Thermodynamic Regularities in Perovskite and K2NiF4 Compounds

It has been found that the enthalpy of formation of perovskite compounds, Δ_fH° (ABO₃, B = transition metais), from binary oxides can be well characterized in terms the tolerance factor, t≡(r_A+ r_o)√2 (r_B+ r_o), where r_A and r_B are the radii of A-site ions with 12-coordination and B-site ions with 6-coordination, respectively, and Δ_fH°=−168 + 270(1 − t) kJ·mol⁻¹ for A^IB^VO₃, Δ_fH°=−125 + 1000(1 − t) kJ·mol⁻¹ for A^IIB^IVO₃, and Δ_fH°=− 90 + 720(1 − t) kJ·mol⁻¹ for A^IIIB^IIIO₃. Although the thermodynamic data of K₂NiF₄ compounds are not extensive, a similar regularity can be found when use is made of the radii of A-site ions with 9-coordination for the K₂NiF₄ compounds. These correlations will be quite useful in predicting.     

Fate of the chlorine and fluorine in a sub-bituminous coal during pyrolysis and gasification

The fate of the chlorine and fluorine present in a sub-bituminous coal from Indonesia during pyrolysis and gasification has been studied with fixed and entrained bed reactors. The rate profile for HCl evolved in the temperature programmed pyrolysis exhibits the main and shoulder peaks at 480 and 600 °C, respectively. Model experiments and subsequent Cl 2p XPS measurements show that HCl reacts with metal impurities and carbon active sites at 500 °C to be retained as inorganic and organic chlorine forms, from which HCl evolves again at elevated temperatures. It is suggested that the HCl observed in the coal pyrolysis may originate from the above-mentioned chlorine functionalities formed by secondary reactions involving the nascent char. In the CO₂ gasification of the 900 °C char at 1000 °C and 2.5 MPa, any measurable amounts of HCl and HF could not be detected even at a high conversion of 75 wt% (daf), suggesting the accumulation of these halogens in the residual char. When the coal is injected into an O₂-blown, entrained bed gasifier at 1200-1400 °C under 2.6 MPa, the partial oxidation proceeds to a larger extent at a higher O₂/coal ratio, whereas the chlorine and fluorine are enriched in the remaining char, and the extent of the enrichment at the latter stage of gasification is larger with the fluorine. The XPS measurements of the chars reveal the presence of the broad F 1 s peak, which can cover a wide range of binding energies attributable to inorganic and organic fluorine. The halogen enrichment during gasification is discussed in terms of secondary reactions of HCl and HF with char.     

Synthesis and Photocrosslinking Reaction of N-Allylcarbamoylmethyl Cellulose Leading to Hydrogel

Summary The reaction of the carboxymethyl cellulose sodium salt (Na-CMC) (degrees of substitution (DS) = 1.2) with N-hydroxysuccinimide (Su-OH) in the presence of 1-hydroxybenzotriazole and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC) was carried out in water to obtain the Su-OH ester of carboxymethyl cellulose, Su-CMC, with the DS values of 0.19 – 1.04. N-Allylcarbamoylmethyl cellulose (Allyl-CMC), which was prepared from the reaction of Su-CMC with an excess amount of allylamine, was crosslinked by UV-irradiation. In addition, the photocrosslinked Allyl-CMC film was swollen with water to form a hydrogel having a relatively high water-swelling property, e.g., the degree of swelling (ds) was ca. 360% for Allyl-CMC with the DS of 0.93.     

Anomalous oxide scale formation under exposure of sodium containing gases for solid oxide fuel cell alloy interconnects

Reactivity of oxide scale on Fe-Cr alloy with Na-containing gases was examined to estimate the stability against sodium (Na): vapors of NaCl and Na₂SO₄ exposures with air flow at 1073 K. The identified reaction phases were Cr-Mn spinel, Cr₂O₃, and alloy from the X-ray diffraction of surface with no Na-reaction products. However, the protective oxide scales (Mn-Cr spinel and Cr₂O₃ layers) on the Fe-Cr alloy were partially decomposed by reacting with Na to form Na-compounds inside the oxide scale/alloy interfaces. In some parts, anomalous oxide scales were found around the oxide scale/Fe-Cr alloy interfaces, with forming Na-rich compounds: the compounds were distributed inner parts of oxide scales around oxide scale/alloy interfaces. The stability of oxide scales and degradation were discussed based on the observed distribution of elements.     

