Selectivity and mechanism for skeletal isomerization of alkanes over typical solid acids and their Pt-promoted catalysts

Selectivities for skeletal isomerizations of n-butane and n-pentane catalyzed by typical solid acids such as Cs_2.5H_0.5PW₁₂O₄₀ (Cs2.5), SO₄²⁻/ZrO₂, WO₃/ZrO₂, and H-ZSM-5 and their Pt-promoted catalysts were compared. High selectivities for n-butane and low selectivity for n-pentane were observed over Cs2.5 and SO₄²⁻/ZrO₂, while H-ZSM-5 was much less selective, and WO₃/ZrO₂ was highly selective for both reactions. The Pt-promoted solid acids were usually selective for these reactions in the presence of H₂ except for Pt-H-ZSM-5 for n-butane isomerization. Both the acid strength and pore structure would be factors influencing the selectivity. Mechanism of skeletal isomerization of n-butane was investigated by using 1,4-¹³C₂-n-butane over Cs2.5 and Pt–Cs2.5. It was concluded that n-butane isomerization proceeded mainly via monomolecular pathway with intramolecular rearrangement on Pt–Cs2.5, while it occurred through bimolecular pathway with intermolecular rearrangement on Cs2.5. The higher selectivity on Pt–Cs2.5 would be brought about by the monomolecular mechanism. In the skeletal isomerization of cyclohexane, Pt–Cs2.5/SiO₂ was highly active and selective, while Pt–Cs2.5 was less selective. Control in the acid strength of Cs2.5 by the supporting would be responsible for the high selectivity.     

Stereocomplex formation between enantiomeric poly(lactic acid). VIII. Complex fibers spun from mixed solution of poly(D-lactic acid) and poly(L-lactic acid)

To obtain poly(lactic acid) (PLA) complex fibers, spinning was performed by wet and dry methods from 5–10 g/dL chloroform solutions of poly(D-lactic acid) (PDLA) and poly(L-lactic), both with a viscosity-average molecular weight of 3 × 10⁵. The dope was extruded from a monohole nozzle into coagulation baths from ethanol and chloroform for wet spinning and into a drying column kept at 60°C for dry spinning. Scanning electron microscopic observation of the as-spun fibers showed that the surface of the wet-spun fiber had large basins with diameters of 50–100 μm and many pores with diameters from sub μm to 10 μm, whereas the surface of dry-spun fiber had a microporous structure with the pore diameter of 1–3 μm. The tensile strength of the wet-spun complex fiber was very low and could not be drawn at high temperatures, in contrast to the dry-spun fiber. The tensile strength of dry-spun complex fiber increased upon hot drawing and showed the tensile strength of 94 kg/mm² by drawing at 160°C to the draw ratio of 13. Differential scanning calorimetry revealed that the complex fibers contained both the stereocomplex crystallites (racemic crystallites) and the crystallites of the single polymers, PDLA and PLLA, regardless of the spinning methods. The ratio of the racemic crystallites to the single-polymer crystallites increased with the draw ratio of the complex fiber. © 1994 John Wiley & Sons, Inc.     

High-Temperature Active Oxidation of Chemically Vapor-Deposited Silicon Carbide in CO─CO2 Atmosphere

Active oxidation behavior of CVD-SiC in CO─CO₂ atmospheres was investigated using a thermogravimetric technique in the temperature range between 1823 and 1923 K. The gas pressure ratio, P _CO2/ P _CO, was controlled between 10⁻⁴ and 10⁻¹ at 0.1 MPa. Active oxidation rates (mass loss rates) showed maxima at a certain value of P _CO2/ P _CO, ( P _CO2/ P _CO )^*, In a P _CO2/ P _CO region lower than the ( P _CO2/ P _CO)^* a carbon layer was formed on the SiC surface. In a P _CO2/ P _CO region higher than the ( P _CO2/ P _CO)^*, silica particles or a porous silica layer was observed on the SiC surface.     

