Nucleation Effects of Nucleobases on the Crystallization Kinetics of Poly(L‐lactide)

The effects of nucleobases, especially uracil, on the nonisothermal and isothermal crystallization, melting behavior, spherulite morphology, and crystalline structure of bio‐based and biodegradable PLLA are studied. The melt‐ and cold‐crystallization rates of PLLA increase with increasing uracil loading. The melting behavior of nonisothermally melt‐ and cold‐crystallized PLLAs depends on the uracil content. The isothermal crystallization kinetics is analyzed based on an Avrami model. The incorporation of uracil changes the t_1/2/T_c profile of PLLA due to the more distinct heterogeneous nucleation effects at small supercooling. The crystalline structure of PLLA is not affected by uracil presence. The nucleation density increases and the spherulite size decreases by uracil incorporation.

     

Optical and adhesive properties of composite silica-impregnated Ca-α-SiAlON:Eu2+ phosphor films prepared on silica glass substrates

The compaction of a Eu-doped Ca-α-SiAlON phosphor powder was performed by electrophoretic deposition (EPD). The effect on the adhesion and optical properties of the silica precursor as both a binder of the powder and a filler of the air voids were evaluated. The adhesion of the silica impregnated composite film to the silica glass substrate was characterized by the tape test. The improvement of the external quantum efficiency was confirmed from the PL spectra measurement after the silica impregnation. The temperature dependence of the external quantum efficiency was also investigated in order to discuss the advantage of using the silica precursor as a binder for high-brightness LED applications.     

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.     

Effect of oxygen flow rate on the structural and electrochemical properties of lithium nickel oxides synthesized by the sol–gel method

The structural and electrochemical properties of LiNiO₂ powders were investigated as a function of the oxygen flow rate employed in the preparation of lithium nickel oxide. It was found that oxygen played an important role in the synthesis of highly crystallized LiNiO₂(R3¯m). In the crystallization process of LiNiO₂, a deficiency of oxygen in the calcination reactor induced the formation of impurities and cubic rock-salt structure (Fm3m) in LiNiO₂ powders. For LiNiO₂ prepared at higher oxygen flow rates, the electrode delivered high discharge capacities with relatively good retention rates. But very low electrode capacity was obtained from LiNiO₂ prepared at lower oxygen flow rates.     

Fractionation and enrichment of CLA isomers by selective esterification with Candida rugosa lipase

A commercial product of CLA contains almost equal amounts of cis-9,trans-11 (c9,t11)-CLA and trans-10,cis-12 (t10,c12)-CLA. We attempted to enrich the two isomers by a two-step selective esterification using Candida rugosa lipase that acted on c9,t11-CLA more strongly than on t10,c12-CLA. An FFA mixture containing CLA isomers was esterified with an equimolar amount of lauryl alcohol in a mixture of 20% water and the lipase. When the esterification of total FA reached 50%, two isomers were fractionated in a good yield: t10,c12-CLA was enriched in FFA, and c9,t11-CLA was recovered in lauryl esters. The FFA were esterified again to enrich t10,c12-CLA. At 27.3% esterification of total FA, the t10,c12-CLA content in FFA increased to 64.8 wt% with 89.3% recovery: The ratio of the content of t10,c12-CLA to that of two isomers was 95.9%. Lauryl esters obtained by the single esterification were employed for enrichment of c9,t11-CLA. After the esters were hydrolyzed, the resulting FFA were esterified again with lauryl alcohol. At 62.0% esterification of total FA, the c9,t11-CLA content in lauryl esters increased to 73.3 wt% with 79.4% recovery: The ratio of the content of c9,t11-CLA to that of two isomers was 95.6%. In a 600-g-scale purification, molecular distillation was effective in separating the reaction mixture into lauryl alcohol, FFA, and lauryl ester fractions.     

