Sintering of the Mechanochemically Activated Powders of Hexagonal Boron Nitride

Pressureless sintering of hexagonal boron nitride (BN) was performed using a powder activated by mechano-chemical treatments. Physical properties of the sintered BN bodies depend on the type of starting powder and the conditions of the treatments. The BN body, which was obtained at 2000°C using an appropriate activated powder, was 99 wt% pure and was excellent in mechanical and physical properties, in spite of its low density (1.64 g/cm³).     

Potential bile acid metabolites. 24. An efficient synthesis of carboxyl-linked glucosides and their chemical properties

A facile and efficient synthesis of the carboxyl-linked glucosides of bile acids is described. Direct esterification of unprotected bile acids with 2,3,4,6-tetra-O-benzyl-d-glucopyranose in pyridine in the presence of 2-chloro-1,3,5-trinitrobenzene as a coupling agent afforded a mixture of the α- and β-anomers (ca. 1∶3) of the 1-O-acyl-d-glucoside benzyl ethers of bile acids, which was separated effectively on a C₁₈ reversedphase chromatography column (isolated yields of α- and β-anomers are 4–9% and 12–19%, respectively). Subsequent hydrogenolysis of the α- and β-acyl glucoside benzyl ethers on a 10% Pd−C catalyst in acetic acid/methanol/EtOAc (1∶2∶2, by vol) at 35°C under atmospheric pressure gave the corresponding free esters in good yields (79–89%). Chemical specificities such as facile hydrolysis and transesterification of the acyl glucosides in various solvents were also discussed.     

Comparative study on the preparation and properties of radiation‐grafted polymer electrolyte membranes based on fluoropolymer films

In this study the fluoropolymers, poly(ethylene‐co‐tetrafluoroethylene) (ETFE) and poly(vinylidene fluoride) (PVDF) films, together with the radiation‐induced crosslinked polytetrafluoroethylene (cPTFE) film were compared on the basis of their preparation and properties of radiation‐grafted polymer electrolyte membranes. The polymer electrolyte membranes were prepared by radiation grafting of styrene into the base films and subsequent sulfonation. The proton conductivity and chemical stability of the three types of membranes with a similar ion exchange capacity (IEC) near 1.0 mmol/g were investigated and are discussed in detail. Although the ETFE‐based polymer electrolyte membrane was relatively more stable, its proton conductivity was lower than those of the PVDF‐ and cPTFE‐based membranes. On the other hand, the cPTFE‐based membrane showed a significantly higher proton conductivity, but its chemical stability was shorter than that of the ETFE‐based membrane. It is considered that the difference in the preparation and properties of the polymer electrolyte membranes was due to the difference in the degree of crystallinity as well as in the chemical structure of the fluoropolymer base films. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1966–1972, 2007     

Effect of crosslinkers on the preparation and properties of ETFE‐based radiation‐grafted polymer electrolyte membranes

This study concerns a comparative study of three crosslinkers, divinylbenzene (DVB), 1,2‐bis(p,p‐vinylphenyl)ethane (BVPE), and triallyl cyanurate (TAC) crosslinked poly(ethylene‐co‐tetrafluoroethylene) (ETFE)‐based radiation‐grafted membranes, which were prepared by radiation grafting of p‐methylstyrene onto ETFE films and subsequent sulfonation. The effect of the different types and contents of the crosslinkers on the grafting and sulfonation, and the properties such as water uptake, proton conductivity, and thermal/chemical stability of the resulting polymer electrolyte membranes were investigated in detail. Introducing crosslink structure into the radiation‐grafted membranes leads to a decrease in proton conductivity due to the decrease in water uptake. The thermal stability of the crosslinked radiation‐grafted membranes is also somewhat lower than that of the noncrosslinked one. However, the crosslinked radiation‐grafted membranes show significantly higher chemical stability characterized in the 3% H₂O₂ at 50°C. Among the three crosslinkers, the DVB shows a most pronounced efficiency on the crosslinking of the radiation‐grafted membranes, while the TAC has no significant influence; the BVPE is a mild and effective crosslinker, showing the moderate influence between the DVB and TAC crosslinkers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4565–4574, 2006     

Bis-(monoacylglyceryl) phosphate and acyl phosphatidylglycerol isolated from human livers of lipidosis induced by 4,4′-diethylaminoethoxyhexesterol

Bis-(monoacylglyceryl) phosphate and acyl phosphatidylglycerol were isolated from the liver of two patients with lipidosis induced by 4,4′-diethylaminoethoxyhexesterol. Identification was based upon the results of alkaline hydrolysis, acetolysis, IR spectrometry, and upon the determination of molar ratio of phosphorus-glycerol-ester. The contents of the bis-(monoacylglyceryl) phosphate were 10 and 16% total phospholipid phosphorus in them. The bis-(monoacylglyceryl) phosphate contained mainly docosahexaenoic (42%), oleic (29%), and linoleic acid (14%) and had the hemolytic activity of ca. one-eighth lysolecithin from egg yolk. Acidic lipids from the liver also were found to contain a lipid which is less polar than bis-(monoacylglyceryl) phosphate. The results of lipid analysis showed that the lipid possessed the structure of an acyl phosphatidylglycerol, and its content was ca. 2% total phospholipid phosphorus. Accumulation of 4,4′-diethylaminoethoxyhexesterol and its derivatives was found in clinical cases by thin layer chromatography and IR spectrometry. This fact suggested that human liver has an ability to metabolize the drug.     

