Stability of tetragonal ZrO2 phase in Al2O3 prepared from Zr-Al organometallic compounds

Zr-Al organometallic compounds have been spray-dried and heated at temperatures 600 to 1400°C to prepare ZrO₂-Al₂O₃ composite powders. The powders consist of balloon-like particles 0.5 to 2 m in diameter with homogeneously dispersed tetragonal ZrO₂ grains 0.1 to 0.2 m in diameter. The tetragonal fraction of ZrO₂ in the composite powders is higher than that in the powders prepared from sols of Zr(OBuⁿ)₄ and Al[OCH(CH₃)₂]₃. The fraction is affected by the organofunctional group in the Zr-Al compounds.Zr(OBuⁿ)₄ = Zr(OC₄Hgⁿ)₄; Al[OCH(CH₃)₂]₃ = Al(OPrⁱ)₃.     

Thermal properties of ethylene ionomers

The annealing effect of ethylene ionomers annealed at various temperatures and for various periods was studied by differential scanning calorimetry. Two endothermic melting peaks were observed for all the ethylene ionomers annealed. The melting peak at the lower temperature, which was assigned to bundlelike crystal owing to a Hoffman-Weeks relationship, shifted to a higher temperature with the annealing temperature and period, indicative of recrystallization. There is physical cross-linking consisting of ionic aggregates, such as multiplets and clusters in ethylene ionomers. The crystallization kinetics of ethylene ionomers was fundamentally similar, but different from that of low-density polyethylene. Crystallization and recrystallization suggested a mobile ethylene chain in both amorphous regions and ionic aggregates even in the presence of cross-linking.     

Direct Observation of Internal Structure in Spray-Dried Alumina Granules

The internal structure of spray-dried alumina granules was characterized by optical microscopy by immersing them in a liquid having a refractive index close to that of alumina. This method provides a unique technique for the detailed analysis of the internal structure of spray-dried granules.     

Crystalline complex between poly(γ-methyl l-glutamate) and dimethyl phthalate

The crystalline complex between poly(γ-methyl l-glutamate) (PMLG) and dimethyl phthalate (DMP) has been formed in films cast from a solution in dichloroethane. It has the stoichiometry of 1 mol of DMP to three or four residues of PMLG and shows two definite characteristics in X-ray diffraction patterns; one is the large hexagonal unit cell with the edge of around 28 Å and another the ‘extra’ 5.07 Å meridional reflection which can not be interpreted by a PMLG α-helical conformation. The structural examination for the films with various DMP contents is carried out by X-ray, viscoelastic, and d.s.c. measurements and the following structure is proposed for the crystalline complex. Four PMLG are associated to form a group which is hexagonally packed and DMP molecules, located in the gaps between groups, form a specific favourable helical structure along PMLG chains in which the van der Waals stacking of benzene rings of DMP is significant.     

Different support effect of M/ZrO2 and M/CeO2 (M = Pd and Pt) catalysts on CO adsorption: A periodic density functional study

CO adsorption over Pd₄ and Pt₄ cluster supported by c-ZrO₂(1 1 1) and CeO₂(1 1 1) catalyst systems was investigated using periodic density functional method in order to clarify the support effect on CO activation. We found that the support increases the CO activation for bridge and three-fold sites but decreases for the atop site. Moreover, it was found that the support changes the site preference for the CO adsorption. Bridge site on both the Pt₄/c-ZrO₂ and Pt₄/CeO₂ show larger CO adsorption energies than those on the other sites while the atop site is energetically preferable on isolated Pt₄ cluster. c-ZrO₂ supported Pd shows the largest CO activation with large charge transfer from the catalyst to the CO molecule. This reveals that ZrO₂ supported Pd can be a good catalyst for CO activation because of its higher probability to the three-fold site CO adsorption. We also found that positively charged M₄ clusters on the support keep their strong electron-donating properties and have enough charge density to contribute to the activation of an adsorbed CO molecule by a charge transfer.     

