Energy-level alignment at model interfaces of organic electroluminescent devices studied by UV photoemission: trend in the deviation from the traditional way of estimating the interfacial electronic structures

The electronic structures of model interfaces of organic electroluminescent (EL) devices were investigated with UV photoemission spectroscopy (UPS). Interfaces of TTN (tetrathianaphthacene) and TCNQ (tetracyanoquinodimethane) were also studied as extreme cases for hole transport and electron transport material, respectively. For all organic/metal interfaces studied, the work function of metal electrode was changed by deposition of organic layer, i.e., the vacuum level was shifted at the interface, indicating the invalidity of the traditional energy level alignment model where a common vacuum level was assumed at organic/metal interface. At TCNQ/Au, DP-NTCI/Al, which are acceptor/metal interfaces, upward shift of the vacuum level of organic layer relative to that of metal was observed, suggesting the formation of interfacial dipole due to electron-transfer from metal to acceptor. At other organic/metal interfaces, TPD(N, N'-diphenyl-N, N'-(3-methylphenyl)-1, 1'-biphenyl-4, 4'-diamine)/Au or ITO (indium tin oxide), ALq/sub 3/ (tris(8-hydroxyquinolino) aluminum)/Al, DP-NTCl(N, N'-diphenyl-1,4,5,8- naphthyltetracarboxylimide)/Al or Au, downward shift of the vacuum level was observed. Such downward shift has been also observed in our previous study for porphyrin/metal interfaces, and seems to be a trend for organic/metal interfaces at which no electron-transfer from metal to organic layer occurs. This trend suggests that the traditional model tends to underestimate (overestimate) the barrier height for hole (electron) injection. On the other hand, the vacuum level shift at ALq/sub 3//TPD interface was less than 0.1 eV, leading to an apparent applicability of the traditional model. However, it is not always the case for organic/organic interfaces: finite shift of 0.2 eV was observed at TTN/TCNQ interface due to electron-transfer from TTN to TCNQ. Possible origins of vacuum level shift at organic/metal interfaces were also discussed.     

Experimental characterization of high-speed impact damage behavior in a three-dimensionally woven SiC/SiC composite

This paper discusses high-speed impact damage in a three-dimensionally woven SiC/SiC composite (3D-CMC). The impact damage was introduced by a steel ball projectile in 3D-CMC plates with and without thermal exposure. The surface and internal damages were observed by optical microscopy and X-ray CT. A crater was observed on the collision surface. The X-ray CT measurement revealed that multiple pyramid-shaped cone cracks were generated beneath the crater when the impact speed was relatively low. At an impact speed exceeding the critical speed, a spall fragment was ejected from the back surface, while no internal damage was observed in the fragment. The spall fracture mode differed between the virgin and the thermally-exposed specimens. This difference is the result of embrittlement of the fiber/matrix interface due to oxidation of the carbon coating layer in the thermally-exposed specimen. In addition, it is found that z-yarns improve impact resistance by constraining delamination.     

Adsorption of cationic monomeric and gemini surfactants on montmorillonite and adsolubilization of vitamin E

Adsorption of a cationic gemini surfactant (1,2-bis(dodecyldimethylammonio) ethane dibromide, 12-2-12) and the corresponding monomeric surfactant (dodecyltrimethylammonium bromide, DTAB) on montmorillonite has been characterized with a combination of adsorption isotherm, interlayer spacing and FT-IR spectroscopic data. Adsolubilization of vitamin E into the adsorbed surfactant layers has also been studied. The adsorption isotherm data reveal that the adsorption of the two surfactants is driven by the two factors: one is the cation exchange that occurs on the interlayer basal planes and the other is the hydrophobic interaction between hydrocarbon chains of the surfactants. Although the adsorbed amount measured in the saturation region (in mol g(-1)) is almost identical for the two surfactants, the conformation of the intercalated surfactant molecules differs significantly from each other. The adsorption of DTAB results in a lateral bilayer arrangement in the limited interlayer space, whereas 12-2-12 gives a normal bilayer arrangement in the expanded interlayer space. Adsolubilization of vitamin E takes place into the adsorbed surfactant layers, and interestingly, all the vitamin E molecules added in the montmorillonite suspensions are hybridized at lower surfactant concentrations due to the great specific surface area of the clay material. Since the maximum adsolubilization amount is usually obtained just below the critical micelle concentration, the gemini surfactant is deemed to be more efficient than the corresponding monomeric one to achieve the great adsolubilization amount.     

