An XPS and reduction study of PrCoO3

The perovskite-type oxide PrCoO₃ has been studied by means of X-ray photoelectron spectroscopy (XPS), reduction in H₂ and X-ray diffraction. Two types of oxygen were detected: lattice oxygen (binding energy = 528.4 eV) and adsorbed oxygen (binding energy = 530.9 eV). The increase in relative intensity of the peak corresponding to the latter species after reduction of PrCo0₃ to 3e^– per molecule is assigned to the formation of hydroxyl groups. Temperature-programmed reduction (TPR) results showed two reduction steps: to 1 e^– per molecule (Co^3.1 Co²⁺) at 475 to 635 K, and to 3e^– per molecule (Co²¹ Co⁰) at 725 to 815 K. Reduction in the first and second steps occurs according to the contracting sphere model and the nucleation mechanism, respectively. Reduction of Co³⁺ to Co²⁺ causes minimal structural changes in the perovskite. Reduction to 3e^– per molecule yielded Pr₂O₃ and metallic cobalt. After this reduction and reoxidation at 973 K, the perovskite structure was regained. By XPS and TPR it was shown that PrCo0₃ is more easily reducible than LaCo0₃. It is concluded that the cation in the A position of the structure plays a significant role in the bulk and surface properties of LnCo0₃ (Ln, lanthanide elements) oxides.     

Influence of preparation conditions on characteristics of the YBa2Cu3O7−δ compound

Synthesis of ceramic YBa₂Cu₃O_7– by solid-state reaction was performed under different conditions. Different values of cooling rate and oxygen flow were used, and no significant influence on superconducting characteristics of the samples was observed. A major influence on their mechanical properties was found.     

Influence of the stress,strain, and temperature on the surface roughness of an AlSl 52100 steel due to an orthogonal cut

In recent years, the finite element method (FEM) has become the main tool for simulating the metal cutting process because research based on trial and error is time consuming and requires high investment. Early studies were done by different investigators. In this research AISI 52100, hardened steel (62 HRC) was selected for an orthogonal machining process as well as metal cutting simulation using the software DEFORM-2D. This software is based on a forging process and has been adapted to an orthogonal machining process. The results of simulated cutting forces were compared with experimental cutting force data to validate the orthogonal cut simulation. Also, the surface roughness was measured, and the influence of the stress, strain, and temperature on the surface roughness was studied.     

Cu/SBA-15 as adsorbent for propane/propylene separation

Samples of mesoporous silica SBA-15 were prepared under hydrothermal conditions where Cu cations were incorporated to the structure by impregnation in order to compare the adsorption behavior in the presence and absence of this element. The adsorption/desorption equilibrium isotherms of propylene, propane, and N₂ were measured to evaluate their usefulness in the propane/propylene separation. All the adsorption isotherms of SBA-15 measured in the absence of Cu cations were described by the Freundlich equation, while the adsorption isotherms of propane on Cu/SBA-15 were better represented by the Henry equation and those of propylene were satisfactorily described by the Langmuir model in the range P < 100 Torr. The adsorption uptake of propylene increased and that of propane decreased in Cu/SBA-15 as compared to the amounts observed in the SBA-15 sample. The presence of Cu atoms in the adsorbent lattice increased the selectivity towards propylene. Under some working conditions the adsorbed amount of propylene in Cu/SBA-15 sample was totally reversible and the propane uptake, negligible.     

Semi-interpenetrating polymer networds produced with polyethylene terephthalate oligomer and unsaturated polyester resin

A series of semi-interpenetrating polymer networks (semi-IPN's) based on different compositions of an acyclic polyethylene terephthalate oligomer and unsaturated polyester resin (UP) were prepared. The oligomer was dissolved in the resin containing styrene crosslinker. Later this mixture was crosslinked at room temperature using methyl ethyl ketone peroxide catalyst and cobalt naphtanate as promoter. The tensile strength of the IPN's decreases as the concentration of oligomer increases, whereas, elongation to break increases. A characterization of the oligomer used is also presented.     

Asymptotic solvers for second-order differential equation systems with multiple frequencies

In this paper, an asymptotic expansion is constructed to solve second-order differential equation systems with highly oscillatory forcing terms involving multiple frequencies. An asymptotic expansion is derived in inverse of powers of the oscillatory parameter and its truncation results in a very effective method of dicretizing the differential equation system in question. Numerical experiments illustrate the effectiveness of the asymptotic method in contrast to the standard Runge–Kutta method.     

Crystallinity and thermal properties of ethylene-1-decene copolymers

Summary Three copolymers of ethylene and 1-decene, covering a wide range of compositions, have been synthesized with a MgCl₂-supported Ziegler-Natta catalyst. The analysis by DSC and X-ray shows a great degree of heterogeneity in these copolymers and appreciable levels of crystallinity, corresponding to the orthorhombic lattice of polyethylene, are present even for very high 1-decene contents.     

Strong dependence on pressure of the performance of a Co/SiO2 catalyst in Fischer–Tropsch slurry reactor synthesis

A 10 wt% Co/SiO₂ catalyst was prepared by the incipient wet-impregnation method and tested in Fischer–Tropsch synthesis in a slurry reactor under conditions approaching industrial practice. The catalyst precursor was investigated by X-ray diffraction (XRD), temperature-programmed reduction (TPR), transmission electron microscopy (TEM) and photoelectron spectroscopy (XPS). The XPS and XRD techniques revealed the presence of a crystalline Co₃O₄ spinel-type phase, while-in addition-TEM and XPS analyses pointed to the formation of another amorphous Co₃O₄ spinel phase, both species interacting weakly with the silica substrate. The influence of total pressure on the conversion, selectivity and stability of the catalyst was studied. Upon increasing the overall pressure from 20 to 40 bar, not only activity increased but also the catalyst are not deactivating. These results are explained in terms of an increase of gases solubility in the solvent, this increment of CO concentration in the liquid phase favours carbonyl species formation and the cobalt particles segregation that implies an increase in the metal surface area.     

Styrene-butadiene branched star-shaped asphalt modifiers: Synthesis and mechanical characterization

Abstract

The synthesis and the corresponding characterization of styrene-butadiene (SB), branched, star-shaped copolymers was investigated as part of a research project on asphalt modification using polymers with precise molecular structures. The method of anionic polymerization was followed to prepare samples of block copolymers of SB, a synthesis method that controls chain-architecture, molecular weight distribution, monomer distribution, and the average molecular weight. The research studies are the synthesis of block copolymers including linear, three- and four-arms constructs, depending on the coupling agent used. The techniques of nuclear magnetic resonance (1NMR), differential scanning calorimetry (DSC), gel permeation chromatography (GPC), and rheology were carried out to characterize the copolymers. From the results of the 1NMR, DSC, and GPC analyses, all star-shaped copolymers investigated showed a similar block copolymer composition. Furthermore, the rheological behavior of one of the synthesized star-shaped copolymers was nearly the same as a four-branched commercial copolymer. Rheologically, the four-arm block copolymer sample had the largest storage modulus (G′) among the branched copolymers synthetized, indicating that such architecture produces a highly structured material. In regard to polymer-modified asphalt formulations, the three-branched copolymer architecture yielded better elastic behavior than the four-branch version. In summary, the findings of this investigation provide new insight about a polymer system that may offer advantages in industrial asphalt paving applications.