Crystallization process and some properties of novel transparent machinable calcium-mica glass-ceramics

Bulk glass having a calcium-mica composition (Ca_0.5Mg₃AlSi₃O₁₀F₂) is homogeneous glass. The crystallization mechanism of the mica is surface crystallization and transparency is lost completely when crystallization occurs on the surface. In this study, by decreasing SiO₂ and increasing CaO and Al₂O₃ from the chemical composition of Ca_0.5Mg₃AlSi₃O₁₀F₂, and moreover by replacing a small amount of K₂O instead of CaO, the phase separation appears in the glasses. Because of this phase separation, the mica begins to be crystallized not only on the surface but also in the bulk at lower temperatures. Consequently, the novel transparent machinable mica glass-ceramic can be obtained by heating the glasses having the chemical composition of Ca_0.6Mg₃Al_1.2Si_2.8O₁₀F₂ and K_0.01Ca_0.595Mg₃Al_1.2Si_2.8O₁₀F₂. As a larger amount of calcium-mica is separated, the bending strength decreases and the fracture toughness increases. Furthermore, by replacing K⁺ ion instead of Ca²⁺ ion in the interlayer of calcium-mica, the interlayer bonding strength becomes high, resulting in the increase of the bending strength.     

A Novel Preparation Method for Foamed Silica Ceramics by Sol-Gel Reaction and Mechanical Foaming

A simple method for obtaining silica foam has been developed by combining sol-gel reaction and mechanical foaming without added organic pore formers, in order to reduce generation of CO₂ and harmful gases by decomposition of the organic compounds. The silica foam was prepared by mechanically foaming the silica sol and controlling the viscosity change and gelling. The gelation time of the silica sol can be varied from 10 minutes to 3 hours by changing the pH, temperature and concentration of the surfactant added as a foam stabilizer. The dried silica gel foam was calcined at 600°C then fired at 1000°C to obtain sintered silica foam. The porosity and average pore size of the silica foam was 84% and 140 m, respectively. The bending strength and gas permeability of the sintered silica foam was 2.4 MPa and 9.4 × 10^–11 m², respectively.     

The effect of molding conditions on mechanical and morphological properties at the interface of film insert injection molded polypropylene‐film/polypropylene matrix

An extensive study on the peel strength between a polypropylene (PP) film and PP substrate fabricated using film insert injection molding technique was carried out through a 180° peel test. Injection molding conditions such as barrel temperature, injection speed and holding pressure were varied to gauge their effects on the mechanical and morphological properties. Morphological observations were made at the film‐substrate interfacial regions by means of transmission electron microscopy (TEM). The injection molded products, with the films still attached, were subjected to bending and impact tests to determine if there is any relationship between film‐substrate adhesion and bulk properties. Observation of the load‐displacement curves during the peel test revealed three unique and interesting curves, corresponding to different peeling and film fracture mechanisms. Increases in injection speed, barrel temperature and holding pressure lead to increased bonding between the film and substrate surfaces. The enhancement of bonding between these two polymer surfaces could be attributed to polymer‐polymer interdiffusion. Substantiating evidence from TEM, which shows the fading of the interface as the bond strengthens, further boosts the accuracy of this assumption. The hope that the films could contribute to enhancing bulk properties has been diminished since the bending properties appeared to be similar with or without the film attached. Polym. Eng. Sci. 44:2327–2334, 2004. © 2004 Society of Plastics Engineers.     

Rh/γ-Al2O3 Catalytic Layer Integrated with Sol–Gel Synthesized Microporous Silica Membrane for Compact Membrane Reactor Applications

An efficient and compact catalytic membrane reactor for reforming of CH₄ was developed by integrating a hydrogen perm-selective silica membrane with an Rh/-Al₂O₃ catalyst layer. The catalytic layer was sandwiched between the outer surface of the -Al₂O₃ support tube and the silica membrane with an aim of improving the heat and mass transfer rates through the system and to simplify the reactor geometry. The system showed improved efficiency for reforming of CH₄ at comparatively lower operating temperatures and steam to C molar ratios than the conventional fixed-bed steam reforming systems. Under optimized conditions, a nearly 25-30% improvement from the equilibrium conversion level was achieved as a result of abstraction of hydrogen from the product stream by the silica membrane integrated with the catalyst layer. The performance of the system was evaluated as a function of various process parameters. Because of the compactness and efficiency, the present system emerges as a promising alternative to the conventional membrane reactors, which possess separate catalytic and membrane units.     

