Polybenzoxazine alloys and blends: Some unique properties and applications

Polybenzoxazine (PBZ), a novel class of high performance thermosetting phenolic resin, has been developed in order to overcome many shortcomings of conventional phenolic materials from either novolac or resole type resins. The paper first provides the overview of this high temperature material including main types, chemical structure of each type, and properties of the polymer, especially the synergistic behavior in thermal properties. It then describes the manufacturing technique to produce the monomeric resin as well as some applications of the polymer.     

Plasma-tolerant structure for organic light-emitting diodes with aluminum cathodes fabricated by DC magnetron sputtering: Using a Li-doped electron transport layer

We fabricate aluminum cathodes that are almost free from plasma damage by DC magnetron sputtering for organic light-emitting diodes (OLEDs). While sputtering is widely known to have numerous advantages over conventional evaporation for mass production of devices, it can cause serious damage to organic layers. In this report, we fabricate devices that are free from plasma damage by introducing a 1%-Li-doped electron transport layer (ETL). The difference of external electroluminescence quantum efficiency between OLEDs with the structure ITO/α-NPD/ETL/Al (where ITO is indium tin oxide and α-NPD is N,N′-di(1-naphthyl)-N,N′-diphenylbenzidine) with Al cathodes deposited by conventional evaporation or sputtering is 0.1%, and their driving voltage is identical. We find that the Li-doped ETL should be thicker than 40 nm. Analysis of the depth profile of the ETL by time-of-flight secondary ion mass spectrometry indicates that considerable damage from sputtering extended to a depth of approximately 30 nm, suggesting that high-energy particles penetrated about 30 nm into the ETL.     

Steam gasification of coal cokes in an internally circulating fluidized bed of thermal storage material for solar thermochemical processes

A laboratory-scale prototype windowed internally circulating fluidized-bed reactor made of quartz sand and coal coke particles was investigated for steam gasification using concentrated Xe-light radiation as the energy source. The quartz sand was used as a chemically inert bed material for the fluidized bed, while the coal coke particles functioned as the reacting particles for the endothermic gasification reaction. The advantages of using quartz sand as the bed material for the directly irradiated gasification reactor are as follows: (1) The bed height is maintained at a constant level during the gasification. (2) The quartz sand functions as a thermal transfer/storage medium inside the reactor. The gasification performances such as the production rates of CO, H₂, and CO₂; carbon conversion; and light-to-chemical energy conversion were evaluated for the fluidized-bed reactor with a thermal transfer/storage medium (quartz sand). The effects of using the bed material (quartz sand) on the gasification performance are described in this paper.     

Preparation and Properties of Ethylene Vinyl Acetate (EVA)/Organoclay/Compatibilizer Nanocomposites: Effects of Organoclay Loading and Methyl Ethyl Ketone

Ethylene vinyl acetate (EVA)/organoclay/compatibilizer nanocomposites were produced using a melt compounding technique in an internal mixer, Haake Rheometer, at 120°C and 50 rpm rotor speed. Effects of organoclay loading (from 2 to 10 phr—parts per hundred of resin and methyl ethyl ketone (MEK), used as a compatibilizer, on the processing properties, tensile properties, morphology, thermal degradation, and water absorption behavior of EVA/organoclay nanocomposites were studied. Results indicate that the presence of organoclay increase the processing torque, tensile properties, thermal degradation, and resistance to water absorption. The optimum organoclay loading was achieved at 2 phr. This was caused by the dispersion state of individual silicate layers (intercalation/exfoliation) in EVA matrix. The intercalation/exfoliation structure affects the properties of EVA/organoclay nanocomposites as evidenced from the morphology studies such as x-ray diffraction (XRD) and transmission electron microscopy (TEM) evaluation. The addition of MEK has the ability to improve the tensile properties, thermal degradation, and slightly reduces the resistance of water permeation of EVA/organoclay nanocomposites. The enhanced properties were seen as a result of the better matrix and filler interaction. The EVA/organoclay/MEK nanocomposites shows better intercalation/exfoliation of individual silicate layers in the EVA matrix as indicated by TEM. Moreover, the XRD evaluation shows that intercalation/exfoliation of the organoclay was formed in the EVA matrix.     

Off/on Switching of Electric Current as a Strategy for One-Pot Synthesis of Bromoarylpyridines by Cross-Coupling/ C−H Bromination

An “OFF/ON” electric current switching protocol was developed as a new strategy for one-pot organic synthesis. Suzuki-Miyaura coupling of 2-bromopyridines with arylboronic acids in an electrochemical cell was performed without applying an electric current, and subsequently, the Pd-catalyzed electrochemical C−H bromination was conducted using the already-present Pd catalyst to obtain 2-(2-bromoaryl)pyridines as products. The one-pot synthesis of bromoarenes can also be achieved without adding an external Br source in the second step. Furthermore, an OFF/ON/OFF two-times switching protocol also realized the formation of an N-containing teraryl derivative.     