Triterpene alcohols and sterols of Spanish olive oil

Nine Spanish olive oils, including three each of virgin (pressed oil), refined virgin, and B-residue (solvent-extracted pomace oil) oils from different commercial sources, have been analyzed for their unsaponifiable matter (USM). Four sterolic fractions separated from the oils have been analyzed by preparative thin-layer chromatography (TLC); these fractions are triterpene alcohols, 4-methylsterols, sterols and triterpene dialcohols. The compositions of the four sterolic fractions were determined as their acetates by gas-liquid chromatography (GLC) on an OV-17 glass capillary column. Identification of each component was carried out by argentation TLC, GLC and combined gas chromatography-mass spectrometry (GC-MS); 44 components were identified, of which four: 24-methylene-31-nor-9(11)-lanostenol, 24-methyl-31-nor-E-23-dehydrocycloartanol, 24-ethyl-E-23-dehydrolophenol and 5,E-23-stigmastadienol, were considered to be new sterols from natural sources. Several characteristics, including the content of triteterpene dialcohols in the USM and that of C-24(28) unsaturated sterols in each of the four sterolic fractions, which can be used to distinguish between virgin and B-residue olive oils, were observed.     

Decomposition of Carbon Dioxide to Carbon with Active Wustite at 300°C

Active wustite (FeδO, with a δ value of 0.98) was prepared by keeping normal wustite (δ value of 0.94) in a N₂ atmosphere at 300°C for 10 min. This reaction is given by (4δ₂–3)Fe_δ1O→(4δ₁–3)Fe_δ2O + (δ₂–δ₁)Fe₃O₄ where δ₁= 0.94 and δ₂= 0.98. The equation indicates that the normal wustite undergoes eutectoid decomposition into active wustite and stoichiometric magnetite (Fe₃O₄). Carbon dioxide (1.013 × 10⁵ Pa) was almost completely (100%) decomposed into carbon (zero valence) by the active wustite at the low temperature of 300°C, which was associated with the transformation of the active wustite into the stoichiometric magnetite. The internal pressure of the reaction cell eventually became a vacuum.     

Changes in the Peeled Surfaces of Copper Thin Films Deposited on Polyimide Substrates After Heat Treatment

Peel strength between a copper (Cu) thin film and a polyimide (pyromellitic dianhydride-oxydianiline, or PMDA-ODA) substrate is reduced by heat treatment at 150°C in air. In this work, we investigated the peel strength, the morphology of the interface between Cu films and polyimide substrates using optical microscopy and electron microscopy, and chemical change of the interface using Auger electron spectroscopy (AES) and micro X-ray photoelectron spectroscopy (XPS). The analysis showed that CuO “lumps” were present on the peeled surface of PMDA-ODA after heat treatment at 150°C in air. The peeled surfaces of other polyimide substrates were also analyzed: biphenyl dianhydride-para phenylene diamine (BPDA-PDA) and biphenyl dianhydride-oxydianiline (BPDA-ODA). CuO lumps were present on the peeled surface of BPDA-ODA after the heat treatment, but not that of BPDA-PDA. Compared with the adhesion strength for the Cu thin film, the adhesion strength was high for the Cu/PMDA-ODA and Cu/BPDA-ODA laminates, but the adhesion strength was very low for the Cu/BPDA-PDA laminate. This low strength is the reason that CuO lumps were not detected on the peeled surface of the BPDA-PDA substrate. These CuO lumps were related to the adhesion degradation of the Cu/polyimide laminates after the heat treatment.     

Synthesis of High Density and Transparent Forsterite Ceramics Using Nano-Sized Precursors and Their Dielectric Properties

Forsterite (Mg₂SiO₄) ceramics were prepared using Mg(OH)₂ and SiO₂ as precursors, and the effect of powder characteristics of Mg(OH)₂ on calcination and sintering was investigated. The use of highly dispersed Mg(OH)₂ powder (HD powder) resulted in a lower calcination temperature. Forsterite powder of high homogeneity and small particle size prepared from the HD powder enabled synthesis of high-density forsterite ceramics by ordinary sintering without applying external pressure. Moreover, transparent forsterite ceramics were successfully synthesized through addition of excess Mg to the precursors to compensate for Mg evaporated during the sintering process. Subsequent dielectric measurements revealed that the transparent forsterite ceramics had a very low dielectric loss (tan δ<10⁻⁴).     

Segmented conjugated polymer based on poly(α-thiophenediyl)benzylidine

Summary Segmented polymers with random sequences of conjugated and non-conjugated blocks are produced by partial dehydrogenation of poly(-thiophenediyl)benzylidene. The fraction of conjugated block was controlled by the elimination time. The polymers gave photoluminescence. Absorption coefficients of the polymers increased with the rate of dehydrogenation, and the highest fluorescence intensity were achieved around 9 % conjugation conversion. The polymers were characterized by ¹H- and ¹³C-n.m.r. and infrared spectra, and were soluble in common organic solvents, which suggests a good processability.