Characterization and CO2 sorption properties of poly[methacryloxypropylheptacyclopentyl‐T8‐silsesquioxane‐ co‐3‐methacryloxypropyltris(trimethylsiloxy)silane]

Poly[methacryloxypropylheptacyclopentyl‐T8‐silsesquioxane (MAPOSS)‐co‐3‐methacryloxypropyltris(trimethylsiloxy)silane (SiMA)] was synthesized through free radical polymerization. The physical and carbon dioxide (CO₂) sorption properties of the copolymer membranes were investigated in terms of the MAPOSS content. As the MAPOSS content increases, the membrane density increased, suggesting a decrease in the fractional free volume. In addition, the thermal stability was improved with increasing the MAPOSS content. These are because of the polyhedraloligomericilsesquioxane (POSS) units that restrict the high mobility of poly(SiMA) segments. The glass transition temperature, T_g of the copolymers was single T_g based on the differential scanning calorimetry, suggesting that the copolymers were random and not phase separation. Based on the CO₂ sorption measurement, the POSS units play a role in reducing Henry's dissolution by suppressing the mobility of the poly(SiMA) component, while POSS units increase the nonequilibrium excess free volume, which contributes to the Langmuir dissolution. Based on these results, the introduction of MAPOSS unit is one of the effective ways to improved the thermal stability and CO₂ sorption property due to the enhancement of the polymer rigidity. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Grazing-incidence wide-angle X-ray diffraction study on molecular aggregation state of imprinted polyimide film before and after hard baking

Nanoimprint lithography (NIL) was carried out on precursor of polyimide (PI), poly(amic acid) film, and then hard baking to obtain imprinted PI film. The molecular aggregation states of imprinted PI films before and after hard baking were investigated by grazing-incidence wide-angle X-ray diffraction comparing with the one of flat PI film. It was found that NIL and hard baking can strongly affect the molecular aggregation states of PI film. Before hard baking, PI chain is aligned parallel to the line direction on the line. After hard baking, the alignment in ordered domain was changed to that the PI molecule of which chain axis is perpendicular to the line direction is significantly increased, while, PI molecule of which chain axis is parallel to the line direction is decreased after hard baking. Through comparing with the flat PI, crystallinity of imprinted PI film has been significantly enhanced.     

Annealing effect on temperature coefficient of resistivity in La1−xSrxMnO3 ceramics

We investigated annealing effects of La_1?xSr_xMnO₃ (x = 0–0.6) on electrical resistivity and the temperature coefficient of resistivity (TCR). The annealed samples’ resistivity was lower than those of non-annealed samples. For example, annealing changed the resistivity of x = 0.3 at 25 °C from 4.50 × 10^?5 to 3.71 × 10^?5 Ω m. Remarkable difference in TCR was observed after annealing, for x = 0.3, 0.45, and 0.5. For x = 0.3, the TCR after annealing was 4000 ppm/°C, which was 1250 ppm/°C greater than that before annealing. We investigated (1) crystal phase, (2) Mn average valence, (3) Mott insulator–metal transition temperature, and (4) microstructure. The microstructure was remarkably varied for annealed x = 0.3 and 0.5. The average grain size of the x = 0.3 increased from 1.60 up to 2.38 μm. Results show that annealing affects resistivity and TCR because of grain growth during annealing.     