Preparation and Luminescence Spectra of Calcium- and Rare-Earth (R = Eu, Tb, and Pr)-Codoped α-SiAlON Ceramics

Rare-earth-doped oxynitride or nitride compounds have been reported to be luminescent and may then serve as new phosphors with good thermal and chemical stabilities. In this work, we report the photoluminescence (PL) spectra of europium-, terbium-, and praseodymium-doped Ca-α-SiAlON ceramics. The highly dense ceramics were prepared by hot pressing at 1750°C for 1 h under 20 MPa in a nitrogen atmosphere. Europium-doped Ca-α-SiAlON displayed a single broad emission band peaking at λ= 550–590 nm depending on the europium concentration. The emission bands in the spectra of europium-doped Ca-α-SiAlONs were assigned to the allowed transition of Eu²⁺ from the lowest crystal field component of 4 f ⁶5 d to ⁸S_7/2 (4 f ⁷) ground-state level. The emission spectra of terbium- and praseodymium-doped Ca-α-SiAlON ceramics both consisted of several sharp lines, which were attributed to the ⁵D₄→⁷F _j ( j = 3, 4, 5, 6) transitions of Tb³⁺ and ³P₀→³H _j ( j = 3, 4, 5) transitions of Pr³⁺, respectively. In particular, the terbium-doped α-SiAlON ceramics showed a strong green emission among these phosphors.     

Electrophoretic Deposition Behavior of Aqueous Nanosized Zinc Oxide Suspensions

The rheological behavior and electrophoretic deposition (EPD) of ZnO nanopowder (nano-ZnO) in aqueous media have been described. A cationic polyelectrolyte (polyethylenimine, PEI) was used to disperse and modify the surfaces of the ZnO nanoparticles. The rheological properties of the ZnO aqueous suspension were investigated by measuring the viscosity versus the pH and amount of dispersant. The EPD processing was conducted via cathodic electrodeposition, using stable suspensions with low viscosity, and the depositional behavior was investigated. Bubble-free nano-ZnO deposits with uniform microstructures were successfully obtained, which was an indication of good sintering behavior.     

Phase Transformation and Texture in Hot-Forged or Annealed Liquid-Phase-Sintered Silicon Carbide Ceramics

Starting from three powder mixtures of 80 vol% SiC (100α, 50α/50β, 100β) and 20 vol% YAG, liquid-phase-sintered silicon carbide ceramics were prepared by hot pressing at 1800°C for 1 h under 25 MPa, and then by hot forging or annealing at 1900°C for 4 h under an applied stress of 25 MPa in argon. The phase transformation and texture development in the as-hot-pressed, hot-forged, and annealed SiC ceramics were investigated via X-ray diffraction (XRD) and the pole figure measurements. The 6H → 4H polytypic transformation was observed in samples consisting of both α- and β-SiC phases when subjected to compressive deformation but absent in the case of annealing, suggesting the deformation-enhanced solubility of aluminum in SiC. Deformation was also found to enhance the 3C → 4H transformation in the sample containing entirely β-phase, which is due to the accelerated solution-precipitation process assisted by grain boundary sliding. The current study showed that the β- →α-phase transformation had little effect on texture development in SiC. Hot forging generally produced the strongest texture, with the calculated maximum of 2.2 times random in samples started with pure α-SiC phase. The mechanism for texture development was explained based on the microstructural observations.     

Transformation of Lower Alkanes into Aromatic Hydrocarbons over ZSM-5 Zeolites

Much attention has been paid to the transformation of lower alkanes such as propane and butanes into aromatic hydrocarbons from both industrial and academic points of view. The aromatic hydrocarbons can be utilized as a booster for high octane number gasoline and are fundamental raw chemicals in petroleum chemistry. The activation of lower alkanes is an intriguing subject. In early work, Csicsery [1-5] described dehydrocyclodimerization of lower alkanes over bifunctional catalysts such as platinum on alumina and Cr₂O₃ on alumina.     

Application of chrysotile-derived polymer to microlithography

A novel silicon-containing polymer, SCMR (silylated clay minerals resist), has been developed for microlithography. SCMR was synthesized by reaction of the silicate sheet of chrysotile with dimethylvinylchlorosilane (DMVCS) and/or trimethylchlorosilane (TMCS). The structure of SCMR is estimated as a mixture of R₁R₂R₃SiO, SiO₃(OH), and SiO₄ (R₁, R₂, R₃: methyl or vinyl group). The silicon content of SCMR is 40–45 wt% and its O₂-RIE resistance is 50 times as high as that of a novolak-based photoresist. SCMR has a high thermal stability and its profiles are not changed up to 300°C. SCMR is a negative working E-beam resist and has a high sensitivity, 2 µC/cm², and a high resolution, 0.2-µm line and space. CMPR (clay minerals positive resist), consisting of SCMR and an acid generator, has been developed for a positive working E-beam resist. It has a high sensitivity, 0.2 µC/cm².