Effect of temperature and heating rate on the sintering of leucite-based dental porcelains

The aim of this work was to determine the effect of temperature and heating rate on the densification of four leucite-based dental porcelains: two low-fusion (Dentsply-Ceramco and Ivoclar) and two high-fusion commercial porcelains (Dentsply-Ceramco). Porcelain powders were characterized by differential thermal analysis (DTA), X-ray diffraction (XRD), particle size distribution, helium picnometry, and by scanning electron microscopy. Test specimens were sintered from 600 to 1050 °C, with heating rates of 55 °C/min and 10 °C/min. The bulk density of the specimens was measured by the Archimedes method in water, and microstructures of fracture surfaces were analyzed by scanning electron microscopy (SEM). The results showed that densification of specimens increased with the increase in temperature. The increase in the heating rate had no effect on the densification of the porcelains studied. Both high-fusion materials and one of the low-fusing porcelains reached the maximum densification at a temperature that was 50 °C lower than that recommended by the manufactures.     

Colorimetric chemosensor for ATP based on phthalimide-appended poly(2,5-dimethoxyaniline)

We have designed a colorimetric conjugated polymer (PDMAp) for selective ATP sensing based on poly(2,5-dimethoxyaniline) bearing phthalimide which can form hydrogen bonds with adenine. PDMAp have been synthesized via chemical oxidative polymerization with CSA and DDQ and dedoping with an aqueous ammonia solution. PDMAp was displayed to signal the colorimetric selective detection for ATP over various nucleotides such as ADP, AMP, CTP, TTP, and GTP in DMSO–water (9:1, v/v) mixture. The absorption spectral change can be attributed to a doping process of ATP to PDMAp through hydrogen bonds between phthalimide and adenine as well as electrostatic interactions between the phosphate group of ATP and the backbone of PDMAp.     

Separation of aromatic components from light cycle oil by solvent extraction

To improve the versatility of light cycle oil (LCO), separation of aromatic compounds from LCO by solvent extraction was investigated. LCO was analyzed to identify 35 components: 19 aromatics and 16 alkanes. The batch liquid–liquid equilibrium extraction of LCO was performed using furfural, sulfolane, and methanol as extraction solvents. In each solvent, the aromatics present in LCO were selectively extracted relative to the alkanes. The separation selectivities of aromatics relative to alkanes were larger in sulfolane than in the other solvents. Among the aromatic components, di- and tricyclic compounds were selectively extracted relative to the monocyclic ones.     

Structural Changes of Scandia-Doped Zirconia Solid Solutions: Rietveld Analysis and Raman Scattering

Powder X-ray diffractometry (XRD) and Raman scattering measurements were used to study the structural changes of compositionally homogeneous metastable ZrO₂ solid solutions induced by ScO_1.5 doping. The crystal structures of monoclinic, tetragonal, cubic, and rhombohedral (Sc₂Zr₇O₁₇, ß-phase) solid-solution phases have been refined by using the Rietveld analysis of the XRD data at room temperature of arc-melted ZrO₂- X ScO_1.5 ( X = 0, 2, …, 20, and 22 mol%) samples. The results can be interpreted as indicating that the structures of the monoclinic and tetragonal phases approach those of the tetragonal and cubic phases, respectively, by ScO_1.5 doping. Raman scattering, as well as XRD, was useful to investigate the phase assemblage. Moreover, we could obtain Raman spectra of the ß-phase probably for the first time.     

Structural motif of phosphate-binding site common to various protein superfamilies: all-against-all structural comparison of proteinmononucleotide complexes

In order to search for a common structural motif in the phosphate-bindingsites of protein–mononucleotide complexes, we investigatedthe structural variety of phosphate-binding schemes by an all-against-allcomparison of 491 binding sites found in the Protein Data Bank.We found four frequently occurring structural motifs composedof protein atoms interacting with phosphate groups, each ofwhich appears in different protein superfamilies with differentfolds. The most frequently occurring motif, which we call thestructural P-loop, is shared by 13 superfamilies and is characterizedby a four-residue fragment, GXXX, interacting with a phosphategroup through the backbone atoms. Various sequence motifs, includingWalker's A motif or the P-loop, turn out to be a structuralP-loop found in a few specific superfamilies. The other threemotifs are found in pairs of superfamilies: protein kinase andglutathione synthetase ATPase domain like, actin-like ATPasedomain and nucleotidyltransferase, and FMN-linked oxidoreductaseand PRTase.     

Wide Color Variation in SiNO Thin Films Dispersed with Precipitated TiN Nano Particles

Amorphous thin films of Ti_1?ySi_y(N,O) with y ≥ 0.38 were prepared by reactive sputter deposition in a nitrogen atmosphere. Thermal annealing of the films in an ammonia flow above 800°C yielded Si(N,O) amorphous thin films dispersed with precipitated TiN nanosized particles. The film color changed with Si content y and the annealing conditions, from carrot orange to cream yellow in the as‐deposited films due to their oxynitride nature, and from dark green to canary yellow and from iron blue to horizon blue at respective annealing temperatures of 800°C and 900°C due to metallic nature of the TiN nanosized particles precipitated in the annealing.