Comparison of YAG: Eu phosphors synthesized by supercritical water in batch and continuous reactors

Luminescent yttrium aluminum garnet (YAG, Y₃Al₅O₁₂) nanoparticles doped with Eu (10 at%) were synthesized in batch-type and continuous-type supercritical water (SCW) reactors. In the case of the continuous-type SCW method, the particles of YAG: Eu phosphors were much smaller and demonstrated a uniform spherical-like shape. Inversely, in the case of the batch-type SCW method, a needle-like or elliptical-like shape was formed because a finite amount of time was required to reach SCW conditions from ambient conditions. However, the emission intensity of YAG: Eu phosphors synthesized by using the batch-type SCW method was stronger. Therefore, it is concluded that the continuous-type SCW method is superior to the batch-type SCW method from the viewpoint of the particle size and shape, but the luminescence property of phosphors in the continuous-type SCW method needs to be improved. In addition, a calcination process slightly improved the luminescence intensities of YAG: Eu phosphors generated by using either the batch-type or continuous-type SCW methods.     

Structure and properties of collagen‐konjac glucomannan‐sodium alginate blend films

A new kind of blend film was made by mixing the solutions of collagen, konjac glucommnnan (KGM), and sodium alginate. The structure of the blend film was characterized by FTIR, XRD, atomic absorption spectrophotometer, and SEM, respectively. The effects of weight ratio between the polymers on light transmittance, tensile strength, elongation at break, water permeability, and water absorption of the film were studied. The results showed that there were strong interactions and good compatibility between collagen, KGM, and sodium alginate in the film. The film possesses good mechanical properties. Therefore, it can be applied in biomedicine as a new type of biomaterial. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Synthesis and physicochemical characterization of amphiphilic block copolymer self‐aggregates formed by poly(ethylene glycol)‐block‐poly(ϵ‐caprolactone)

Diblock copolymers with different poly(ε‐caprolactone) (PCL) block lengths were synthesized by ring‐opening polymerization of ε‐caprolactone in the presence of monomethoxy poly(ethylene glycol) (mPEG‐OH, MW 2000) as initiator. The self‐aggregation behaviors and microscopic characteristics of the diblock copolymer self‐aggregates, prepared by the diafiltration method, were investigated by using ¹H NMR, dynamic light scattering (DLS), and fluorescence spectroscopy. The PEG–PCL block copolymers formed the self‐aggregate in an aqueous environment by intra‐ and/or intermolecular association between hydrophobic PCL chains. The critical aggregation concentrations of the block copolymer self‐aggregate became lower with increasing hydrophobic PCL block length. On the other hand, reverse trends of mean hydrodynamic diameters were measured by DLS owing to the increasing bulkiness of the hydrophobic chains and hydrophobic interaction between the PCL microdomains. The partition equilibrium constants (K_v) of pyrene, measured by fluorescence spectroscopy, revealed that the inner core hydrophobicity of the nanoparticles increased with increasing PCL chain length. The aggregation number of PCL chain per one hydrophobic microdomain, investigated by the fluorescence quenching method using cetylpyridinium chloride as a quencher, revealed that 4–20 block copolymer chains were needed to form a hydrophobic microdomain, depending on PCL block length. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3520–3527, 2006     

Relation of swelling and Tg depression to the apparent free volume of a particle‐filled,epoxy‐based adhesive

The effect of hygrothermal aging on a particle‐filled, epoxy‐based adhesive was studied using a gravimetric sorption technique. This study has explored moisture sorption characteristics as well as the associated behaviors of swelling and the depression of the glass transition temperature (T_g). We observed that the diffusion of water in this adhesive has a non‐Fickian behavior, and the depression of T_g proceeds to a definite value that is independent of the final equilibrium water content of the system. Our observations suggest that water diffuses into the polymer in a dual‐sorption mode, in which water resides in two populations. In one population, water is considered to occupy apparent free volume of the adhesive, and the second population water infiltrates polymer structure and forms hydrogen‐bonded clusters. Our results show that hygrothermal aging temperature and swelling do not alter the apparent free volume of this adhesive. We conclude that the constant value of T_g depression at saturation implies that only water in the apparent free volume is responsible for the T_g depression, whereas the swelling proceeds through the formation of hydrogen bonds in the adhesive. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1436–1444, 2003     

The Chemistry of Water Treatment Processes Involving Ozone,Hydrogen Peroxide and Ultraviolet Radiation

Advanced oxidation processes are defined as those which involve the generation of hydroxyl radicals in sufficient quantity to affect water purification. The theoretical and (practical yield of OH from O₃ at high pH, 0₃/H₂0₂, O₃/UV and H₂O₂/UV systems is reviewed. New data is presented which illustrates the importance of direct photolysis in the O₃/UV process, the effect of the H₂0₂:0₃ ratio in the O₃/H₂O₂ process, and the impact of the low extinction coefficient of H₂O₂ in the H₂0₂/UV process.     

