incorporation of the silica structures in the PI matrix also increased both T_g and thermal stability of the resulting films. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2053–2061, 2006     

Phase Behavior and Mechanical Properties of Siloxane-Urethane Copolymer

Two series of siloxane-urethane copolymers were prepared from polydimethylsiloxane (PDMS) with a molecular weight of 1000 or 1800 which was used as a soft segment, 4,4′-diphenylmethane diisocyanate (MDI) and 1,4-butanediol (1,4-BD). Differential scanning calorimetry (DSC) demonstrated that the position (T_gs) and breadth (ΔB) of soft-segment glass transition of copolymers remained constant as the hard-segment content increased. Heat capacities at soft-segment glass transition of the copolymer (ΔCp) were 0.195∼0.411 J/g^○C and heat capacities of pure PDMS (ΔCp₀) were 0.571∼0.647 J/g^○C, leading to the various ΔCp/ΔCp₀ ratios. The ΔCp/ΔCp₀ ratios decreased as the increasing of hard-segment content, showing poor phase separation. The FTIR spectrum confirmed the occurrence of hydrogen bonding in ether end-group of pure PDMS. The ether group of the soft segment led to interfacial mixing between soft and hard segments. The tan δ of the soft segment determined by dynamic mechanical testing (DMA) also identified the mixing of soft and hard segments. The mechanical properties of the copolymer were directly related to either the soft and hard segment contents or the chain lengths of soft and hard segments. The hard segment that reinforced the soft segment and interfacial thickness between soft and hard segment dominated the mechanical properties.     

Anisotropically ordered liquid crystalline epoxy network on carbon fiber surface

Summary Anisotropic orientation of liquid crystalline epoxy(LCE) resin on carbon fiber(CF) surface was investigated and it was correlated with curing behavior and thermomechanical properties of LCE. Anisotropic orientation of a LCE resin was spontaneously induced on CF surface along a long molecular axis of CF during curing and the anisotropic orientation was maintained after curing. Curing of LCE was accelerated by alignment of LCE on CF and anisotropic orientation of LCE enhanced dynamic modulus of CF reinforced LCE composites.     

Universal yield stress function for biocompatible chitosan based-electrorheological fluid: Effect of particle concentration

Electrorheological (ER) response of biocompatible particles suspended in an insulating silicone oil, was investigated under several different applied external electric field strengths. Chitosan, a biodegradable polysaccharide, was used as anhydrous ER materials. The effect of particle volume concentration on their ER response was examined by focusing on the measurement for rheological and electrical properties. The yield stress of chitosan suspended in silicone oil system as a function of applied electric field strength showed different value of slopes for different particle concentrations, however, all data points collapse onto a universal scaling function.     

Morphology and mechanical properties of liquid crystalline copolyester and poly(ethylene 2,6-naphthalate) blends

Blends of poly(ethylene 2,6-naphthalate) (PEN) and a liquid crystalline copolyester (LCP), poly(benzoate-naphthoate), were prepared in a twin-screw extruder. Specimens for mechanical testing were prepared by injection molding. The morphology and mechanical properties were investigated by scanning electron microscopy (SEM) and an Instron tensile tester. SEM studies revealed that finely dispersed spherical domains of the liquid crystalline polymer (LCP) were formed in the PEN matrix, and the inclusions were deformed into fibrils from the spherical droplets with increasing LCP content. The morphology of the blends was found to be affected by their composition and a distinct skin-core morphology was found to develop in the injection molded samples of these blends. Mechanical properties were improved with increasing LCP content, and synergistic effects have been observed at 70 wt% LCP content whereas the elongation at break was found to be reduced drastically above 10 wt% of LCP content. This is a characteristic typical of chopped-fiber-filled composites. The improvement in mechanical properties is likely due to the reinforcement of the PEN matrix by the fibrous LCP phase as observed by scanning electron microscopy. The tensile and modulus mechanical behavior of the LCP/PEN blends was very similar to those of the polymeric composite, and the tensile strength and flexural modulus of the LCP/PEN 70/30 blend were two times the value of PEN homopolymer and exceeded those of pure LCP, suggesting LCP acts as a reinforcing agent in the blends.     

Enhancement of combustion efficiency with mixing ratio during fluidized bed combustion of anthracite and bituminous blended coal

In order to investigate the effect of mixing ratio of bituminous coal to blended coal on the enhancement of combustion efficiency, combustion experiments of blended coal with anthracite and bituminous are done in a laboratory scale fluidized bed combustor (10.8 cm ID and 170 cm height). The gross heating values of anthracite and bituminous coal used in this study are 2,810 cal/g and 6,572 cal/g, respectively. Experimental parameters are fuel feed rate, superficial gas velocity and mixing ratio of bituminous coal to blended coal. The combustion efficiency increases with the mixing ratio of bituminous coal due to the lower unburned carbon losses and higher burning velocity of bituminous coal. The rate of combustion in the combustor was increased with mixing ratio resulted from a higher burning velocity of bituminous coal. The measured combustion efficiency experimentally is about 3.5-12.4% higher than that of the calculated value based on the individual combustion of anthracite and bituminous coal under the same operating conditions. The optimum mixing ratio (MR) of bituminous coal determined is around 0.75 in this study. This paper is dedicated to Professor Dong Sup Doh on the occasion of his retirement from Korea University.     

Organic Nanoparticles with Polypropyleneoxide Chains as Support for Metallocene Catalysts: Ethylene Homopolymerization and Ethylene/α-olefin Copolymerization

Summary Novel organic nanoparticles functionalized with nucleophilic polypropyleneoxide (PPO) chains on their surfaces for supporting metallocene catalysts in heterogeneous olefin polymerization are presented. The nanoparticles (60–100 nm) were obtained by miniemulsion polymerization of styrene, divinylbenzene and PPO functionalized styrene. It is demonstrated that Me₂Si(2MeBenzlnd)₂ZrCl₂/MAO supported on these nanoparticles is suitable for the homopolymerization of ethylene, resulting in excellent product morphologies and high activities. lt is shown that by varying the MAO/Zr ratios and Zr concentrations the activities and productivities of the catalysts as well as the qualities of the polyethylene products can be tuned. These new supported catalysts are also suitable for the copolymerization of ethylene with several comonomers (1-hexene, 1-octene, 1-decene or norbornene). As the obtained product properties like crystallinity, melting temperature or bulk density match the results of silica supported systems, these organic nanoparticles can be considered as alternative carriers in comparison to the established inorganic ones.