Sol—Gel Synthesis of Strontium-Doped Lanthanum Manganite

Strontium-doped lanthanum manganite powders were prepared using a peroxide acetate salt based solution. The stable sol was peptized by reacting ammonium hydroxide with the precursor solution. The amorphous dried gel powders exhibit a high energy level, due to their high cations coordination and small particles, to develop the perovskite phase. This crystalline phase development from powders containing monocarboxylate ligands was characterized by thermal analysis (TG, DTG, DTA), X-ray diffraction, and IR spectroscopy. The transformation from amorphous powders into a crystallized homogeneous oxycarbonate phase in a first stage corresponds to an exothermal DTA peak at 270°C. X-ray diffraction patterns and IR spectra showed similar behavior of the powders after complete organic removal, during the conversion into perovskite phase starting at approximately 630°C and achieved about 700°C and achieved about 700°C, as well as during the sintering process.     

Aging Behavior of xPb(Fe2/3W1/3)O3· (1 –x)Pb(Fe1/2Nb1/2)O3 Ceramic

The aging behavior of a series of lead perovskite dielectrics with the compositions x Pb(Fe_2/3W_1/3)O₃·(1 – x )Pb(Fe_1/2-Nb_1/2)O₃, where 0 ≤ x ≤ 1, and the effect of dopants were studied. Below the Curie temperature ( T _c), the capacitance and the dissipation factor (tan δ) decrease approximately linearly with logarithmic time. The aging rate depends on the temperature difference, Δ T , between the aging temperature and T _c, and on the dopant concentration, but is independent of the measurement frequency between 1 and 1000 kHz. The maximum aging rate is about 3% per decade of time for capacitance and 5% per decade for tan δ at 1 mol% dopant concentration, and increases to 6.3% for capacitance and 8.5% for tan δ at 0.7 mol% dopant concentration. These results are consistent with an aging mechanism caused by changing ferroelectric domain structure with time, as proposed for BaTiO₃.     

Harnessing the Melting Peculiarities of Ultra‐High Molecular Weight Polyethylene Fibers for the Processing of Compacted Fiber Composites

Summary: Compacted fiber composites offer unique properties due to their lack of an extraneous matrix. The conditions of processing ultra‐high molecular weight polyethylene (UHMWPE) fibers were simulated in a heated pressure cell. In situ X‐ray diffraction measurements were used to follow the relevant transitions and the changes in the degree of crystallinity during melting and crystallization. The results strongly support the suggestion that the hexagonal crystal phase, in which the chain conformation is extremely mobile on the segmental level, constitutes the physical basis of compaction technologies for processing UHMWPE fibers into a single‐polymer composite. This report suggests that using a pseudo‐phase diagram outlining the occurrence of different phases during slow heating and the degree of crystallinity can provide valuable insight into the technological parameters relevant for optimal processing conditions.

Degree of crystallinity as a function of pressure and temperature in a region relevant to compaction processes.     

dc Electrical Degradation of Perovskite-Type Titanates: I, Ceramics

The rate of the resistance degradation of doped SrTiO₃ ceramics is investigated as a function of various external and material parameters. The effects of the mutually interrelated parameters dc voltage, dc electric field, and thickness of the dielectric are described by power laws. Electron microscopic potential contrast studies show a Maxwell-Wagner polarization leading to a concentration of the electric field at the grain boundaries during the degradation. Based on this finding, the voltage step per grain boundary, ΔΘ_gb, is introduced as a rate-determining parameter which allows an explanation of the influence of the grain size on the degradation rate as well as the difference in the power laws for ceramic and single-crystal samples.     

Oxidative coupling of methane over LaCoO3−δ-based mixed oxides

The catalytic activity of LaCoO_3–-based mixed oxides for the oxidative coupling of methane has been tested by TPR and cyclic reaction. Characterization has been done by XRD, TGA and Mössbauer spectrometry. It is likely that the perovskite-crystal structure containing hypervalent metal ions has an important role and that unique structural oxygen species in the perovskite contribute to the partial oxidation of methane.     