A rechargeable lithium metal battery operating at intermediate temperatures using molten alkali bis(trifluoromethylsulfonyl)amide mixture as an electrolyte

The physicochemical properties of molten alkali bis(trifluoromethylsulfonyl)amide, MTFSI (M = Li, K, Cs), mixture (x_LiTFSI = 0.20, x_KTFSI = 0.10, x_CsTFSI = 0.70) were studied to develop a new rechargeable lithium battery operating at intermediate temperature (100–180 °C). The viscosity and ionic conductivity of this melt at 150 °C are 87.2 cP and 14.2 mS cm⁻¹, respectively. The cyclic voltammetry revealed that the electrochemical window at 150 °C is as wide as 5.0 V, and that the electrochemical deposition/dissolution of lithium metal occurs at the cathode limit. A Li/MTFSI (M = Li, K, Cs)/LiFePO₄ cell showed an excellent cycle performance at a constant current rate of C/10 at 150 °C; 95% of the initial discharge capacity was maintained after 50 cycles. Except for the initial few cycles, the coulombic efficiencies were approximately 100% for all the cycles, indicating the stabilities of the molten MTFSI mixture and all the electrode materials.     

Annealing effects on Zn1−xMgxO/CIGS interfaces characterized by ultraviolet light excited time-resolved photoluminescence

Annealed Zn_1−xMg_xO/Cu(In,Ga)Se₂ (CIGS) interfaces have been characterized by ultraviolet light excited time-resolved photoluminescence (TRPL). The TRPL lifetime of the Zn_1−xMg_xO/CIGS film increased on increasing the annealing temperature to 250 °C, whereas the TRPL lifetime of the CdS/CIGS film had little change by annealing at temperatures lower than 200 °C. This is attributed to the recovery of physical damages by annealing, induced by sputtering of the Zn_1−xMg_xO film. The TRPL lifetime abruptly decreased with annealing at 300 °C. The diffusion of excess Zn from the Zn_1−xMg_xO film into the CIGS interface is clearly observed in secondary ion mass spectroscopy (SIMS) depth profiles. These results indicate that excess Zn at the vicinity of the CIGS surface acts as non-radiative centers at the interface. The TRPL lifetime of the Zn_1−xMg_xO/CIGS film annealed at 250 °C reached values to be comparable to that of the as-deposited CdS/CIGS film. Performance of the Zn_1−xMg_xO/CIGS cells varied with the annealing temperature in the same manner as the TRPL lifetime. The highest efficiency of the Zn_1−xMg_xO/CIGS solar cells was achieved for annealing at 250 °C. The results of the TRPL lifetime on annealing show that the cell efficiency is strongly influenced by the Zn_1−xMg_xO/CIGS interface states related to the damages and diffusion of Zn.     

Demulsification of oil-in-water emulsion under freezing conditions: Effect of crystal structure modifier

The demulsification of oil-in-water (O/W) emulsions under freezing conditions is connected to fat crystallization in the oil droplet. Therefore, demulsification can be prevented by the use of oil with a low melting point, and also by lowering the O/W ratio. However, an oil with a low melting point, such as sunflower, is rather expensive, and the O/W ratio has a significant effect on the texture of emulsions. We searched for an oil that is suitable for the production of a freeze-stable emulsion and found that soybean oil has unique characteristics. Normally, emulsions are more unstable at lower temperatures; soybean oil emulsion is unstable at −10°C and stable at −20°C. This unique characteristic results from the following two reasons. First, the solid fat content of soybean oil is almost the same at −10 and −20°C. Second, small crystals form a larger network over a period of time, and the higher temperature promotes faster restructuring. This structure formation was microscopically observed with the use of a thermostated stage. Structure formation was suppressed with the addition of a crystal structure modifier, polyglycerol fatty acid full ester, which also suppressed coalescence.     

Photoswitching of electron transfer property of diarylethene–viologen linked molecular layer constructed on a hydrogen-terminated Si(111) Surface

An organic monolayer with diarylethene and viologen moieties as a photochromic and an electroactive group, respectively, was constructed on a hydrogen-terminated Si(111) surface by sequential surface reactions. Photoswitching behaviour of electron transfer from the Si electrode to viologen moiety, larger and smaller current after UV and visible irradiation, respectively, was observed. This photoswitching behaviour can be explained by a change in molecular conductivity of diarylethene moiety, which separates Si surface and viologen moiety, as a result of ring closing and opening induced by UV and visible irradiation, respectively.