Fast online acquisition and analysis for parison swell and sag in blow molding

It is critical to quantitatively and reliably characterize the effects of swell and sag phenomena on the final parison dimensions in extrusion blow molding. To achieve this goal, an online image acquisition and analysis technique was developed. The successive images of parison were automatically taken using the online acquisition apparatus. These images were then analyzed by the combined use of the conventional digital image processing method and the new one developed by the authors. So the development of parison diameter and thickness swells with the extrusion time could be determined online. On the basis of the online obtained actual swell values, the pure swell and sag components were quantitatively determined. The developed technique was tested through a series of experiments using several resins under different processing parameters and die types. Shown in the present article were the results for a converging die under three different die gaps and a high‐density polyethylene. Some new phenomena were observed using the proposed technique. The results showed that the technique yields fast and accurate determination of the evolution of diameter, thickness, and length of parison during its extrusion. The technique can be employed as a part of the closed loop control for blow molded part thickness. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2399–2406, 2006     

Faceting of High-Angle Grain Boundaries in Titanium-Excess BaTiO3

The grain boundaries in BaTiO₃ with excess Ti of 0.5, 0.3, and 0.1 at.% sintered at 1300° or 1250°C have been examined by scanning electron microscopy (SEM), electron backscattered diffraction pattern (EBSP), and transmission electron microscopy (TEM). In the 0.1% Ti-excess specimen, large grains growing abnormally form high-angle grain boundaries when they impinge on each other as verified by EBSP. A large fraction of these grain boundaries are faceted with hill-and-valley shapes. In the 0.5% Ti-excess specimen, large grains growing abnormally are elongated in the directions of their {111} double twins. These grains often form flat grain boundaries parallel to their {111} planes with the fine matrix grains, and the grain-boundary segments between the large impinging grains with high misorientation angles are often also parallel to the {111} planes of one of the grains. These grain boundaries are expected to be singular. Most of the grain boundaries between the randomly oriented fine-matrix grains in the 0.3 at.% Ti-excess specimen are also faceted with hill-and-valley shapes at finer scales when observed under TEM. The facet planes are parallel to {111}, {011}, and {012} planes of one of the grain pairs and are also expected to be singular. These high-angle grain boundaries lying on low index planes of one of the grain pairs are similar to those observed in other oxides and metals.     

Effect of low molecular weight polybutadiene as processing aid on properties of silica‐filled styrene–butadiene rubber compounds

Because silica has strong filler–filler interactions, a silica‐filled rubber compound shows a poor filler dispersion compared to a carbon black‐filled one. Improvement of the filler dispersion in silica‐filled styrene–butadiene rubber (SBR) compounds was studied using low molecular weight polybutadiene (liquid PBD) with the high content of 1,2‐unit. By adding the liquid PBD to the silica‐filled SBR compound, the filler dispersion and flow property are improved. The cure time and cure rate become faster as the 1,2‐unit content of the liquid PBD increases for the compounds containing the liquid PBD. The crosslink density increases linearly with increase in the 1,2‐unit content of the liquid PBD. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3135–3140, 2003     

Synthesis of biodegradable PU/PEGDA IPNs having micro-separated morphology for enhanced blood compatibility

Summary New biodegradable hydrophobic polyurethane (PU)/hydrophilic poly (ethylene glycol) diacrylate (PEGDA) IPN was simultaneously synthesized with changing the molecular weight of PEGDA to investigate the effect of crosslinking density on the degree of phase separation. PU was modified using biodegradable poly(-caprolactone)diol and the hydroxy group of PEG was substituted to crosslinkable acrylate group having double bond, which induce photo-polymerization. The sturucture of PEGDA was confirmed by NMR. Because the reaction rate of PEGDA was faster than that of PU, the continuous matrix of the micro-separated PU/PEGDA IPNs having amphiphilic character was made of hydrophilic PEGDA-rich phase. All IPNs have sea-island morphology resulting from the suppressed phase separation. The effect of the degree of phase separation on blood compatibility was investigated.     

Reactivity,chemical structure,and molecular mobility of urea–formaldehyde adhesives synthesized under different conditions using FTIR and solid‐state 13C CP/MAS NMR spectroscopy

This study was conducted to investigate the effects of reaction pH condition and hardener type on the reactivity, chemical structure, and molecular mobility of urea–formaldehyde (UF) resins. Three different reaction pH conditions, such as alkaline (7.5), weak acid (4.5), and strong acid (1.0), were used to synthesize UF resins, which were cured by adding four different hardeners (ammonium chloride, ammonium sulfate, ammonium citrate, and zinc nitrate) to measure gel time as the reactivity. FTIR and ¹³C‐NMR spectroscopies were used to study the chemical structure of the resin prepared under three different reaction pH conditions. The gel time of UF resins decreased with an increase in the amount of ammonium chloride, ammonium sulfate, and ammonium citrate added in the resins, whereas the gel time increased when zinc nitrate was added. Both FTIR and ¹³C‐NMR spectroscopies showed that the strong reaction pH condition produced uronic structures in UF resin, whereas both alkaline and weak‐acid conditions produced quite similar chemical species in the resins. The proton rotating‐frame spin–lattice relaxation time (T_1ρH) decreased with a decrease in the reaction pH of UF resin. This result indicates that the molecular mobility of UF resin increases with a decrease in the reaction pH used during its synthesis. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2677–2687, 2003