Structure and gas permeation properties of asymmetric polyimide membranes made by dry–wet phase inversion: Influence of the polyimide molecular weight

In this article, we report the influence of the polyimide molecular weight (1.2 × 10⁵, 2.6 × 10⁵, and 4.1 × 10⁵) on the structure and the gas permeation properties of asymmetric polyimide membranes made by the dry–wet phase‐inversion process. The apparent skin layer thickness of the asymmetric membrane increased with increasing molecular weight, and the thicknesses of the membranes prepared from the three polyimides with a casting polymer solution containing 8.0 wt % butanol were 132, 350, and 739 nm, respectively. That is, the gas permeance in the asymmetric membranes increased with decreasing molecular weight. In contrast, the gas selectivity of the asymmetric membranes did not depend on the skin layer thickness. The solvent evaporation in the dry phase‐inversion process and the nonsolvent diffusion in the dry process were important factors that determined the formation of the asymmetric membrane. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

低能离子束辅照对溅射镀TiN膜生长的影响

用诱导型等离子体辅助磁控溅射装置在Si（100）表面低温沉积TiN膜，研究了高密度低能量（≈20eV）离子束辅照对溅射镀TiN膜生长、结构和性能的影响．结果表明，高密度低能离子束辅照会改变TiN膜的择优生长方向并使薄膜致密化。即使沉积温度低于150℃，当入射基板离子数和Ti原子数的比值Ji／JTi≥4.7时，沉积的TiN膜仍可具有完全的（200）面择优生长，薄膜微观结构致密，硬度达到25GPa，残余压应力小．     

Gas Effusion Spectra of Fullerenes

Gas effusion spectra of fullerenes are studied. Three peaks of toluene are found in gas effusion spectra dp/dT-T. Two peaks of oxygen are found in gas effusion spectra dN/dt-T of samples kept in the air after annealing to avoid the toluene. These phenomena confirmed to be reversible are discussed by treating fullerenes as intercalated materials.     

Three-dimensional scanner of a pipe with tilt detection

The 3D quantitative measurement system for a sewer pipe is introduced. Two parallel lasers are rotated by the motor and draw the two annular streaks on the inside surface of the pipe. The circular laser streaks are recorded by the CCD camera. The measurement of the cross-section is established by analyzing the recorded streaks. The tilt of the robot against the axis of the pipe is detected by the deviation between two parallel lasers. It enables us to measure the vertical cross section of the pipe regardless the tilt of the system to the pipe. Experimental result shows the feasibility of the system. This work was presented in part at the 13th International Symposium on Artificial Life and Robotics, Oita, Japan, January 31–February 2, 2008     

Environmentally friendly coloured materials: cellulose/titanium dioxide/inorganic pigment composite spherical microbeads prepared by viscose phase-separation method

In order to develop environmentally friendly coloured materials, cellulose composite spherical microbeads hybridised with titanium dioxide (TiO₂) particles and inorganic pigment were prepared by a phase-separation method using viscose and an aqueous solution containing sodium polyacrylate. Findings regarding the relationships between cellulose xanthate and the electronic characteristics of TiO₂ particles used in the cellulose/inorganic material composite sphering process are also reported. These findings suggest that the location of TiO₂ particles in cellulose microbeads is related to electrical repulsion between the xanthate (CSS⁻) group and TiO₂. The use of TiO₂ powder as colour pigment is limited, as its colour is white. The cellulose composite spherical microbeads covered with TiO₂ and Fe₂O₃ particles were developed by addition of iron oxide (Fe₂O₃). Their surfaces were viewed by laser microscope and using SEM images. These composite microbeads retained the photocatalytic property of TiO₂. Cellulose/TiO₂/Fe₂O₃ composite spherical microbeads with both colour function and photocatalytic properties were successfully prepared.     

Resonance Effect on the Tunneling Reaction: H+H2→H2+H in Solid Hydrogen

The tunneling abstraction reaction: H+H₂H₂+H in -irradiated solid hydrogen has been studied using electron spin resonance (ESR) and electron-nuclear double resonance (ENDOR) spectroscopy and gas-chromatography. The rate constant for the tunneling reaction in solid hydrogen was found to decrease with the increase in the concentration of ortho-H₂ molecules in solid hydrogen. We concluded that the decrease in the rate constant is due to the energy level mismatching between reactant species of H+H₂ trapped and product species of H₂+H trapped in the reverse induced by inhomogeneous intermolecular interactions between ortho-H² molecules in solid hydrogen. This result indicates that resonance effects play an important role in tunneling reactions in solids.     

Absorption and Fluorescence Spectra of Nitrobenzanthrones

To identify nitrobenzanthrones (NBAs) such as 3-nitro-7 H -benz[ de ]anthracene-7-one (3-NBA) on the basis of their electronic spectral data, we have synthesized 1-, 2-, 3-, 9-, and 10-NBAs and measured their absorption and emission spectra. The first strong absorption band of the NBAs appeared in the region 350-440 nm; the band of 10-NBA was red-shifted by about 20 nm. The molar absorptivities of 3- and 9-NBA were about two times as large as those of the others. The fluorescence spectra of the NBAs varied more largely with the position of the nitro group compared to the absorption spectra. The quantum yields of fluorescence were very small, ranging from ～10 m 2 for 2- and 10-NBA to ～10 m 4 for 1- and 3-NBA. 3-NBA exhibited a characteristic spectrum with two broad bands at 450 and 530 nm. On excitation causing an n ~ * transition in the NBAs, their fluorescence intensities increased by a factor of 10. Phosphorescence was observed at 77 K for all compounds though that of 1-NBA was very weak. These results give the promise of characterizing individual isomers of NBAs on the basis of their spectroscopic data.     

Decomposition and regeneration of methane in the absence and the presence of a hydrogen-absorbing alloy CaNi5

Suitable catalysts for the decomposition of methane into carbon and hydrogen and for the regeneration of methane by hydrogenation of the carbon have been looked for in a series of transition metals and precious metals supported on various carriers. The most active catalyst for both reactions was Ni/SiO₂. The carbon formed on this catalyst was thermodynamically less stable than graphite. The different rate equations for the decomposition of methane obtained for the fresh and carbon deposited Ni/SiO₂ suggest that the rate-determining steps are different for the two catalysts. The highest number of carbon atoms deposited per one Ni atom was 31 at 773 K. However, the number of methane molecules recovered easily at 773 K was limited to 1.5 per Ni atom.

A physical mixture of Ni/SiO₂ and CaNi₅, a hydrogen-absorbing alloy, enhanced the decomposition rate of methane, enabling the complete conversion of methane at 773 K beyond the thermodynamic limitation. The presence of CaNi₅ at 273 K separated from the catalyst in a reaction system further enhanced the decomposition of methane due to an increased hydrogen-absorbing capacity of the CaNi₅ at low temperatures. The carbon deposited on Ni/SiO₂ in this case was reactive to be hydrogenated back to methane at 773 K, giving an average 7.5 CH₄ molecules per one Ni atom.