Carbonization of adamantane to a graphitizable carbon

Adamantane was carbonized in sealed tubes to 1073 K. Despite the non-planar molecular structure of adamantane, the resulting carbon was graphitizable. Using i.r. and u.v. spectrometry, mass spectrometry and X-ray diffraction, it was found that adamantane begins to decompose at ≈ 823 K to yield such planar molecules as phenanthrene, methyl-phenanthrene and pyrene. These molecules lead to a graphitizing carbon through a carbonization process which is similar to that of a pitch.     

Adsorption of aromatic amines and o-substituted derivatives of phenol from organic solutions by activated carbons-effect of surface acidity

In order to study the effect of surface acidity of activated carbons on their adsorption characteristics, three kinds of aromatic amines and four kinds of o-substituted phenols were adsorbed from organic solutions by twelve kinds of activated carbons of different acidity and of known pore-structure. It was demonstrated that the surface acidity had a marked effect on the adsorption characteristics and that the effect was linked with the polarity of the solvents.     

Glycoconjugated polymer 6. Synthesis of poly[styrene-<Emphasis Type="Italic">block</Emphasis>-(styrene-<Emphasis Type="Italic">graft</Emphasis>-amylose)] via potato phosphorylase-catalyzed polymerization

Summary The potato phosphorylase-catalyzed polymerization of α-D-glucose-1-phosphate (G-1-P) onto poly[styrene-block-(4-vinylbenzyl maltohexaoside)] (1) was performed at the molar ratios of [G-l-P]₀ and [maltohexaose]₀ of 35, 80, and 250. The product was found to be soluble in dimethyl sulfoxide, which was a good solvent for amylose, and showed the complex-formation with iodine, indicating that the product was assignable to poly[styrene-block-(styrene-graft-amylose)] (2). The quantitative analysis of the liberated phosphoric acid gave the average degree of polymerization o f the glucose unit (n) as 27, 5 1, and 180 for 2-I, 2-II, and 2-III, respectively. Received: 29 November 2002/Accepted: 22 December 2002 Correspondence to Toyoji Kakuchi     

TEM,XPS and SIMS Analyzes on Grain Boundary of Lanthanum Chromites

The morphological characteristics, chromium valence state, and cation transport in the vicinity of grain boundary in La_1-xCa_xCrO₃ were investigated by using TEM/EDS, XPS and SIMS techniques. The width of grain boundary was around 1 nm where anomalous enrichment of calcium was observed. Higher valence state of chromium such as Cr⁶⁺(d⁰) was detected in the grain boundaries whereas Cr³⁺(d³) and Cr⁴⁺(d²) were dominant in the bulk. Very fast interdiffusion of alkaline earths was observed in the Sr²⁺-La_0.75Ca_0.25CrO₃ system. All observed phenomena were correlated by assuming the A-site vacancy which may be induced by the formation of Cr⁶⁺ at grain boundaries.     

Chemical Potential Diagrams for Rare Earth-Transition Metal-Oxygen Systems: I, Ln-V-O and Ln-Mn-O System

The thermodynamic properties of double oxides in rare earth-transition metal (V and Mn)-oxygen ternary systems have been collected and evaluated to examine their stability using chemical potential diagrams plotted as log (α_A/α_B) vs log ( P (O₂)). The thermodynamic regularities of perovskites, pyrochlores, and other compounds have been discussed in terms of the effective ionic radii across a series of rare earths. The obtained regularities have been used to estimate tentatively the thermodynamic properties of some rare-earth vanadium and manganese oxides.