Studies on phase separation rate in porous polyimide membrane formation by immersion precipitation

Phase separation rate during porous membrane formation by immersion precipitation was investigated by light scattering in a polyimide/N‐Methylpyrrolidone (NMP)/water system. In the light scattering measurement, plots of scattered intensity against scattered angle showed maxima in all cases, which indicated that phase separation occurred by a spinodal decomposition (SD). Characteristic properties of the early stage of SD, such as an apparent diffusion coefficient D_app and an interphase periodic distance Λ, were obtained. The growth process of Λ was also followed by light scattering. The growth rate had the same tendency as D_app when water content in the nonsolvent bath and the polymer concentration in the cast solution were changed. The pore size of the final membrane increased with decreasing water content, which was opposite to the tendency of Λ growth rate. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 292–296, 2003     

Effect of wet-jet milling on the c-axis orientation of hydroxyapatite ceramics fabricated using a strong magnetic field

Controlling the crystal orientation of hydroxyapatite, an inorganic material that is a major component of human hard tissues is important to fabricate better artificial bones and artificial tooth roots. To obtain highly oriented hydroxyapatite ceramics under a strong magnetic field, a good dispersion of the raw materials in the slurry must be obtained. This study investigates the effect of wet-jet milling of a slurry on the orientation of hydroxyapatite ceramics fabricated using a strong magnetic field. Although the prolonged ball milling with ZrO₂ balls of the raw powder fractures the primary particles of hydroxyapatite, wet-jet milling is used to successfully pulverize agglomerated hydroxyapatite raw powder without changing the morphology of the primary particles. Evidently, ceramics with a highly oriented c-axis of hydroxyapatite are obtained by molding the wet-jet milled slurry in a strong rotating magnetic field. They exhibit anisotropy in fracture toughness, and the fracture toughness calculated from the crack length perpendicular to the rotating axis is higher than that calculated from the crack length parallel to it. Furthermore, these values are higher than those of randomly oriented hydroxyapatite ceramics, which may be owing to the crystal orientation dependence of the fracture toughness of the hydroxyapatite grains and grain boundaries.     

Stabilization of Microcapsules Using a Freeze-Dried Gelatin Matrix: Aqueous Redispersibility and the Ingredient Activity

Microcapsules are of great interest to the food and pharmaceutical industries as vehicles to deliver active ingredients to the gastrointestinal tract. Drying plays an important role in stabilizing microcapsules to prolong their lifetime; however, drying often produces undesirable changes in the microcapsules, such as irreversible aggregation of the microcapsules and activity loss of the encapsulated ingredient. In this work, poly(epsilon-caprolactone) microcapsules containing a model bioactive compound (tocopherol) were prepared and stabilized in a freeze-dried gelatin matrix. This dried product was rehydrated and the aqueous redispersibility of the microcapsules and the tocopherol activity were investigated. The experimental results suggested that a kinetic balance between dehydration (caused by freezing) and gel network formation is a critical factor that affects the redispersibility and ingredient activity of the products. It was further suggested that a hydrogel-based product could be strategically freeze dried to maximize product quality by tuning its freezing process; that is, by employing a controllable dehydration process.     

Fabrication of Functionally Graded SiO2‐Mo Material by Centrifugation and Floc‐Casting of Highly Concentrated Slurry

To fabricate functionally graded materials, a highly concentrated slurry of SiO₂‐Mo system was prepared and centrifugal force was applied in an attempt to achieve a graded composition. Subsequently, we formed a homogeneous green body with compositional gradation by floc‐casting at 80°C, which was then fired at 1750°C for 10 min in Ar. The sintered body had compositional ratios of SiO₂ and Mo as well as electrical conductivities that changed gradually along the direction of centrifugal force. The results demonstrate that centrifugation and control of slurry characteristics such as flocculation are effective in fabricating functionally graded SiO₂‐Mo materials.     

Electron spin resonance investigation of small spin probes in aqueous and vesicle phases of mixed membranes made from poly(oxyethylene) hydrogenated castor oil and hexadecane

Small spin probes in the vesicle and aqueous phases of mixed membranes made from poly(oxyethylene) hydrogenated castor oil (HCO) and hexadecane were investigated by ESR (electron spin resonance) spectroscopy. Partitioning (partition coefficients), rotational correlation times, and activation energies of the spin probes in the vesicle phase were determined. The quantitative results obtained by an ESR simulation indicated that the spin probe DTBN (di-tert-butyl nitroxide), in the vesicle of the mixed membrane, was partitioned similar to that of TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl) at 50 degrees C, and the partitioning for both probes showed no abrupt change across the temperatures examined. The results differed considerably from conventional analyses of the high-field signal intensities. Activation energies obtained by the simulation for DTBN and TEMPO were 21 and 20 kJ/mol, respectively. In addition, the hyperfine values of 15.8 (DTBN) and 16.1 G (TEMPO) in the vesicle phase were consistent with the activation energies and supported the probe environments in the membrane. Thus, the present ESR results provided detailed information regarding the probe behavior in the membrane.     

