Structural Distortion and Compositional Gradients Adjacent to Epitaxial LiMn2O4 Thin Film Interfaces

Thin film electrode materials are key components in the development of high rate, high capacity solid‐state Li‐ion batteries. Detailed knowledge of the epitaxial film/substrate(current‐collector) interface structures, which provides insights into epitaxial growth mechanisms and the effects of microstructure on electrochemical properties, is essential for efficient materials and device design. Here we report the epitaxial growth mechanism of a typical cathodic LiMn₂O₄ thin film by exploring the detailed structural and compositional variations in the vicinity of a film/substrate interface using state‐of‐the‐art scanning transmission electron microscopy. Direct observation of atom columns shows the epitaxial film forms an atomically flat and coherent heterointerface with the substrate, but that the crystal lattice is tetragonally distorted with a measurable compositional gradient from the interface to the crystal bulk. The growth mechanism is interpreted in terms of a combination of chemical and physicomechanical effects, namely a complex interplay between the internal Jahn‐Teller distortions induced by oxygen non‐stoichiometry and the lattice misfit strain.     

Novel synthesis of branched polystyrenes by quasi‐living radical copolymerization using photofunctional inimer

Branched polystyrenes were prepared by quasi‐living radical copolymerization of N,N‐diethylaminodithiocarbamoylmethylstyrene (inimer: DTCS) with styrene under UV irradiation. DTCS monomers play an important role in this copolymerization system as an inimer capable of initiating living radical polymerization of the vinyl group. Two monomers (DTCS and styrene) showed equal reactivity toward both propagating species, and the copolymer composition was the same as the comonomer feed. This result means that both the branching and chain length of the hyperbranched molecules can be controlled statistically by the feed monomer ratios. The compact nature of the branched macromolecules is demonstrated by viscosity measurements compared to the linear analogues. © 2001 Society of Chemical Industry     

Persistence and partitioning of eight selected pharmaceuticals in the aquatic environment: Laboratory photolysis, biodegradation, and sorption experiments

We selected eight pharmaceuticals with relatively high potential ecological risk and high consumption—namely, acetaminophen, atenolol, carbamazepine, ibuprofen, ifenprodil, indomethacin, mefenamic acid, and propranolol—and conducted laboratory experiments to examine the persistence and partitioning of these compounds in the aquatic environment. In the results of batch sunlight photolysis experiments, three out of eight pharmaceuticals—propranolol, indomethacin, and ifenprodil—were relatively easily photodegraded (i.e., half-life < 24 h), whereas the other five pharmaceuticals were relatively stable against sunlight. The results of batch biodegradation experiments using river water suggested relatively slow biodegradation (i.e., half-life > 24 h) for all eight pharmaceuticals, but the rate constant was dependent on sampling site and time. Batch sorption experiments were also conducted to determine the sorption coefficients to river sediments and a model soil sample. The determined coefficients (K_d values) were much higher for three amines (atenolol, ifenprodil, and propranolol) than for neutral compounds or carboxylic acids; the K_d values of the amines were comparable to those of a four-ring polycyclic aromatic hydrocarbon (PAH) pyrene. The coefficients were also higher for sediment/soil with higher organic content, and the organic carbon-based sorption coefficient (log K_oc) showed a poor linear correlation with the octanol-water distribution coefficient (log D_ow) at neutral pH. These results suggest other sorption mechanisms—such as electrochemical affinity, in addition to hydrophobic interaction—play an important role in sorption to sediment/soil at neutral pH.     

Effect of the preparation condition on the properties of titania-silica derived from tetraisopropyl titanate(IV) and tetraethyl orthosilicate

Titania-silica mixed oxide was prepared by hydrolyzing tetraethyl orthosilicate and tetraisopropyl titanate(IV) with a mixture of ethanol and 0.01 N aqueous acetic acid. Surface Ti content, BET surface area, and the number of acid sites increased with an increase in 0.01 N aqueous acetic acid. Thus hydrolysis of both alkoxides occurred simultaneously with a large amount of the acetic acid solution, and there was extensive interaction between TiO₂ and SiO₂ phases. With small amount of 0.01 N aqueous acetic acid, however, titanium hydroxide was first formed and, then, it was covered with the silica phase produced in a later stage of the hydrolysis. Increase in the acetic acid solution also led to the formation of a large amount of tetrahedral Ti species, which were active for the epoxidation of oct-1-ene usingt-butyl hydroperoxide as an oxidant.     

