Kinetic and morphological study of a magnesium ethoxide‐based Ziegler–Natta catalyst for propylene polymerization

BACKGROUND: Kinetic and morphological aspects of slurry propylene polymerization using a MgCl₂‐supported Ziegler–Natta catalyst synthesized from a Mg(OEt)₂ precursor are investigated in comparison with a ball‐milled Ziegler–Natta catalyst. RESULTS: The two types of catalyst show completely different polymerization profiles: mild activation and long‐standing activity with good replication of the catalyst particles for the Mg(OEt)₂‐based catalyst, and rapid activation and deactivation with severe fragmentation of the catalyst particles for the ball‐milled catalyst. The observed differences are discussed in relation to spatial distribution of TiCl₄ on the outermost part and inside of the catalyst particles. CONCLUSION: The Mg(OEt)₂‐based Ziegler–Natta catalyst is believed to show highly stable polymerization activity and good replication because of the uniform titanium distribution all over the catalyst particles. Copyright © 2008 Society of Chemical Industry     

Phase-transformation and grain-growth kinetics in yttria-stabilized tetragonal zirconia polycrystal doped with a small amount of alumina

Microstructure development during sintering in 3 mol% Y₂O₃-stabilized tetragonal zirconia polycrystal doped with a small amount of Al₂O₃ was investigated in the isothermal sintering conditions of 1300–1500 °C. At the low sintering temperature at 1300 °C, although the density was relatively high, the grain-growth rate was much slow. In the specimen sintered at 1300 °C for 50 h, Y³⁺ and Al³⁺ ions segregated along grain boundaries within the widths of about 10 and 6 nm, respectively. In grain interiors, the cubic-phase regions were formed by not only a grain-boundary segregation-induced phase-transformation mechanism but also by spinodal decomposition. The grain-growth behavior was kinetically analyzed using the grain-size data in 1300–1500 °C, which indicated that the grain-growth rate was enhanced by Al₂O₃-doping. These phase-transformation and grain-growth behaviors are reasonably explained by the diffusion-enhanced effect of Al₂O₃-doping.     

Effect of oxide film on oxygen reduction current for the platinum-cobalt alloy electrodes in PEFC

Effect of surface oxide on Pt-Co alloy electrodes on the oxygen reduction reaction (ORR) was investigated in 0.5 M sulfuric acid solution by electrochemistry, ellipsometry, laser Raman scattering spectroscopy, and XPS. The oxide as thick as 1-2 nm increases the overpotential of ORR and falls down efficiency of PEFC. The thickness of the oxide films is precisely determined by ellipsometry. The oxide film 1.9 nm thick was formed on Pt-50 mol% Co electrode by constant potential oxidation at 1.20 V and the film 1.5 nm thick remains on the electrode at 0.6 V at which ORR already starts. The remaining oxide decreases the current density of ORR and increases the overpotential. On pure Pt electrode, the similar influence of the oxide film was observed.     

Development of systems reliability analysis code SECOM-2 for seismic PSA

An integrated code system SECOM-2, developed at the Japan Atomic Energy Research Institute (JAERI), has the following functions for systems reliability analysis in seismic probabilistic safety assessments (PSAs): (1) calculation of component failure probability, (2) extraction of minimal cut sets (MCSs) from a given fault tree (FT), (3) calculation of frequencies of accident sequences and core damage, (4) importance analysis with several measures with consideration of unique parameters of seismic PSAs, (5) sensitivity analysis, and (6) uncertainty analysis. This paper summarizes the special features of SECOM-2 to perform the analyses mentioned above. At JAERI, using an integrated FT which represents seismically induced core damage due to all initiating events as a system model to calculate core damage frequency of a nuclear power plant, SECOM-2 can calculate conditional point estimate probabilities of system failures, losses of safety functions, and core damage as a function of earthquake motions. The point estimate is computed by a method which gives an exact numerical solution using the Boolean arithmetic model method. As for consideration of correlation of component failure, which has been an important issue in seismic PSAs, a new technique based on direct FT quantification by a Monte Carlo simulation is being added to SECOM-2. Adding this technique, the core damage frequency can be calculated not only with the upper bound approximation based on MCSs but also with a near exact solution taking into account the correlation among all components. This paper also presents the preliminary results of a seismic PSA of a generic BWR plant in Japan performed at JAERI to demonstrate the functions of the SECOM-2 code.     

