Effect of steric hindrance on hydrogen‐bonding interaction between polyesters and natural polyphenol catechin

The phase behaviors for the blends of poly(3‐hydroxypropionate) (PHP), poly(L ‐lactide) (PLLA), poly(D ‐lactide) (PDLA), and poly(D,L ‐lactide) (PDLLA) with catechin were investigated by differential scanning calorimetry. In PLLA/catechin, PDLA/catechin, and PDLLA/catechin blends, two glass transitions were detected when the catechin content was ≥40 wt %, whereas in PHP/catechin blends only one glass transition was observed over the whole range of blend compositions. The former and the latter results should reflect the inhomogeneous and the homogeneous nature of the blends, respectively, in the amorphous phase. These different phase behaviors should arise from the differences in the chemical structures between PHP and PLLA/PDLA/PDLLA, which dominates the strength and the number of intermolecular hydrogen‐bonding interactions between the ester carbonyl groups of polyesters and the phenol groups of catechin. As detected by FTIR spectroscopy, in comparison with PHP, the steric hindrance of side‐chain methyl groups of PLLA, PDLA, and PDLLA might restrain the formation of hydrogen bonds between their ester carbonyl groups and the phenol hydroxyl groups of catechin, even weakening the strength of such hydrogen bonds. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3565–3573, 2004     

Photoluminescence properties of porous silicon layers prepared by electrochemical etching in extremely dilute HF solutions

Dilute HF solutions with concentrations down to 0.03% have been used to obtain luminescent porous silicon (PSi) layers on p-type Si wafers. The experimental results show that with a constant etching time of 30 min, PSi layers with sufficient luminescence efficiencies can be formed for HF concentrations as low as 0.1%. Because of a significantly lowered critical current density, only very low etching current densities of  ≤0.1 mA cm⁻² can result in the formation of luminescent PSi samples in 0.1% HF solutions. A notable result is that these low etching current densities cannot be used to form luminescent PSi layers in concentrated ( ≥1%) HF solutions. The behavior of PL intensity as a function of etching current density has been analyzed over a wide range of HF concentration. The PL intensity is determined by the ratio of the etching current density to the critical current density, suggesting that the presence of silicon oxides plays an important role in the formation of luminescent Si nanostructures in PSi layers.     

Fracture Resistance Behavior of High‐Thermal‐Conductivity Silicon Nitride Ceramics

Silicon nitride ceramics were prepared from a high‐purity silicon powder doped with 2 mol% Y₂O₃ and 5 mol% MgO as sintering additives via a route of sintering of reaction‐bonded silicon nitride (SRBSN). The materials sintered at 1900°C for 3, 6, 12, and 24 h had thermal conductivities of 109, 125, 146, and 154 W/m/K, and four‐point bending strengths of 786, 676, 608, and 505 MPa, respectively. The fracture toughness values, determined by the single‐edge‐precracked‐beam (SEPB) method, were 8.4, 8.6, 9.7, and 10.7 MPa m^1/2 for the materials sintered for 3, 6, 12, and 24 h, respectively, which were similar to the results measured by the chevron‐notched‐beam (CNB) test method. The materials sintered for longer times (12 and 24 h) showed stronger R‐curve behaviors over longer range of crack extension, in comparison with the materials sintered for shorter times (3 and 6 h).     

Characteristics of menhaden oil ethanolysis by immobilized lipase in supercritical carbon dioxide

Ethanolysis of menhaden oil was performed with 1,3-regiospecific lipase to produce diglycerides and monoglycerides containing polyunsaturated fatty acids, and fatty acid ethyl esters. Immobilized lipases like lipozyme TL-IM (Thermomuces lanuginosa immobilized on silica gel) were used for enzymatic ethanolysis. Ethanolysis was carried out in different processes (solvent free, organic solvent and supercritical fluid system) to compare the reaction rate and yield obtained by menhaden oil ethanolysis. Organic solvent (hexane) and supercritical carbon dioxide (SC-CO₂) were used as reaction medium. The reaction products were analyzed by gas chromatography (GC), thin layer chromatography (TLC) and high performance liquid chromatography (HPLC). Higher amounts of ethanol as a substrate caused substrate inhibition which dramatically decreased the reaction rate of ethanolysis. To elucidate the effect of pressure, enzymatic ethanolysis was performed in SC-CO₂ at pressures ranging from 75 to 121 bar. Enzymatic ethanolysis of menhaden oil in SC-CO₂ decreased by substrate inhibition. Reaction rate and optimum amount of ethanol used were depended on SC-CO₂ density individually. Kinetic model with substrate inhibition (dead-end inhibition) by excess ethanol was set up to measure the reaction and inhibition rates.     

