Extended Open-Chain Polyenides as Versatile Delocalized Anion Ligands for Metal Chain Clusters

Although small cyclic- and open-chain unsaturated hydrocarbon anions such as cyclopentadienide and open-chain pentadienide are used as the strongly electron-donating auxiliary ligands for metal complexes, more extended π-conjugated unsaturated hydrocarbon anions have rarely been used in coordination chemistry, despite their potential ability to serve as the multiply bridging π-ligands for metal clusters. This work reports isolation of metal chain clusters bearing the multi-dentate, open-chain extended unsaturated hydrocarbon anion ligands. The extended open-chain π-conjugated polyenyl ligands could effectively stabilize oxidized palladium chains, including an unprecedented [Pd₄]⁴⁺ chain.     

The required sample size in measuring oblique incidence absorption coefficient Experimental study

It is an important issue to clarify the minimum required size of a specimen for the accurate measurement of oblique incidence absorption coefficient. Investigation is made on the basis of experimental studies in a laboratory, using Aoshima's time stretched pulse technique. Measurements are carried out for glass fiber with thickness of 50 and 100 mm as highly absorbing materials and for ceramic with a thickness of 52 mm as relatively low absorbing material. The tested surface areas range from 0.0625 to 42 m² for glass fiber and from 0.1563 to 39.168 m² for ceramics. The absorption coefficients are determined at incidence angles from 0 to 45° in increments of 15°. With consideration of an active surface bounded by ellipse orbit, the minimum required surface area is 16 m² with a ratio of length to width of about 1.25. This value is twice the area size of the active surface, which is calculated from the geometry of source and microphone, and the width of the temporal window.     

Study on crystalline properties of Er-Si-O compounds in relation to Er-related 1.54 μm photoluminescence and electrical properties

Er-Si-O crystalline compounds, which exhibit superlattice structures and sharp and strong Er-related 1.54 μm photoluminescence (PL) spectra at room temperature have been formed by self-assembling growth mechanism. Oxidation of the starting materials which have Si and Er at an atomic ratio of 2:1 are prepared and then oxidation and succeeding high-temperature annealing in Ar above 1250 °C cause a self-assembled superlattice-structured Er-Si-O crystalline compounds. The control of the ratio of Si and Er, as well as the following oxidation and annealing processes, is found to be sensitive to the crystalline properties, PL spectra and electrical properties. In this study, Er-Si-O crystalline thin films are formed on Si substrates by sol-gel and MOMBE methods, and their crystalline properties such as crystalline orientation and concentration ratio of Er, Si and O are investigated. Crystalline Er-Si-O films of high orientation are successfully grown on Si(1 0 0) and its inclined surface. The PL and excitation spectra, fluorescence decay and the electrical properties are found to be strongly related to the crystalline properties. Excess O causes a broader 1.54 μm PL spectra, slower fluorescence decay, lower carrier-mediated excitation and higher resistivity. A precise control of O is found to be necessary to grow superlattice-structured Er-Si-O compounds, which are semiconducting and are excitable via carrier-mediated excitation mechanism.     

Long-wavelength light emission from InAs quantum dots covered by GaAsSb grown on GaAs substrates

We fabricated InAs quantum dots (QDs) with a GaAsSb strain-reducing layer (SRL) on a GaAs(0 0 1) substrate. The wavelength of emission from InAs QD is shown to be controllable by changing the composition and thickness of the SRL. An increase in photoluminescence intensity with increasing compositions of Sb and thickness of the GaAsSb SRL is also seen. The efficiency of radiative recombination was improved under both conditions because the InAs/GaAsSb/GaAs hetero-interface band structure more effectively suppressed carrier escape from the InAs QDs.     

