Sulfur exchange on Co---Mo/Al2O3 hydrodesulfurization catalyst using S radioisotope tracer

A commercial Co---Mo/Al₂O₃ catalyst was labeled with the radioisotope ³⁵S in hydrodesulfurization (HDS) of ³⁵S-labeled dibenzothiophene (³⁵S-DBT) in a high-pressure flow reactor at 50 kg/cm². Then, HDS of 4-methyldibenzothiophene (4-MDBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) or sulfur exchange of H₂S were carried out on the labeled catalyst at 50 kg/cm² and 260–360°C. The amounts of labile sulfur participating in the reaction were determined from the radioactivity of ³⁵S---H₂S released from the ³⁵S-labeled catalyst. In the HDS reactions, the amount of labile sulfur participating in the reaction decreased in the order: DBT> 4-MDBT> 4,6-DMDBT. In the sulfur exchange reaction with H₂S, the adsorption of H₂S on the catalyst reached saturation above a H₂S partial pressure of 0.36 kg/cm². It was suggested that the release of H₂S from the labile sulfur may be the rate determining step of the HDS reaction.     

High tensile strength fiber of poly[(R)‐3‐hydroxybutyrate‐co‐(R)‐3‐hydroxyhexanoate] processed by two‐step drawing with intermediate annealing

High tensile strength fibers of poly[(R)‐3‐hydroxybutyrate‐co‐(R)‐3‐hydroxyhexanoate] [P(3HB‐co‐3HH)], a type of microbial polyesters, were processed by one‐step and two‐step cold‐drawn method with intermediate annealing. Thermal degradation behaviors were characterized by differential scanning calorimeter and gel permeation chromatography measurements. Thermal analyses were revealed that molecular weights decreased drastically within melting time at a few minute. One‐step cold‐drawn fiber with drawing ratio of 10 showed tensile strength of 281 MPa, while tensile strength of as‐spun fiber was 78 MPa. When two‐step drawing was applied for P(3HB‐co‐3HH) fibers, the tensile strength was led to 420 MPa. Furthermore, the optimization of intermediate annealing condition leads to enhance the tensile strength at 552 MPa of P(3HB‐co‐3HH) fiber. Wide‐angel X‐ray diffraction measurements of these fibers suggest that the fibers with high tensile strength include much amount of the planer‐zigzag conformation (β‐form) as molecular conformation together with 2₁ helix conformation (α‐form). © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41258.     

Effect of Annealing Ambient on the Self-Formation Mechanism of Diffusion Barrier Layers Used in Cu(Ti) Interconnects

Copper (titanium) [Cu(Ti)] films with low titanium (Ti) concentration were found to form thin Ti-rich barrier layers at the film/substrate interfaces after annealing, which is referred to as self-formation of the barrier layers. This Cu(Ti) alloy was one of the best candidates for interconnect materials used in next-generation ultra-large-scale integrated (ULSI) devices that require both very thin barrier layers and low-resistance interconnects. In the present paper, in order to investigate the influences of annealing ambient on resistivity and microstructure of the Cu alloys, the Cu(7.3at.%Ti) films were prepared on the SiO₂ substrates and annealed at 500°C in ultra-high vacuum (UHV) or argon (Ar) with a small amount of impurity oxygen. After annealing the film at 500°C in UHV, the resistivity was not reduced below 16 μΩ-cm. Intermetallic compounds of Cu₄Ti were observed to form in the films and believed to cause the high resistivity. However, after subsequently annealing in Ar, these compounds were found to decompose to form surface TiO _x and interfacial barrier layers, and the resistivity was reduced to 3.0 μΩ-cm. The present experiment suggested that oxygen reactive to titanium during annealing played an important role for both self-formation of the interfacial barrier layers and reduction of the interconnect resistivity.     

Coal liquefaction mechanism using a tritium tracer method

To determine the behavior of hydrogen in tetralin, the reaction of tetralin with tritiated gaseous hydrogen was studied in a flow reactor at 400–450°C, 2.5–9.8 MPa for various residence times. The amount of hydrogen exchange between tetralin and tritiated hydrogen was estimated from the balance of hydrogen and tritium. Although yields of methylindan and naphthalene, and the hydrogen-exchange ratio (HER) of tetralin increased monotonously with residence time, these values were scarcely influenced by the reaction pressure at every temperature. It was thought that the formation of tetralyl radicals in this system would be the rate-determining step for both the conversions of tetralin into methylindan and naphthalene, and the hydrogen exchange of tetralin. Conversions of tetralin into methylindan and naphthalene, and the hydrogen-exchange reaction using the autoclave were very close to those using the flow reactor.     

Point Estimation of Reliability of a System Comprised of k Elements from the Same Gamma Model

Unbiased minimum variance estimates of reliability are obtained for series, parallel, and standby redundant systems when the components are from a single Gamma distribution with known shape parameter and unknown scale parameter. The results obtained here generalize some of the results of Rutemiller [9] for the exponential model.     

FireNet-MLstm for classifying liver lesions by using deep features in CT images

Multimedia Tools and Applications - Nowadays working in the medical imaging domain remains a big challenge, since the collecting such datasets is so complex, deep learning techniques have...     