Decomposition of nitric oxide over perovskite oxide catalysts: effect of CO2, H2O and CH4

Direct nitric oxide decomposition over perovskites is fairly slow and complex, its mechanism changing dramatically with temperature. Previous kinetic study for three representative compositions (La_0.87Sr_0.13Mn_0.2Ni_0.8O_3−δ, La_0.66Sr_0.34Ni_0.3Co_0.7O_3−δ and La_0.8Sr_0.2Cu_0.15Fe_0.85O_3−δ) has shown that depending on the temperature range, the inhibition effect of oxygen either increases or decreases with temperature. This paper deals with the effect of CO₂, H₂O and CH₄ on the nitric oxide decomposition over the same perovskites studied at a steady-state in a plug-flow reactor with 1 g catalyst and total flowrates of 50 or 100 ml/min of 2 or 5% NO. The effect of carbon dioxide (0.5–10%) was evaluated between 873 and 923 K, whereas that of H₂O vapor (1.6 or 2.5%) from 723 to 923 K. Both CO₂ and H₂O inhibit the NO decomposition, but inhibition by CO₂ is considerably stronger. For all three catalysts, these effects increase with temperature. Kinetic parameters for the inhibiting effects of CO₂ and H₂O over the three perovskites were determined. Addition of methane to the feed (NO/CH₄=4) increases conversion of NO to N₂ about two to four times, depending on the initial NO concentration and on temperature. This, however, is still much too low for practical applications. Furthermore, the rates of methane oxidation by nitric oxide over perovskites are substantially slower than those of methane oxidation by oxygen. Thus, perovskites do not seem to be suitable for catalytic selective NO reduction with methane.     

Ammoxidation of toluene over Y-Ba-Cu-Co-O perovskites

Ammoxidation of toluene over the perovskites YBa₂Cu₃O_6.1, YBa₂Cu₂CoO_6.7 and YBaCuCoO_4.9 was investigated at 400 °C. At low partial pressures of O₂ benzonitrile was selectively formed, while CO₂ was the main product at high pressures of O₂. Systematic differences in activity were observed for the three phases and are related to the crystal contents of Cu and Co. At low O₂ pressures, Cu-sites are active for nitrile formation, while Co-sites give CO₂. At high O₂ pressures, the activity for CO₂ of Cu-sites increases more than that of Co-sites due to filling of near-surface oxygen vacancies.     

A novel preparation method for NiCo2O4 electrodes stacked with hexagonal nanosheets for water electrolysis

In this paper, we describe the preparation of a porous nanosheet-stacked NiCo₂O₄ composite electrode using a novel electrophoretic deposition (EPD) calcination method. The effects of the deposition time and voltage, and of the calcination temperature have been investigated. The microstructure of the deposited films in the electrodes before and after calcination has also been investigated. The electrocatalytic properties of the electrodes have been investigated using cyclic voltammetry and polarization curves. The electrode films produced using this new technique have a porous structure composed of stacked hexagonal NiCo₂O₄ nanosheets. The resulting electrodes exhibit good electrocatalytic properties for water electrolysis.     

Phase stability and magnetic properties of SrFe18O27 W-type hexagonal ferrite

W-type ferrite is a member of the hexagonal ferrite family and a potential permanent magnet material. However, its synthesis conditions are not fully understood yet. Samples were sintered either at 1400°C in air and quenched, or at 1300°C at reduced oxygen partial pressure. The precise stability conditions of this W-type ferrite were investigated in the temperature range of 1200°C-1400°C using thermogravimetry, XRD, and electron microscopy. At 1300°C, the ferrite is stable at oxygen partial pressures of . At more oxidizing conditions, the ferrite decomposes into M-type ferrite and hematite, while at more reducing atmospheres Sr₄Fe₆O₁₃ and magnetite are formed. The nonstoichiometry δ of SrFe_18−δO₂₇ was derived from thermal analysis data at 1300°C as function of oxygen partial pressure and was found to be mainly due to cation vacancies. Magnetization measurements show that this W-type ferrite exhibits M_s = 103 emu/g at T = 4 K, which agrees well with a ferrimagnetic spin arrangement according to Gorter's model. As alternative, Zn-substituted W-ferrite was found to be stable in air at 1200°C with a large M_s = 123 emu/g at 4 K.     

Synthesis of Compositionally Homogeneous Sr(CuxZn1−x)1/2W1/2O3

A complex perovskite of Sr(Cu _x Zn_{1- x} )_1/2 W_1/2O₃ (SCZW) is synthesized by a new combination of wet and dry processess. Mixed oxides containing Cu²⁺ and Zn²⁺ (CZ) are prepared by the wet process (coprecipitate method). SCZW is obtained by the dry process (mixed-oxide method) from a mixture of CZ, SrCO₃, and WO₃. SCZW has practically no compositional, unlike solid solutions prepared by the conventional dry method. The wet–dry process method is useful because the wet process is applied to only B-site cations having the same valence.