Morphology development of 10‐μm scale polymer particles prepared by SPG emulsification and suspension polymerization

Classicalparticle morphologies, core‐shell, hemisphere, sandwich, and so on, were all reproducible by starting from ca. 10‐μm uniform droplets composed of monomers, initiator, solvents, and polymer, and polymerizing them by subsequent suspension polymerization. SPG (Shirasu porous glass) membrane was employed to form uniform size droplets having the coefficient of variation (CV) around 10%. Styrene (ST) and acrylic monomers were used as monomers, and their polymers were dissolved in the droplets to investigate the development of phase separation. When hydrophilic methyl methacrylate (MMA) was polymerized in the droplets with a mixed solvent consisting of hydrophilic hexanol (HA) and hydrophobic benzene and hexadecane (HD), the resulting morphology shifted from hemisphere to sandwich and eventually to PMMA/solvent core‐shell with increasing hydrophilicity of the mixed solvent. The sandwich was converted to the core‐shell after several weeks elapsed. As styrene was added to MMA, the morphology shifted from hemisphere core/solvent shell to raspberry core/solvent shell as the fraction of ST increased. The domain of the mixed solvent in the raspberry core was reduced with increasing the hydrophilicity of the mixed solvent. All these morphologies were eventually converted to the copolymer core/solvent shell. When a mixed monomer of styrene and MMA dissolving polystyrene (PS) was polymerized, the resulting morphology shifted from salami to core‐shell with increasing the MMA fraction in the comonomer. The salami particles were then swollen with toluene, and after the swelling, toluene was removed under the different temperature and pressure. The final particle morphology converted to the core‐shell with a milder rate of toluene removal which was predicted from the thermodynamic model. When styrene and cyclohexyl acrylate (CHA), a pair with widely different reactivity ratios, were copolymerized, salami morphologies, with tiny CHA‐rich domains dispersed in the matrix, were obtained even at a higher fraction of CHA in comonomer. Effects of glass transition temperature of the polymers, molecular weight, and the composition of copolymers were taken in consideration whenever the final morphologies were discussed. By these experiments, the authors tried to demonstrate an advantage of using large uniform spheres for the particle morphology studies. SPG emulsification technique was a potential tool because of its free formulation of the droplets, and the subsequent polymerization could undergo without the breakup or coalescence of the droplets. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2200–2220, 2001     

Estimation of Stress Exponent and Activation Energy for Rapid Densification of 8 mol% Yttria‐Stabilized Zirconia Powder

The rapid densification behavior of 8 mol% Y₂O₃‐stabilized ZrO₂ polycrystalline (8Y‐SZP) powder compacts at the initial stage of pressure sintering (relative density () below 0.92) has been investigated using an electric current‐activated/assisted sintering (ECAS) system. Data points corresponding to a fixed heating rate were extracted from the densification rate () versus ρ and versus temperature (T) curves. These curves were obtained experimentally by consolidation at a fixed current. Under fixed current ECAS, the heating rate () decreases continuously over sintering time. Using a quasi‐ constant heating rate (CHR) method, data points were extracted to plot vs. ρ, vs. T, and ρ vs. T curves at a fixed . The stress exponent (n), estimated from a log‐log plot of grain size (d)‐corrected /ρ and effective stress (σ_eff) at 1300–1400 K, shows an almost constant value of 1. In addition, the activation energy (Q) for rapid densification, estimated from an Arrhenius plot of d‐corrected /ρ also shows an almost constant value of 350 kJ/mol, which is considerably lower than the previously reported value of the activation energy for Zr⁴⁺ lattice diffusion of about 440 kJ/mol. These results suggest that rapid densification of 8Y‐SZP by ECAS seems to proceed by diffusional creep controlled by grain‐boundary diffusion of Zr⁴⁺ ions.     

Improvement of electrochemical properties of PEO–LiTFSI electrolyte by incorporation of boroxine polymers with different backbone lengths

A series of boroxine polymers (BP) with different backbone lengths were synthesized. Polymer electrolytes prepared by blending poly(ethylene oxide) (PEO) and BP with Li(N(SO ₂CF₃)₂) (LiTFSI) were evaluated. Better performance was observed by addition of BP in the PEO based polymer electrolyte. The effect of the backbone length of BP on electrochemical properties of PEO–BP–LiTFSI electrolyte systems was investigated. Compared with the PEO–LiTFSI system, about five times higher ionic conductivity at low temperature and five times higher lithium ion transference number at 70°C were achieved by incorporation of long chain BP in the electrolyte. Short chain BP exhibited outstanding performance in decreasing interfacial resistances on both anode and cathode surfaces. Good battery performance was also observed for these BP containing hybrid polymer electrolytes.     

Synergistic Effects of Polybenzimidazole and Aramide on Enhancing Flame-Retardancy and Solubility

Aromatic and functional polymers with processibility derived from biobased starting materials are prerequisite considering sustainable society. Poly(2,5-benzimidazole)s are rigid-rod polymers to show ultrahigh thermal stability such as flame retardance, while usually suffer from poor solubility. Here, poly(benzimidazole-co-amide)s are synthesized from two biobased monomers, 3,4-diaminobenzoic acid and a semirigid comonomer, 4-aminohydrocinnamic acid. The copolymers with an amide composition of 80 mol% and higher are soluble in widely used polar solvents to fabricate the films keeping high flame retardance, which is comparable with popular high-performance polymers such as aromatic polyimides, polyetheretherketone, polyphenylene sulfide, etc.     