Simple evaluation of aortic arch calcification by chest radiography in hemodialysis patients

Vascular calcification is associated with a poor prognosis in dialysis patients. It can be assessed with computed tomography but simple inoffice techniques may provide useful information. We compared the results obtained with a simple noninvasive technique with those obtained using multidetector computed tomography for aortic arch calcification volume (AoACV) in chronic hemodialysis (HD) patients. The enrolled study subjects were 63 (32 men and 31 women) maintenance HD patients. Calcification of the aortic arch was semiquantitatively estimated with a AoAC score (AoACS) on plain chest radiology. The AoACV was increased, with a mean value of 6.6 ranging from 0% to 36.5%. The coefficient of intraobserver variation was less than 2.5%. Aortic arch calcification score was highly correlated with AoACV (r=0.635, P<0.001). Multiple regression analysis showed age (F value=12.62, P<0.001) and pulse pressure (F value=4.54, P=0.037) to be significant independent determinants of AoACS. In conclusion, a simple measurement of AoACS may be useful for inoffice imaging to choose a therapeutic regimen in HD patients.     

Reaction joining of SiC ceramics using TiB2-based composites

SiC ceramics were reaction joined in the temperature range of 1450–1800 °C using TiB₂-based composites starting from four types of joining materials, namely Ti–BN, Ti–B₄C, Ti–BN–Al and Ti–B₄C–Si. XRD analysis and microstructure examination were carried out on SiC joints. It is found that the former two joining materials do not yield good bond for SiC ceramics at temperatures up to 1600 °C. However, Ti–BN–Al system results in the connection of SiC substrates at 1450 °C by the formation of TiB₂–AlN composite. Furthermore, nearly dense SiC joints with crack-free interface have been produced from Ti–BN–Al and Ti–B₄C–Si systems at 1800 °C, i.e. joints TBNA80 and TBCS80, whose average bending strengths are measured to be 65 MPa and 142 MPa, respectively. The joining mechanisms involved are also discussed.     

Space charge field effect on light emitting from tetracene field-effect transistor under AC electric field

By applying square wave AC voltage to the Au source electrode of tetracene based field-effect transistor (FET), electroluminescence (EL) was obtained. The results suggest that electrons and holes were injected alternately from the source electrode and recombined each other, and lead to the EL. This type of EL was localized at the interface between the source electrode and tetracene, and enhanced periodically with two relaxation times in accordance with the applied AC voltage cycle. We modeled the carrier behavior in the FET and explained the decay of EL, taking into account the space charge field contribution. Finally, using an AC voltage superposed on DC bias voltage, it was shown that electron injection was prompted only by space charge field.     

Highwall Stability due to Punch Mining at Opencut Coal Mines

Conventional highwall mining extracts coal with an auger machine or a continuous miner from exposed seams at the base of opencut or strip operations. However, under poor strata and high stress conditions, highwall mining cannot be conducted due to pillar and roof failures. In such cases, punch highwall mining is more effective than the conventional highwall mining. This paper describes conventional highwall mining and punch highwall mining systems and discusses the stability of the highwall due to punch highwall mining at opencut coal mines.     

Quantum Effects on Hydrogen Isotopes Adsorption in Nanopores

We have investigated the applicability of simulations and theoretical techniques for exploring the selectivities of hydrogen isotopes. We have simulated the adsorption isotherms of H₂ in an idealized carbon slit pore at 77 K by using the grand canonical Monte Carlo simulations with the Feynman-Hibbs effective potential (FH-GCMC) and the rigorous path integral method (PI-GCMC), and we obtained good agreement between the isotherms from both simulations. This suggests that FH-GCMC, which uses the approximative Feynman-Hibbs treatment, is as useful as PI-GCMC for exploring H₂ adsorption at 77 K. Moreover, we show that the ideal adsorption solution theory (IAST) can predict the selectivity of D₂ over H₂ in the interstices of single-wall carbon nanotube (SWNT) bundles at 77 K (below 0.1 MPa) very well by comparing the obtained results with the mixture adsorption FH-GCMC simulations. This indicates that IAST is also applicable to the estimation of the selectivity of D₂ over H₂ at moderate pressures and at 77 K from experimental single-component adsorption isotherms. We also demonstrate that the FH-GCMC simulation can reproduce the experimental adsorption isotherms of H₂ and D₂ in aluminophosphate AlPO₄-5 at 77 K. Finally, we analyze the selectivity of D₂ over H₂ by IAST with the experimental single-component adsorption isotherms of H₂ and D₂ at 77 K for a variety of adsorbents: AlPO₄-5, activated carbon fibers (ACFs), HiPco SWNT, and SWNHs. The selectivities predicted by the experimental adsorption data based on the results from the FH-GCMC simulations are presented and discussed.     

An efficient hybrid conventional method to fabricate nacre-like bulk nano-laminar composites

Bulk nano-laminar composites were fabricated by a novel technique called Hot-press Assisted Slip Casting (HASC) which combines hot-pressing and slip-casting to improve alignment and volume fraction of the reinforcement. Alumina flakes were used as filler in an epoxy matrix. Microstructure of composites and alignment of flakes were characterized by Scanning Electron Microscope (SEM). Three point bending test and Vickers hardness test were done for mechanical characterization of composites. Flexural tests on Chevron-notched specimens revealed a high work-of-fracture in the case of the fabricated composites reaching to 254 J/m². Fracture surface of three point bending samples were examined by SEM. Main fracture mechanism is debonding of flakes from the matrix. With its high volume fraction (60%) of reinforcement phase and high degree of flake alignment, a nacre-like microstructure was achieved with a relatively efficient, cost effective and simple hybrid conventional method.