A case of interstitial pneumonia induced by an ACE inhibitor (temocapril hydrochloride)]

A 51-year-old woman who had been treated for years for rheumatoid arthritis presented with a persistent dry cough and shortness of breath three weeks after administration of the ACE inhibitor temocapril hydrochloride against essential hypertension. Chest radiography and computed tomography showed diffuse reticular shadows and ground-grass opacities in both lung fields. Bronchoalveolar lavage fluid analysis showed an increase of lymphocytes and CD8+ T cells (93.3% of lymphocytes), and a decrease of the CD4/8 ratio of the T cell subset (0.04). Histopathological analysis of trans-bronchial lung biopsy specimens showed infiltration of lymphocytes into the alveolar septa and exudation of alveolar macrophages, signs characteristic of interstitial pneumonia. A drug lymphocyte stimulation test was positive for temocapril, but negative for other drugs. On the basis of these findings, we diagnosed temocapril hydrochloride-induced interstitial pneumonia.     

The separation of fission-product rare elements toward bridging the nuclear and soft energy systems

Based on the present state of the art of the separation technology, recycling of fission-product rare elements (FRE) in the FBR spent fuel is discussed. The rad.-waste fractionation is in accordance with the present society's trend toward zero-emission, and the mean of salt-free method utilizing electrochemistry agrees with the principles of the newly established green chemistry. A catalytic electrolytic extraction method is proposed to separate the target, radioactive but potentially strategic elements, Pd, Ru, Rh, Re (Tc), Te and Se dissolved in the HLLW. It avoids secondary waste arising. This method is particularly feasible for the separation of Pd where cyclic reaction of metal cations such as Pd(II) or Fe(II), acting as promoters or mediators and already contained in HLLW, accelerates the electrochemical deposition of Ru, Rh and Re. Elemental separation not only offers alternative material resources to meet expanding demands for catalysts in Fuel Cell/Soft Energy system but is also the first step for transmutation or other selective strategies for waste management of long-lived fission products (LLFP).     

Electron microscopic visualization of collagen aggregates without chemical staining.

Lateral, uni-directional aggregates of collagen, segment-long-spacing crystallites (SLS), were made by dialyzing collagen solutions against acetic acid containing ATP, and were examined by transmission electron microscopes without electron staining. There detected were at least 20 dark (electron dense) cross-striations within SLS. The banding pattern was compared with the biochemical and biophysical properties of the amino acid side chains along the collagen molecule. The banding pattern of unstained SLS was mostly correlated with the intramolecular distribution of basic amino acid residues. Since basic amino acids have relatively large side chains, the distribution of mass (molecular weight of amino acids) along the molecule (local density profile) partially explained the cross-striation. Addition of fractions of molecular weight of ATP to basic residues made the local density profile much better correlate to the banding pattern. We conclude that the electron microscopic banding pattern of unstained SLS was generated by the local amount of material or local density profile along the collagen aggregates, which was enhanced by ATP bound to positively charged basic residues. The concept that the electron density correlates with the amount of material is fundamental in electron microscopy, and it has been proven with biological materials in this paper.     

Observing the Stimulated Raman Gain Spectra of Solutions Using an Infrared Pump Pulse with Narrow Linewidth and a Low-Noise CW Probe Laser

Stimulated Raman gain (SRG) spectroscopy using infrared pump pulses with narrow linewidth and a low-noise cw probe infrared laser was proposed. High-resolution Raman spectra of solutions were obtained. The SRG spectra of crystal GaP, benzene, and toluene were measured to confirm the spectral resolution and sensitivity over the terahertz (THz) region. We discuss the polarization dependence of the spectral measurement of carbon tetrachloride. Our system can detect organic molecules in aqueous solutions.     

Correlation between the hot plate ignition test and other laboratory-scale flammability tests on rubber conveyor belts with fabric skeletons

The hot plate ignition test was conducted on ten different conveyor rubber belts with fabric skeletons. In this test, a 25 × 25 mm² belt sample was placed on a stainless steel plate in an electric furnace and heated. The ‘ignition temperature’ was determined on each sample in almost the same way as proposed in Canada. The test results were compared with those from other laboratory-scale flammability tests (i.e. the small-scale flame tests, the Oxygen Index test and the laboratory-scale gallery test). The calculated results of both sample and rank correlation coefficients imply that the ‘10 signition temperature’ in this hot plate ignition test has a correlation with the results from both the Oxygen Index test and the laboratory-scale gallery test, but that it has very little or no correlation with those from the small-scale flame tests. On the other hand, it is found that the ‘60 s ignition temperature’ in this test has a far better correlation both with the results from the small-scale flame tests and with the time to ignition in the laboratory-scale gallery test than the ‘10 s ignition temperature’.