Thermal behaviour of TiO2-encapsulating polymers

Comparing the thermal properties of TiO₂ encapsulating polystyrene and poly(methyl methacrylate) with those of TiO₂ dispersion polymers it was found that the encapsulating polymers have two thermal relaxation regions. The activation energy of those thermal relaxation regions was determined using the Wunderlich method and it was found that the values are similar to the activation energy for the dynamic dispersion. It is suggested that the low-temperature thermal relaxation is caused by the local change of conformation of molecular chains, while the high-temperature thermal relaxation is similar to that of the normal glass transition temperature including the interaction with TiO₂. In addition, the thermal behaviour near the degradation point in different atmospheres indicates that the encapsulating polymer has a specific structure for adsorbing a large amount of oxygen.     

Poly(L‐lactide). X. Enhanced surface hydrophilicity and chain‐scission mechanisms of poly(L‐lactide) film in enzymatic,alkaline, and phosphate‐buffered solutions

Attempts were carried out to enhance the surface hydrophilicity of poly(L ‐lactide), that is, poly(L ‐lactic acid) (PLLA) film, utilizing enzymatic, alkaline, and autocatalytic hydrolyses in a proteinase K/Tris–HCL buffered solution system (37°C), in a 0.01N NaOH solution (37°C), and in a phosphate‐buffered solution (100°C), respectively. Moreover, its chain‐scission mechanisms in these different media were studied. The advancing contact‐angle (θ_a) value of the amorphous‐made PLLA film decreased monotonically with the hydrolysis time from 100° to 75° and 80° without a significant molecular weight decrease, when enzymatic and alkaline hydrolyses were continued for 60 min and 8 h, respectively. In contrast, a negligible change in the θ_a value was observed for the PLLA films even after the autocatalytic hydrolysis was continured for 16 h, when their bulk M_n decreased from 1.2 × 10⁵ to 2.2 × 10⁴ g mol^?1 or the number of hydrophilic terminal groups per unit weight increased from 1.7 × 10^?5 to 9.1 × 10^?5 mol g^?1. These findings, together with the result of gravimetry, revealed that the enzymatic and alkaline hydrolyses are powerful enough to enhance the practical surface hydrophilicity of the PLLA films because of their surface‐erosion mechanisms and that its practical surface hydrophilicity is controllable by varying the hydrolysis time. Moreover, autocatalytic hydrolysis is inappropriate to enhance the surface hydrophilicity, because of its bulk‐erosion mechanism. Alkaline hydrolysis is the best to enhance the hydrophilicity of the PLLA films without hydrolysis of the film cores, while the enzymatic hydrolysis is appropriate and inappropriate to enhance the surface hydrophilicity of bulky and thin PLLA materials, respectively, because a significant weight loss occurs before saturation of θ_a value. The changes in the weight loss and θ_a values during hydrolysis showed that exo chain scission as well as endo chain scission occurs in the presence of proteinase K, while in the alkaline and phosphate‐buffered solutions, hydrolysis proceeds via endo chain scission. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1628–1633, 2003     

A convenient method for preparation of monofluorocarboxylic acids

Monofluoro esters were prepared by the reaction of hydroxy esters with N,N-diethyl-1,1,2,3,3,3-hexafluoro propylamine (PPDA). Saponification of these monofluoroesters with enzyme (lipase MY) was attempted to give their corresponding monofluorocarboxylic acids in moderate yields.     

Two-stage pyrolysis of heavy oils. 3. Pyrolysis of tar-sand bitumens. Relation between ethylene yield and structural characteristics of heavy oils

Thermal cracking of tar-sand bitumens has been carried out using a two-stage pyrolysis reactor with temperature zones of 440°C and 750–800°C, respectively. Feedstocks were pyrolysed in the first stage into cracked oils, which were carried to the second stage for subsequent pyrolysis. Only 12–14 wt% of ethylene was obtained from tar-sand bitumens at the residence time of 1.2 s in the second stage, although 27 and 16 wt% were obtained from Taching and Iranian heavy vacuum residues, respectively. The tar-sand bitumens contain shorter paraffinic straight-chains and have more branched molecules than the vacuum residues of petroleum. A straight-chain paraffin index is proposed, with which a good correlation was obtained between ethylene yield and the fraction of straight-chain paraffin carbons in the heavy oil.     

Nitrous oxide emissions from fertilized upland fields in Thailand

Nitrous oxide (N₂O) emission from fertilized maize fields was measured using a closed chamber at four experimental sites in Thailand. The average measured N₂O flux from unfertilized plots through crop season was 4.16 ± 1.52, 5.05 ± 1.65, 5.25 ± 1.68 and 6.74 ± 2.95 g N₂O-N m^-2 h^-1, at Nakhon Sawan, Phra Phutthabat, Khon Kaen and Chiang Mai, respectively. Increased N₂O emissions by the application of nitrogen fertilizer were 0.22–0.44, 0.19–0.38%, 0.12–0.24 and 0.08–0.15% of the applied N, respectively. Compared to other data, N₂O emission rate to applied nitrogen was not significantly different between the data of Thailand and the Temperate Zone.     

The Direct Synthesis of β-hydroxy-acids by Lithium Naphthalene and Acetic Acid

Lithium naphthalene reacts with acetic acid to give α-anion of lithium acetate. The reaction of this anion with various ketones gives the corresponding β-hydroxy-acids in good yield.     

Performance of solvothermally prepared Ga2O3-Al2O3 catalysts for SCR of NO with methane

The solvothermal reaction of mixtures of aluminum isopropoxide (AIP) and gallium acetylacetonate (Ga(acac)₃) directly yielded the mixed oxides of γ-Ga₂O₃-Al₂O₃. In the solvothermal synthesis, the crystal structure of mixed oxides was controlled by the initial formation of γ-Ga₂O₃ nuclei. The mixed oxides prepared in diethylenetriamine have extremely high activities for selective catalytic reduction (SCR) of NO with methane as a reducing agent. With increasing crystallite size of the spinel structure, the catalytic activity increased. The ratio of the amount of methane consumed by combustion to total methane conversion was proportional to the density of acid sites on the surface of the mixed oxides. The mixed oxide catalysts prepared in diethylenetriamine had lower densities of acid sites and showed a higher methane-efficiency for CH₄-SCR than those prepared in other solvents. These catalysts maintained their high activity even when the reaction was carried out under the severe conditions (i.e., high space velocity and low NO concentration).     

Observation of single-walled carbon nanotubes by photoemission microscopy

Single-walled carbon nanotube networks grown on SiO₂ pillars were studied by means of scanning photoemission microscopy. The individual nanotubes or nanotube bundles growing from the pillar tops were observed in C 1s images. Band bending near catalytic Fe/nanotube contacts in an end-bonded configuration was studied by measuring C 1s spectra along the tube axes. Within our experimental resolution, no band bending was observed. This implies that the depletion width is less than the spatial resolution of the scanning photoemission microscope (90 nm) or that the amount of the band bending is less than 0.1 eV.