Organic Long-Persistent Luminescence from a Thermally Activated Delayed Fluorescence Compound

Organic long-persistent luminescence (OLPL) is one of the most promising methods for long-lived-emission applications. However, present room-temperature OLPL emitters are mainly based on a bimolecular exciplex system which usually needs an expensive small molecule such as 2,8-bis(diphenyl-phosphoryl)dibenzo[b,d]thiophene (PPT) as the acceptor. In this study, a new thermally activated delayed fluorescence (TADF) compound, 3-(4-(9H-carbazol-9-yl)phenyl)acenaphtho[1,2-b]pyrazine-8,9-dicarbonitrile (CzPhAP), is designed, which also shows OLPL in many well-known hosts such as PPT, 2,2′,2″-(1,3,5-benzinetriyl)-tris(1-phenyl-1-H-benzimidazole) (TPBi), and poly(methyl methacrylate) (PMMA), without any exciplex formation, and its OLPL duration reaches more than 1 h at room temperature. Combining the low cost of PMMA manufacture and flexible designs of TADF molecules, pure organic, large-scale, color tunable, and low-cost room-temperature OLPL applications become possible. Moreover, it is found that the onset of the 77 K afterglow spectra from a TADF-emitter-doped film is not necessarily reliable for determining the lowest triplet state energy level. This is because in some TADF-emitter-doped films, optical excitation can generate charges (electron and holes) that can later recombine to form singlet excitons during the phosphorescence spectrum measurement. The spectrum taken in the phosphorescence time window at low temperature may consequently consist of both singlet and triplet emission.     

A study on the preparation of supported metal oxide catalysts using JRC-reference catalysts. I. Preparation of a molybdena–alumina catalyst. Part 4. Preparation parameters and impact index

The effects of the volume and pH of the impregnation solution and of the calcination conditions were examined on the physicochemical and catalytic properties of a 13 wt% MoO₃/Al₂O₃ extrudate catalyst. The Al₂O₃ support and drying procedures (static conditions without flowing air) were fixed in the preparations. In the present series of catalysts, the amount of crystalline MoO₃ was marginally small. It was found that the dispersion of Mo oxide species increased as the volume of the impregnation solution increased, gradually approaching a maximum value. The increase in pH (2–8) of the impregnation solution was found to reduce the dispersion of Mo oxide species. The Mo dispersion increased slightly for the impregnation catalysts as the calcination temperature increased (673–873 K), whereas it decreased for the equilibrium adsorption catalysts. The effects of the calcination atmosphere (with or without flowing air, or with flowing humid air) were very small on the dispersion of Mo oxide species under the present preparation conditions. On the other hand, the methanol oxidation activity of MoO₃/Al₂O₃ was sensitive to the preparation parameters examined here. It was demonstrated by means of EPMA and XPS that a considerable migration of Mo took place during the calcination.

In the present study on the preparation of a 13 wt% MoO₃/Al₂O₃ catalyst, an impact index is proposed to measure the magnitude of the effects of the respective parameter(s) on the physicochemical and catalytic properties. With the Mo dispersion, the effects of the preparation parameter decreased in the order, surface area of the support >> drying process > volume of the impregnation solution > pH, calcination temperature and atmosphere. The size of the impact index for the dispersion of Mo sulfide species is 70–75% of that for the Mo oxide species. The HDS activity of the catalyst was less affected by the preparation parameters than the Mo sulfide dispersion. The preparation parameters affected the segregation of Mo on the outer surface of extrudates in a decreasing order: drying process > volume of the impregnation solution > pH, calcination conditions. It was found that the oxidation of methanol was affected most intensely by the drying procedures. The volume of the impregnation solution, calcination conditions and pH of the impregnation solution also strongly affected the oxidation activity. The impact index suggests that the sensitivity to the preparation variables of the physicochemical and catalytic properties of MoO₃/Al₂O₃ decreases in the order, methanol oxidation activity > surface Mo segregation > Mo oxide dispersion > Mo sulfide dispersion > HDS activity.     

Repeated pneumonia in the middle lobe caused by congenital bronchoesophageal fistula

A 52-year-old woman was admitted to our hospital because of repeated episodes of pneumonia in the middle lobe. She had also experienced coughing during meals. The history and chest CT findings suggested the presence of a bronchoesophageal fistula. An upper GI series revealed a fistula between an esophageal diverticulum and the superior segment bronchus of the right lower lobe. Fiberoptic bronchoscopy done immediately after the upper GI series revealed barium sulfate leaking from the superior segment bronchus of the right lower lobe into the middle lobe bronchus. These findings indicated that the repeated pneumonia in the middle lobe was caused by a congenital bronchoesophageal fistula. Examination of the resected fistula showed that it was a Braimbridge type I bronchoesophageal fistula. Although of at least 49 cases of congenital bronchoesophageal fistulas with esophageal diverticula have been reported in the Japanese medical literature, we know of no previous case in which such a fistula was associated with middle-lobe pneumonia.