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).     

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.     

Bromine addition and successive amine substitution of mesoporous ethylenesilica: Reaction, characterizations and arsenate adsorption

Bromination and subsequent ethylenediamine substitution of the CC double bond in mesoporous ethylenesilica were carried out to explore the characteristics of this periodic mesoporous organosilica. The structures of the products (BrPMO and EDA–BrPMO, respectively) were analysed by IR, Br K-edge EXAFS and NMR spectroscopies, as well as X-ray diffraction and nitrogen adsorption. We showed (1) that the formulae of the two products that formed were [CHBrSiO_1.5]_0.45[CHSiO_1.5]_0.55 and [NH₂CH₂CH₂NHCHSiO_1.5]_0.05 [CHBrSiO_1.5]_0.40[CHSiO_1.5]_0.55, respectively, (2) that the addition of Br₂ at room temperature occurred on the CC double bonds with disturbing the framework structure, (3) that IR absorption band of CC bonds that reacted with Br₂ is significantly different from that of inactive CC bond, (4) that the length of the C–Br bond was considerably longer than in conventional alkyl bromides, and (5) that a large proportion of the ν(C–Br) band remained at the same position in the IR absorption spectrum after the ethylenediamine (EDA) substitution, while a new ν(C–Br) absorption also appeared. The mechanisms of these reactions are discussed at both the micro and mesoscopic levels.

Arsenate adsorption on EDA–BrPMO, in which the EDA is directly bound to the “surface” of the mesopores, was compared with adsorption on EDA–Pr–PMO, which was prepared by the direct synthesis of 3-chloropropyl-functionalized mesoporous ethanesilica followed by the substitution of Cl with EDA. The strength of the adsorption, as measured with the distribution coefficient, was greater for the former adsorbent than the latter. The origin of this difference was attributed to the distance between amino group and the surface.     

Pulsed Electric Current Sintering of Silicon Nitride

Pulsed electric current sintering (PECS) has been used to densify α-Si₃N₄ powder doped with oxide additives of Y₂O₃ and Al₂O₃. A full density (>99%) was achieved with virtually no transformation to β-phase, resulting in a microstructure with fine equiaxed grains. With further holding at the sintering temperature, the α-to-β phase transformation took place, concurrent with an exaggerated grain growth of a limited number of elongated β-grains in a fine-grained matrix, leading to a distinct bimodal grain size distribution. The average grain size was found to obey a cubic growth law, indicating that the growth is diffusion-controlled. In contrast, the densification by hot pressing was accompanied by a significant degree of the phase transformation, and the subsequent grain growth gave a broad normal size distribution. The apparent activation energy for the phase transformation was as high as 1000 kJ/mol for PECS, almost twice the value for hot pressing (∼500 kJ/mol), thereby causing the retention of α-phase during the densification by PECS.     

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.     

碳基钨涂层在退火过程中的组织和结构变化

用真空等离子体喷涂(VPS)技术在C／C复合材料基体上制备了厚度为0．5mm的钨(W)涂层，涂层的表面通过物理气相沉积(PVD)预沉积钨、铼(Re)多层作为碳(C)的扩散势垒。涂层经过1200℃--2000℃的电子束退火，其微观结构和化学构成发生变化。经测量涂层的再结晶温度约为1400℃，再结晶的活性能为63kJ／mol。当退火温度高于1300℃时，涂层表面的多层W、Re结构将由于W、Re和C之间的相互扩散而发生改变，并在1600℃以上退火lh后由于脆性碳化钨在界面的形成而完全失效，碳化钨层的厚度将随着退火漏度的升高和退火时间的延长而迅速增加。