MicroRNA-331-3p Suppresses Cervical Cancer Cell Proliferation and E6/E7 Expression by Targeting NRP2

Aberrant expression of microRNAs (miRNAs) is involved in the development and progression of various types of cancers. In this study, we investigated the role of miR-331-3p in cell proliferation and the expression of keratinocyte differentiation markers of uterine cervical cancer cells. Moreover, we evaluated whether neuropilin 2 (NRP2) are putative target molecules that regulate the human papillomavirus (HPV) related oncoproteins E6 and E7. Cell proliferation in the human cervical cancer cell lines SKG-II, HCS-2, and HeLa was assessed using the 3-(4,5-dimethylthiazol-2-yl)-5-(3-carboxymethoxyphenyl)-2-(4-sulfophenyl)-2H-tetrazolium, inner salt (MTS) assay. Cellular apoptosis was measured using the TdT-mediated dUTP nick end labeling (TUNEL) and Annexin V assays. Quantitative RT-PCR was used to measure the messenger RNA (mRNA) expression of the NRP2, E6, E7, p63, and involucrin (IVL) genes. A functional assay for cell growth was performed using cell cycle analyses. Overexpression of miR-331-3p inhibited cell proliferation, and induced G2/M phase arrest and apoptosis in SKG-II, HCS-2 and HeLa cells. The luciferase reporter assay of the NRP2 3′-untranslated region revealed the direct regulation of NRP2 by miR-331-3p. Gene expression analyses using quantitative RT-PCR in SKG-II, HCS-2, and HeLa cells overexpressing miR-331-3p or suppressing NRP2 revealed down-regulation of E6, E7, and p63 mRNA and up-regulation of IVL mRNA. Moreover, miR-331-3p overexpression was suppressed NRP2 expression in protein level. We showed that miR-331-3p and NRP2 were key effectors of cell proliferation by regulating the cell cycle, apoptosis. NRP-2 also regulates the expression of E6/E7 and keratinocyte differentiation markers. Our findings suggest that miR-331-3p has an important role in regulating cervical cancer cell proliferation, and that miR-331-3p may contribute to keratinocyte differentiation through NRP2 suppression. miR-331-3p and NRP2 may contribute to anti-cancer effects.     

Production of hyaluronic‐acid‐based cell‐enclosing microparticles and microcapsules via enzymatic reaction using a microfluidic system

This article describes the preparation of cell‐enclosing hyaluronic acid (HA) microparticles with solid core and microcapsules with liquid core through cell‐friendly horseradish peroxidase (HRP)‐catalyzed hydrogelation. The spherical vehicles were made from HA derivative possessing phenolic hydroxyl moieties (HA‐Ph) cross‐linkable through the enzymatic reaction by extruding cell‐suspending HA‐Ph aqueous solution containing HRP from a needle of 180 μm in inner diameter into the ambient coaxial flow of liquid paraffin containing H₂O₂ in a microtubule of 600 μm in diameter. By altering the flow rate of liquid paraffin, the diameters of gelatin and HA‐Ph microparticles were varied in the range of 120–220 μm and 100–300 μm, respectively. The viability of the enclosed human hepatoma HepG2 cells in the HA‐Ph microparticles of 180 μm in diameter was 94.2 ± 2.3%. The growth of the enclosed HepG2 cells was enhanced by decreasing the HRP concentration. The microcapsules of 200 μm in diameter were obtained by extruding HA‐Ph aqueous solution containing thermally liquefiable cell‐enclosing gelatin microparticles of 150 μm in diameter using the same microfluidic system. The enclosed cells grew and filled the cavity within 10 days. Spherical tissues covered with a heterogeneous cell layer were obtained by degrading the microcapsule membrane using hyaluronidase after covering the surface with a heterogeneous cell layer. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43107.     

Fabrication of fluorine-terminated diamond-like carbon thin film using a hyperthermal atomic fluorine beam

Surface modification of diamond-like carbon (DLC) film was performed using a hyperthermal atomic fluorine beam on the purpose of production of hydrophobic surface by maintaining the high hardness of DLC film. By the irradiation of atomic fluorine beam of a 1.0 × 10²⁰ atoms/cm², the contact angle of a water drop against the DLC surface increased from 73° to 111°. The formation of CF₃, CF₂ and CF bonding on the modified DLC surface was confirmed from the measurements of X-ray photoelectron spectra and near-edge X-ray absorption fine structure spectra. Irradiation of hyperthermal atomic fluorine beam was concluded to produce insulator fluorine-terminated DLC film, which has high F content on the surface, by the taking of the use of neutral atomic beam as a fluorine source.