Characterization of the ybdT gene product of Bacillus subtilis: Novel fatty acid β-hydroxylating cytochrome P450

We have characterized the gene encoding fatty acid α-hydroxylase, a cytochrome P450 (P450) enzyme, from Sphingomonas paucimobilis. A database homology search indicated that the deduced amino acid sequence of this gene product was 44% identical to that of the ybdT gene product that is a 48 kDa protein of unknown function from Bacillus subtilis. In this study, we cloned the ybdT gene and characterized this gene product using a recombinant enzyme to clarify function of the ybdT gene product. The carbon monoxide difference spectrum of the recombinant enzyme showed the characteristic one of P450. In the presence of H₂O₂, the recombinant ybdT gene product hydroxylated myristic acid to produce β-hydroxyristic acid and α-hydroxymyristic acid which were determined by high-performance liquid chromatography (HPLC) and gas chromatography-mass spectrometry. The amount of these products increased with increasing reaction period and amount of H₂O₂ in the reaction mixture. The amount of β-hydroxyl product was slightly higher than that of α-hydroxyl product at all times during the reaction. However, no reaction products were detected at any time or at any concentration of H₂O₂ when heat-inactivated enzyme was used. HPLC analysis with a chiral column showed that the β-hydroxyl product was nearly enantiomerically pure R-form. These results suggest that this P450 enzyme is involved in a novel biosynthesis of β-hydroxy fatty acid.     

Synthesis and crystal structure analysis of complex hydride Mg(BH4)(NH2)

Complex hydride Mg(BH₄)(NH₂), which consists of double anion BH₄⁻ and NH₂⁻, was synthesized and the crystal structure was analyzed by synchrotron X-ray diffraction. The mixture sample of Mg(BH₄)₂ + Mg(NH₂)₂ prepared by ball milling was reacted and crystallized to Mg(BH₄)(NH₂) by heating at about 453 K. This crystal phase transforms into amorphous phase above 473 K and subsequently the dehydrogenation begins. The crystal structure of Mg(BH₄)(NH₂) was determined from measurement data at 453 K (chemical formula: Mg_0.94(BH₄)₁(NH₂)_0.88, crystal system: tetragonal, space group: I4₁ (No.80), Z = 8, lattice constants: a = 5.814(1), c = 20.450(4) Å at 453 K). Mg(BH₄)(NH₂) is ionic crystal which the cation (Mg²⁺) and the anions (BH₄⁻ and NH₂⁻) are stacking alternately along the c-axis direction. Two BH₄⁻ and two NH₂⁻ tetrahedrally coordinate around Mg²⁺ ion.     

Effects of free stream turbulence on a turbulent boundary layer on a flat plate with zero pressure gradient part IV: Calculation of the flow field

The effects of free stream turbulence on a turbulent boundary layer were calculated by using a k-ϵ two-equation model. The calculations were performed with respect to velocity profiles on a flat plate, wall shear stress, turbulence energy, integral length scales of turbulence, and decay of free stream turbulence, and the results were compared with the experimental results. The energy of the free stream turbulence and the dissipation values at the leading edge of the flat plate were used as the initial calculation conditions. These initial values of dissipation were determined from the integral length scales of the free stream turbulence at the leading edge. The calculated wall shear stress increased with the free stream turbulence and integral length scales of turbulence. The velocity profiles and turbulence energy agreed well with the experimental results, and the effects of free stream turbulence on the wall shear stress agreed fairly well with those observed in experiments. © 1997 Scripta Technica. Inc. Heat Trans Jpn Res. 25 (2): 65–75, 1996     

Prediction of cutting forces and machining error in ball end milling of curved surfaces -II experimental verification

This paper presents the results of a series of experiments performed to examine the validity of a theoretical model for evaluation of cutting forces and machining error in ball end milling of curved surfaces. The experiments are carried out at various cutting conditions, for both contouring and ramping of convex and concave surfaces. A high precision machining center is used in the cutting tests. In contouring, the machining error is measured with an electric micrometer, while in ramping it is measured on a 3-coordinate measuring machine. The results show that in contouring, the cutting force component that influences the machining error decreases with an increase in milling position angle, while in ramping, the two force components that influence the machining error are hardly affected by the milling position angle. Moreover, in contouring, high machining accuracy is achieved in “Up cross-feed, Up cut” and “Down cross-feed, Down cut” modes, while in ramping, high machining accuracy is achieved in “Left cross-feed, Downward cut” and “Right cross-feed, Upward cut” modes. The theoretical and experimental results show reasonably good agreement.     

A useful method for observing intracellular structures of free and cultured cells by scanning electron microscopy

Scanning electron microscopy (SEM) using osmium-maceration methods has been used for analyzing the three-dimensional structure of cell organelles in tissue samples, but it has been quite difficult to observe free and cultured cells with this technique. The present study was performed to develop a method that can be applied to free and cultured cells for SEM studies of intracellular structures after osmium maceration. The method was also applied to light microscopy (LM) and to transmission electron microscopy (TEM). HeLa cells and human leukocytes were fixed with a mixture of 0.5% paraformaldehyde and 0.5% glutaraldehyde followed by an additional fixation with 1% osmium tetroxide. These cells were embedded in low-melting-point agarose. A temperature-responsive dish was also used for collection of cultured cells before embedding. For LM and TEM, the cell-embedded agarose was further embedded in epoxy resin, and semi- and ultrathin sections were examined conventionally. For SEM, the agarose was freeze-fractured in 50% dimethyl sulfoxide, processed for osmium maceration and observed in a high-resolution SEM. Low-melting-point agarose was useful as an embedding medium for SEM, because it was well preserved during prolonged osmication for SEM. Thus, the fine structure of cell organelles was clearly analyzed by SEM after osmium-maceration treatment. These SEM images could also be compared with those of LM and TEM of the agarose-embedded tissues.