Structure and properties of the mesophase of syndiotactic polystyrene. II. Effect of stepwise extraction on the preparation of the mesophase

In this study, a novel stepwise extraction method has been examined. The guest molecules housed between the helices of the clathrate δ form of syndiotactic polystyrene can be removed completely with this method. A systematic study of the preparation of a solvent‐free mesophase (emptied clathrate) membrane, its helical and residual solvent contents, and its structural transformations has been performed. In this first attempt, an enhancement in the TTGG helical content has been observed in the extracted membrane, and a conceptual mechanism is proposed. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 269–273, 2003     

Improvement of gas meter performance using polymer materials

The measuring elements of both dry‐ and wet‐type gas meters are composed of a diaphragm and rotary drum. In this article an explanation on the principle of measuring and the structure of the gas meter for each of these two types was discussed. Such applications were made as follows: synthetic rubber was used for the measuring diaphragm, engineering plastic was employed instead of metal for the measuring drum, and poly(butylene terephthalate) (PBT) was used for the casing, respectively. As a result, an improvement in the gas resistance performance and productivity, which led to a lighter weight, more compactness and a lower cost of productions was achieved. Also the influence of the solubility of the measured gas to the plastic on the measured valve was discussed. Copyright © 2003 John Wiley & Sons, Ltd.     

Kinetic study of the crosslinking reaction of 1,2‐polybutadiene with dicumyl peroxide in the absence and presence of vinyl acetate

The crosslinking reaction of 1,2-polybutadiene (1,2-PB) with dicumyl peroxide (DCPO) in dioxane was kinetically studied by means of Fourier transform near-infrared spectroscopy (FTNIR). The crosslinking reaction was followed in situ by the monitoring of the disappearance of the pendant vinyl group of 1,2-PB with FTNIR. The initial disappearance rate (R₀) of the vinyl group was expressed by R₀ = k[DCPO]^0.8[vinyl group]^−0.2 (120 °C). The overall activation energy of the reaction was estimated to be 38.3 kcal/mol. The unusual rate equation was explained in terms of the polymerization of the pendant vinyl group as an allyl monomer involving degradative chain transfer to the monomer. The reaction mixture involved electron spin resonance (ESR)-observable polymer radicals, of which the concentration rapidly increased with time owing to a progress of crosslinking after an induction period of 200 min. The crosslinking reaction of 1,2-PB with DCPO was also examined in the presence of vinyl acetate (VAc), which was regarded as a copolymerization of the vinyl group with VAc. The vinyl group of 1,2-PB was found to show a reactivity much higher than 1-octene and 3-methyl-1-hexene as model compounds in the copolymerization with VAc. This unexpectedly high reactivity of the vinyl group suggested that an intramolecular polymerization process proceeds between the pendant vinyl groups located on the same polymer chain, possibly leading to the formation of block-like polymer. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4437–4447, 2004     

Structure and properties of the mesophase of syndiotactic polystyrene. VIII. Solvent sorption behavior of syndiotactic polystyrene/p‐chlorotoluene mesophase membranes

A crystalline δ form of a syndiotactic polystyrene (sPS) membrane was prepared from a solution of sPS (1 wt %) and p‐chlorotoluene (p‐CT) by a solution‐casting method. The mesophase (δ empty form) of sPS was obtained by the extraction of the guest solvent from the δ form of sPS by a stepwise solvent‐extraction method. The sPS/p‐CT mesophase membrane [p‐CT (A‐M)] was used for the sorption of 1 mol % p‐CT for different times and for the sorption of different concentrations of p‐CT, chlorobenzene (CB), p‐xylene (p‐X), toluene, and chloroform for 48 h. The presence of solvents in the sPS membrane was confirmed by IR analysis. A thermal study revealed that the sorption amount of 1 mol % p‐CT increased with increasing immersion time, and the sorption amounts of different solvents increased with increasing solvent concentration. Differential scanning calorimetry results showed that the desorption peak temperature increased as the amount of the solvent increased in the clathrated sPS membrane. Wide‐angle X‐ray diffraction results showed that 2θ at 8.25° was slightly shifted toward 8°, and there was no change in the peak position at 10° for p‐CT (A‐M), which was immersed in different solvents (1 mol %); however, the intensity of 2θ at 10° was not similar for all the samples. Among the solvents used for the sorption studies at 1 mol %, p‐CT (A‐M) could sorb more p‐CT and CB than p‐X, toluene, and chloroform. The solvent sorption isotherm was the Langmuir sorption mechanism. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3439–3446, 2004