Synthesis and properties of polyacetylenes carrying N-phenylcarbazole and triphenylamine moieties

Novel acetylene monomers containing N-phenyl-substituted carbazole (Cz) and triphenylamine (TPA) groups, namely, 3-ethynyl-9-phenylcarbazole (1) and p-(N,N-diphenylamino)phenylacetylene (2) were synthesized, and polymerized with several Rh-, W-, and Mo-based catalysts. Poly(1) and poly(2) with high number-average molecular weights (15?500-974?000) were obtained in good yields (77-97%), when [(nbd)RhCl]₂-Et₃N (nbd = norbornadiene) was used as a catalyst. The polymers exhibited UV-vis absorption peaks derived from the Cz and TPA moieties at 250-350 nm and polyacetylene backbone above 350 nm. The UV-vis absorption band edge wavelengths of the polymers were longer than those of the corresponding monomers. Poly(2) exhibited a UV-vis absorption peak at a longer wavelength than poly(1) did, which indicates that poly(2) has main chain conjugation longer than that of poly(1). The molecular weights and photoluminescence quantum yields of the polymers obtained by the polymerization using [(nbd)RhCl]₂-Et₃N were larger than those of the Rh⁺(nbd)[η⁶-C₆H₅B⁻(C₆H₅)₃]-based counterparts. The cyclic voltammograms of the polymers indicated that they had clear electrochemical properties; the onset oxidation voltage of poly(1) was higher than those of N-alkyl-substituted Cz derivatives. The polymers showed electrochromism and changed the color from pale yellow to blue by application of voltage, presumably caused by the formation of charged polaron at the Cz and TPA moieties. The temperatures for 5% weight loss of the polymers were around 350-420 °C under air, indicating the high thermal stability.     

The influence of drawing,twisting, heat setting and untwisting on the structure and mechanical properties of melt spun polypropylene filament

The changes in structure and mechanical properties of melt spun polypropylene filaments were determined as the filaments were successively (i) drawn, (ii) twisted, (iii) annealed, and (iv) untwisted. Filaments spun to two different melt draw down levels were studied. The effects of draw temperature and draw ratio, extent of twist, annealing temperature, and the extent of untwisting were examined. Melt spun and twisted filaments (draw ratio of 1) were also considered. Structural characterization techniques used in this study include wide angle (WAXS) and small angle (SAXS) diffraction, scanning electron microscopy (SEM), birefringence and density measurement. Drawing increased crystalline orientation and at low temperatures disrupted the monoclinic unit. cell existing in the melt spun fibers. The drawing produced considerable fibrillation under all conditions even when carried out at 120°C. The fibrillation quid void formation due to low temperature drawing was more pronounced. The variation of WAXS patterns and mechanical properties of twisted drawn filaments was interpreted by presuming that the fibrils act in a manner analogous to that of the filaments in a continuous filament twisted yarn. In the case of incompletely drawn filaments the effect of additional drawing occurring during twistin must be considered. Twisted fibers annealed at 150°C sowed a drastic reduction in tensile properties, while those annealed at 125°C did not set the twist and caused the fibers to tend to untwist. Annealing at 140°C appeared to give satisfactory heat setting. Annealing of cold drawn and cold drawn and twisted fibers increased the density, removed many defects and reformed a well defined monoclinic crystal structure and a lamellar morphology. Untwisting of heat set filaments tended to give back the properties of hot drawn fibers. In some cases, however, the opening of cracks was noted.     

Phase morphologies and mechanical properties of high‐impact polystyrene (HIPS) and polycarbonate blends compatibilized with polystyrene and polyarylate block copolymer

Phasemorphology and mechanical properties of blends of high‐impact polystyrene (HIPS) and polycarbonate (PC) blends compatibilized with a polystyrene (PS) and polyarylate (PAr) (PS–PAr) block copolymer were investigated. Over a broad range of composition from 50/50 through 30/70, HIPS/PC blends formed cocontinuous structures induced by the flow during the extrusion or injection‐molding processes. These cocontinuous phases had heterogeneity between the parallel and perpendicular directions to the flow. The micromorphology in the parallel direction to the flow consisted of stringlike phases, which were highly elongated along the flow. Their longitudinal size was long enough to be longer than 180 μm, while their lateral size was shorter than 5 μm, whereas that in the perpendicular direction to the flow showed a cocontinuous phase with regular spacing due to interconnection or blanching among the stringlike phases. The PS–PAr block copolymer was found to successfully compatibilize the HIPS/PC blends. The lateral size of the stringlike phases could be controlled both by the amount of the PS–PAr block copolymer added and by the shear rate during the extrusion or injection‐molding process without changing their longitudinal size. The HIPS/PC blend compatibilized with 3 wt % of the PS–PAr block copolymer under an average shear rate of 675 s^?1 showed a stringlike phase whose lateral size was reduced almost equal to the rubber particle size in HIPS. The tensile modulus and yield stress of the HIPS/PC blends could be explained by the addition rule of each component, while the elongation at break was almost equal to that of PC. These mechanical properties of the HIPS/PC blends can be explained by a parallel connection model independent of the HIPS and PC phases. On the other hand, the toughness factor of the HIPS/PC blends strongly depended on the lateral size of the stringlike phases and the rubber particle size in the HIPS. It was found that the size of the string phases and the rubber particle should be smaller than 1.0 μm to attain a reasonable energy absorbency by blending HIPS and PC. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2347–2360, 2001     