Drift velocity of electron swarm in configuration space

In 1977, Tagashira and colleagues reported that the center‐of‐mass drift velocity W_r of an electron swarm defined in time of flight (TOF) takes a larger value than the drift velocity W_v defined in pulsed Townsend (PT) when ionization collisions take place. At the same time, they explained that the larger values of W_r are caused by the ionization generation of electrons at the front side of extending swarm due to higher mean energy. In this paper, a new definition of virtual drift velocity in configuration space W′_r defined in PT is proposed, and calculated data of drift velocities and related quantities such as ionization coefficients and ionization frequencies in Ar in a high E/N range are discussed relative to Tagashira's data. © 2006 Wiley Periodicals, Inc. Electr Eng Jpn, 155(2): 1–7, 2006; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/eej.20131     

Cooperative behavior of various agents in dynamic environment

The multi-agent model is a model in which agents with limited ability cooperate each other to accomplish a goal. In this paper, we introduce a multi-agent model in which agents are created to imitate real ants. There are two different type of agents, each type of which has a particular task. We designed agents to communicate each other by using pheromone considering noise. On this model, we observed cooperative behavior of agents and evaluated conditions to make an order of behavior in the model.     

Extremely enhanced hydrolytic stability of poly(ethylene terephthalate) films

Poly(ethylene terephthalate) (PET) films possessing extremely enhanced hydrolytic stability were developed by combining the improved processes of polymerization, melt extrusion, and biaxial stretching. The PET films obtained from the combined process were better than commercially available PET films with highest hydrolytic stability at present. An accelerated test (at 120°C and 100% relative humidity) was performed to learn the key parameters governing elongation‐based hydrolytic durability of PET films. The results suggested that ultimate hydrolytic stability was because of the combined effects of significant decrease in the content of carboxylic acid terminal groups and enhanced crystallinity. Another reason for this was an increase in ground‐state dimer sites due to intermolecular stacking between terephthalate units. These dimer sites were probably located in the densely packed amorphous regions, as suggested from the intrinsic fluorescence spectrum of PET films. The PET films developed in this study are very useful in outdoor applications such as backsheet materials in solar cell modules. POLYM. ENG. SCI., 58:261–271, 2018. © 2017 Society of Plastics Engineers     

Redox properties of CeO2 and Pt-Rh/CeO2 studied by TAP method

Redox properties of CeO₂ and Pt-Rh/CeO₂ were studied by temporal analysis of products (TAP) method using alternative pulses of CO and O₂. A portion of pulsed CO was oxidized to CO₂ and a portion of CO was adsorbed on the surface. Pulsing ¹⁸O₂ onto the catalyst which has surface species derived from CO, evolved CO₂ contained no ¹⁸O suggesting that the surface species will be carbonate ions.     

Structural and electronic properties of extremely long perylene bisimide nanofibers formed through a stoichiometrically mismatched, hydrogen-bonded complexation

Extremely long nanofibers, whose lengths reach the millimeter regime, are generated via co-aggregation of a melamine-appended perylene bisimide semiconductor and a substituted cyanurate, both of which are ditopic triple-hydrogen-bonding building blocks; they co-aggregate in an unexpected stoichiometrically mismatched 1:2 ratio. Various microscopic and X-ray diffraction studies suggest that hydrogen-bonded polymeric chains are formed along the long axis of the nanofibers by the 1:2 complexation of the two components, which further stack along the short axis of the nanofibers. The photocarrier generation mechanism in the nanofibers is investigated by time-of-flight (TOF) experiments under electric and magnetic fields, revealing the birth and efficient recombination of singlet geminate electron-hole pairs. Flash-photolysis time-resolved microwave conductivity (FP-TRMC) measurements revealed intrinsic 1D electron mobilities up to 0.6 cm(2) V(-1) s(-1) within nanofibers.