The effect of the N-linked glycans on structural features and physicochemical functions of soybean β-conglycinin homotrimers

β-Conglycinin is a trimeric protein consisting of three subunits, α,α′,and β, which are N-glycosylated. The α and α′ subunits contain extension regions in addition to core regions common to all subunits. We purified homogeneous trimers consisting of only α, α′, or β from mutant soybean cultivars containing β-conglycinin lacking one or two subunits: α homotrimers from an α′-lacking mutant, α′ homotrimers from an α-lacking mutant, and β homotrimers from an α-and α′-lacking mutant. Structural features and physicochemical functions of the three homotrimers were examined and compared with those of recombinant homotrimers having no N-linked glycans. The native homotrimers have secondary structures very similar to those of the recombinant ones. In analogy with the recombinant homotrimers, the native ones exhibit different thermal stabilities from one another (β>α′>α), and the native α and α′ homotrimers exhibit better solubility, emulsifying ability, and heat-induced association than the native β homotrimer. Further, the N-linked glycans contribute to solubilities of the three subunits at low ionic strength (μ=0.08) and to the emulsifying ability of the native β homotrimer. N-Linked glycans also prevent heat-induced associations of the native α and α′ homotrimers but do not contribute to the secondary structure and the thermal stability of β-conglycinin.     

Application of polymerizable surfactant in the preparation of polystyrene/nano-Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> composite

Monooctadecyl maleate, as a polymerizable surfactant, was synthesized by the mono-esterification of maleic anhydride and octadecanol, and was utilized to surface-modify nano-Fe₃O₄ particles. A polymerizable magnetic fluid was obtained by directly dispersing modified nano-Fe₃O₄ particles into styrene monomer, and the polystyrene/nano-Fe₃O₄ composite was prepared through free radical polymerization of polymerizable magnetic fluid. The structure and dispersion status in different dispersion phases of modified nano-Fe₃O₄ particles were studied by Fourier transform infrared (FTIR) spectrometry, X-ray diffraction (XRD) and transmission electron microscopy (TEM), respectively. The experimental results show that the nano-Fe₃O₄ particles modified by monooctadecyl maleate with the size of about 7–10 nm can be uniformly dispersed into styrene and fixed in the composite during the procedure of polymerization. Thermogravimetric analysis (TGA) and vibrating sample magnetometry (VSM) indicate that the thermal stability of polystyrene/nano-Fe₃O₄ composite is improved compared to that of pure polystyrene, and the composite is a sort of superparamagnetic materials.     

Microstructure development of steel during severe plastic deformation

The microstructure development during plastic deformation was reviewed for iron and steel which were subjected to cold rolling or mechanical milling (MM) treatment, and the change in strengthening mechanism caused by the severe plastic deformation (SPD) was also discussed in terms of ultra grain refinement behavior. The microstructure of cold-rolled iron is characterized by a typical dislocation cell structure, where the strength can be explained by dislocation strengthening. It was confirmed that the increase in dislocation density by cold working is limited at 10¹⁶m⁻², which means the maximum hardness obtained by dislocation strengthening is HV3.7 GPa. However, the iron is abnormally work-hardened over the maximum dislocation strengthening by SPD of MM because of the ultra grain refinement caused by the SPD. In addition, impurity of carbon plays an important role in such grain refinement: the carbon addition leads to the formation of nano-crystallized structure in iron.     

Shape optimization for a link mechanism

This paper presents a numerical solution for shape optimization problems for link mechanisms, such as a piston-crank mechanism. The dynamic behavior of a link mechanism is described by a differential-algebraic equation (DAE) system consisting of motion equations for each single body and constraints of linkages and rigid motions. In a shape optimization problem, the objective function to maximize is constructed from the external work done by a given external force, which agrees with the kinetic energy of the link mechanism, for an assigned time interval, and the total volume of all the links forms the constraint function. The Fréchet derivatives of these cost functions with respect to the domain variation, which we call the shape derivatives of these cost functions, are evaluated theoretically. A scheme to solve the shape optimization problem is presented using the H ¹ gradient method (the traction method) proposed by the authors as a reshaping algorithm, since it retains the smoothness of the boundary. A numerical example shows that reasonable shapes for each link such that mobility of the link mechanism is improved are obtained by this approach.