Oxidation kinetics for <Emphasis Type="Italic">cis</Emphasis>-9,<Emphasis Type="Italic">trans</Emphasis>-11 and <Emphasis Type="Italic">trans</Emphasis>-10,<Emphasis Type="Italic">cis</Emphasis>-12 isomers of CLA

The autoxidation processes of the cis-9,trans-11 (c9,t11) and trans-10,cis-12 (t10,c12) isomers of CLA were separately observed at ca. 0% RH and different temperatures. The t10,c12 CLA oxidized faster than the c9,t11 isomer at all tested temperatures. The first half of the oxidation process of t10,c12 CLA obeyed an autocatalytic-type rate expression, but the latter half followed first-order kinetics. On the other hand, the entire oxidation process of c9,t11 CLA could be expressed by the autocatalytic-type rate expression. The apparent activation energies and frequency factors for the autoxidation of the isomers were estimated from the rate constants obtained at various temperatures based on the Arrhenius equation. The apparent activation energies for the CLA isomers were greater than those for the nonconjugated n−6 and n−3 PUFA or their esters. However, the enthalpyentropy compensation held during the autoxidation of both the CLA and PUFA. This suggested that the autoxidation mechanisms for the CLA and PUFA were essentially the same.     

Study of crater formation and sputtering process with large gas cluster impact by molecular dynamics simulations

Molecular dynamics (MD) simulations of large argon clusters impacting on silicon solid targets were performed in order to study the transient process of crater formation and sputtering. The MD simulations demonstrate that the initial momentum of incident cluster is transferred to target surface atoms through multiple collision mechanism, where the initial momentum, which is along to the surface normal before impact, is deflected to lateral direction. This momentum transfer process was analyzed by the calculation of the velocity at the crater edge (the interface between cluster and target). In the case of Ar₁₀₀₀ cluster impact on Si(1 0 0) target at low energy per atom less than 40 eV/atom, the maximum value of lateral velocity of the crater edge increases in proportional to the velocity of incident cluster atoms. On the other hand, the crater edge velocity saturates over 40 eV/atom of incident energy per atom. In this case, the whole of constituent cluster atoms are implanted into the target and expand in both lateral and reflective directions at the subsurface region of the target. These MD simulations demonstrated that this collisional process result in the high yield sputtering of the target atoms.     

Mixture distribution measurement using laser induced breakdown spectroscopy in hydrogen direct injection stratified charge

Reduction in cooling loss due to the heat transfer from burning gas to the combustion chamber wall is very important for improving the thermal efficiency in hydrogen engines. The previous research has shown that the direct injection stratified charge can be a technique to reduce the cooling loss and improve thermal efficiency in hydrogen combustion. For effective reductions in cooling loss by the stratified charge, it is very important to know the relation between the fuel injection conditions and mixture distribution. The current research employs the laser induced breakdown spectroscopy as a method to measure the hydrogen concentration distribution in the direct injection stratified charge. Measurement of instantaneous local equivalence ratio by the method clears the characteristics of mixture formation in hydrogen direct injection stratified charge. This research also tries to actively control the mixture distribution using a split fuel injection.     

Thermal Stability of Polycarbosilane-Derived Silicon Carbide Fibers under Reduced Pressures

Three types of polycarbosilane-derived SiC fibers—Nicalon, Hi-Nicalon, and Hi-Nicalon S—were exposed at temperatures of 1573–1773 K under a reduced pressure of 1.3 Pa. The thermal stability of the fibers was investigated through examinations of the gas evolution, grain growth, specific resistivity, fiber morphology, and tensile strength. The thermal decomposition of the silicon oxycarbide phase began at 1523 K; then, active oxidation of the β-SiC crystallites occurred at >1673 K. The active oxidation caused serious damage to the fiber structure, which resulted in significant degradation of the fiber strength. Hi-Nicalon had a tensile strength of ∼0.5 GPa after exposure at 1773 K, although Nicalon and Hi-Nicalon S fibers completely lost their strength, even after exposure at 1673 K. Hi-Nicalon fiber had relatively good thermal stability under reduced pressure.