Catalytic reactions on neutral Rh oxide clusters more efficient than on neutral Rh clusters

Gas phase catalytic reactions involving the reduction of N(2)O and oxidation of CO were observed at the molecular level on isolated neutral rhodium clusters, Rh(n) (n = 10-28), using mass spectrometry. Sequential oxygen transfer reactions, Rh(n)O(m-1) + N(2)O → Rh(n)O(m) + N(2) (m = 1, 2, 3,…), were monitored and the rate constant for each reaction step was determined as a function of the cluster size. Oxygen extraction reactions by a CO molecule, Rh(n)O(m) + CO → Rh(n)O(m-1) + CO(2) (m = 1, 2, 3,…), were also observed when a small amount of CO was mixed with the reactant N(2)O gas. The rate constants of the oxygen extraction reactions by CO for m ≥ 4 were found to be two or three orders of magnitude higher than the rate constants for m ≤ 3, which indicates that the catalytic reaction proceeds more efficiently when the reaction cycles turn over around Rh(n)O(m) (m ≥ 4) than around bare Rh(n). Rhodium clusters operate as more efficient catalysts when they are oxidized than non- or less-oxidized rhodium clusters, which is consistent with theoretical and experimental studies on the catalytic CO oxidation reaction on a rhodium surface.     

High-yield synthesis of semiconductive type-II Si clathrates with low Na content

To develop an efficient synthesis of type-II Si clathrates with low Na content (Na_xSi₁₃₆: x = 0–24), various conditions for annealing the Zintl phase NaSi were examined. The addition of a pre-annealing process under vacuum at 250 °C following the preparation of NaSi resulted in a decrease in the Na content of type-II Si clathrates from 4 to 2 when the pre-annealing duration ranged from 0 to 60 h, while the volume fraction of type-II Si clathrate crystals in the synthesized specimens (type-II/(type-I + type-II + d-Si)) deduced by powder X-ray diffraction and Rietveld analysis was maintained at approximately 85%. These preparation techniques that enable the high-yield synthesis of semiconductive type-II Si clathrates open opportunities for the application of these substances to semiconductor devices.     

Optical band gap of semiconductive type II Si clathrate purified by centrifugation

The optical properties of Si clathrate, which is believed to have potential as a new Si-based material for optical devices, were investigated in this study. Si clathrates with type II structure (Na_xSi₁₃₆) with low Na content (x = 1.3, 2.0) were synthesized by thermal decomposition of NaSi. The synthesized samples were purified by centrifugation using a solution of CH₂Br₂–C₂Cl₄ to remove impurities. Using the obtained high purity samples (Na_1.3Si₁₃₆, 93 wt.%; Na_2.0Si₁₃₆, 90 wt.%), the optical absorption spectra of Na_xSi₁₃₆ were clarified, for the first time, from diffuse reflection measurements. The inclusion of Na in Si₁₃₆ was found to cause free carrier absorption in the infrared region but had little effect on the fundamental absorption edge found in the visible region.     

Studies on surface molecular motion of oligomeric polystyrene by differential scanning calorimetry

There are many studies on the surface molecular motion of polymer films [ 1 ], but no report on surface thermal properties of polymer because of experimental difficulties. The thermal property of oligomeric polystyrene (PS) was investigated by differential scanning calorimetry (DSC) in the present study. In order to increase the ratio of surface area to volume of PS particles, the DSC samples were prepared by mechanically grinding mixtures of PS and Al₂O₃ powders. The grinding mixtures of these powders with low particle size showed a transition at a low temperature of 14–17 °C (much lower than the bulk glass transition temperature, T_g), and this low‐temperature transition was dependent on the size of PS particles. This transition seems to result from the surface molecular motion of the activated surface layer of PS. Copyright © 2000 John Wiley & Sons, Ltd.     

Nonisothermal membrane phenomena across perfluorosulfonic acid-type membranes,Flemion S: part I. Thermoosmosis and transported entropy of water

Solvent transports across the perfluorosulfonic acid-type membrane Flemion S were measured for aqueous electrolyte solutions under a temperature difference and under an osmotic pressure difference. H⁺, Li⁺, Na⁺, K⁺, NH ₄ ⁺ , CH₃NH ₃ ⁺ , (CH₃)₂NH ₂ ⁺ , (CH₃)₃NH⁺, (CH₃)₄N⁺, (C₂H₅)₄N⁺, (n-C₃H₇)₄N⁺ and (n-C₄H₉)₄N⁺ were used as counterions. Water flux across the membrane in HCl solution is higher than that in the other electrolyte solutions because hydrogen ions can exchange with the hydrogen of the neighbor water molecules and contribute to the water transport across the membrane as a proton jump in conductivity. The direction of thermoosmosis across the membrane in HCl, NaCl, (CH₃)₄NCl and (C₂H₅)₄NCl solutions was from the cold side to the hot side and that in LiCl, KCl, NH₄Cl, CH₃NH₃Cl, (CH₃)₂NH₂Cl and (n-C₄H₉)₄NBr solutions was from the hot side to the cold side, although thermoosmosis across anion-exchange membranes always occurs toward the hot side.     

Electric‐field‐induced chain orientation in poly(L‐lactic acid)

The orientational order was studied for melt‐state poly(L ‐lactic acid) under an external direct‐current electric field. A birefringence as high as 1.1 × 10^?2 was recorded against an external field of 1.0 MV/m at 190 °C. The evidence proved that a field–dipole interaction transferred from a randomly coiled conformation to a uniaxially drawn conformation. The field‐induced birefringence was temporally resolved, and the chain orientation and relaxation processes on the order of 100 s were observed in a real timescale after the field was turned on and off. A mechanism of chain orientation was examined with respect to the orientation polarization and viscoelasticity. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4433–4439, 2004     

Field emission from multi-walled carbon nanotubes and its application to electron tubes

Received: 5 December 1997     

Component analysis of proton NMR spectra of linear polyethylene in the α-transition temperature range and phase distribution

Broad-line ¹H NMR spectra of linear polyethylene at temperatures in the α-transition range can be analyzed in terms of contributions from the crystalline and noncrystalline components provided molecular motion in the crystalline region is adequately considered. The spectrum of solid n-C₃₂H₆₆ or n-C₄₄H₉₀ prior to melting is used to take account of the contribution of the crystalline region of the polymer to molecular motions. The temperature dependence of the component distribution in the polymer is briefly discussed for a wide range of temperatures, together with previously reported results at low temperatures. The noncrystalline component is in a rigid glassy state at very low temperatures but with rising temperature it transforms to a mobile glassy state with restricted molecular motion, and transforms partially to the rubbery state at high temperature. The crystalline component remains rigid at low temperature, but some molecular motion is associated with it at higher temperatures in the α-transition range.