Novel CO2 Absorbents Using Lithium-Containing Oxide

We have discovered a series of lithium-containing oxides that immediately react with ambient carbon dioxide (CO₂) up to 700°C. The products react and return reversibly to the oxides at a temperatures higher than about 700°C. The absorption capacity surpasses that of other CO₂ absorbents by a factor of 10. Utilizing these absorbents, the possibility of a CO₂ separation system that operates at around 500°C is proposed. It is generally believed that a CO₂ separation process operable at temperatures higher than 500°C has the special benefit of a small energy penalty. Moreover, the absorption also proceeds at ambient temperature in the atmospheric environment. This property offers the possibility of many other applications, such as air cleaners or cartridges. Therefore, we think these materials have the potential to make a valuable contribution to the realization of CO₂ emission control.     

Sintering Kinetics at Constant Rates of Heating: Effect of Al2O3 on the Initial Sintering Stage of Fine Zirconia Powder

The sinterabilities of fine zirconia powders including 5 mass% Y₂O₃ were investigated, with emphasis on the effect of Al₂O₃ at the initial sintering stage. The shrinkage of powder compact was measured under constant rates of heating (CRH). The powder compact including a small amount of Al₂O₃ increased the densification rate with elevating temperature. The activation energies at the initial stage of sintering were determined by analyzing the densification curves. The activation energy of powder compact including Al₂O₃ was lower than that of a powder compact without Al₂O₃. The diffusion mechanisms at the initial sintering stage were determined using the new analytical equation applied for CRH techniques. This analysis exhibited that Al₂O₃ included in a powder compact changed the diffusion mechanism from grain boundary to volume diffusions (VD). Therefore, it is concluded that the effect of Al₂O₃ enhanced the densification rate because of decrease in the activation energy of VD at the initial sintering stage.     

Osteoinduction by Functionally Graded Apatites of Bovine Origin Loaded with Bone Morphogenetic Protein-2

Bioresorbable and functionally graded apatites (fg-HAp) ceramics, which are characterized by gradations in crystallinity and the grain size of hydroxyapatite (HAp:Ca₁₀(PO₄)₆(OH)₂), were designed using bovine bone by the calcination and partial dissolution–precipitation method. The fg-HAp ceramics had macropores of 100–600 μm originated from spongy bone, and micropores of 10–160 nm. Fg-HAp ceramics loaded with recombinant human bone morphogenetic protein-2 (rhBMP-2/fg-HAp) were implanted into the subcutaneous tissue of rats. Eight weeks after the implantation, the surface and bulk degradations of the fg-HAp-containing body fluid occured, and small pieces of fg-HAp were incorporated into the induced bone and fatty marrow, suggesting that osteoinduction occurred in conjunction with bone remodeling. The rhBMP-2/fg-HAp ceramics developed could become a resorbable biomimetic material with fast bioresorption and osteoinduction characteristics.     

Radiation tolerance of type IIa synthetic diamond detector for 14 MeV neutrons

Radiation tolerance of a type IIa synthetic diamond detector was examined from irradiation of mono-energetic 14 MeV neutrons. Measurements of I–V (current–voltage) characteristics and energy spectrum for 5.486 MeV alpha particles were performed after neutron irradiation. In the I–V characteristics measurement, enhancement of rectification was observed after neutron irradiation of up to 2.0 × 10¹² n/cm². Concurrently with the enhancement of rectification, significant decrease in signal amplitude was observed in energy spectrum measurement for alpha particles. It is considered that these changes were due to increase in the concentration of defects acting as shallow energy levels in the forbidden band. For neutron irradiation of higher than 1.6 × 10¹³ n/cm², weakening of the rectification characteristics and recovery of the signal amplitude were observed. These changes imply that deep energy levels, which were also considered to be introduced by defects, were dominant and weakened the effects of the shallow energy levels. Increase in the concentration of the deep trapping levels resulted in gradual decrease of the signal amplitude and degradation in the energy resolution. The peak for the alpha particles was obtained up to 5.5 × 10¹³ n/cm².     

Photocatalytic microreactor study using TiO2-coated porous ceramics

Two kinds of porous ceramic disks, having through-holes with diameters of 0.1 and 0.05 mm, were coated with TiO₂ using two different starting solutions: titanyl(IV)acetylacetonate and a commercial titania sol (STS-01). The morphology of these porous ceramics before and after TiO₂ coating was observed by SEM. The TiO₂-coated porous ceramics were examined as honeycomb photocatalytic microreactors. The photocatalytic activity was evaluated using the decomposition of methylene blue solution for radiation angles of 0° and 10° with respect to the pore axis. The highest photocatalytic activity was obtained for the porous ceramic having the pore diameter of 0.1 mm, coated with titanyl(IV)acetylacetonate and irradiated with a light angle of 0° with respect to the pore axis.