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1.
Members of the systems Co1−xRhxS2 (0 ≤ x ≤ 0.6) were prepared, and their crystallographic and magnetic properties studied. The observed ferromagnetic moments for compositions where x ≤ 0.2 indicate a ferromagnetic alignment between Co(3d7) and Rh(4d7) electrons. This is the first observation of localized behavior of 4d electrons in the pyrite structure. Members of the systems Co1−xRuxS2 (0 ≤ x ≤ 1) and Rh1−xRuxS2 (0.5 ≤ x ≤ 1) were also prepared and their crystallographic and magnetic properties studied. From comparison with the Co1−xRhxS2 system, it appears that the 4d electrons of Rh(4d7) are localized in the presence of Co(3d7) but are delocalized in the presence of Ru(4d6). The magnetic susceptibility of the Co1−xRuxS2 system is sensitive to the homogeneity of the products and indicates that Ru(4d6) behaves as a diamagnetic ion.  相似文献   

2.
Zusammenfassung Die Frequenzen der Skelettschwingungen von isotaktischem Polypropylen werden mit Hilfe des Valenzkraft-Modells berechnet und mit den im UR-Spektrum gemessenen Frequenzen verglichen. Die übereinstimmung ist so gut, da? eine Zuordnung der Banden zu den Molekelschwingungen gegeben werden kann. Dagegen k?nnen die Intensit?tsverh?ltnisse nicht gekl?rt werden. Herrn Professor Dr.Hellwege danke ich für Anregungen und Diskussionen zu dieser Arbeit. Ferner danke ich den Firmen Kalle, Wiesbaden, und Farbwerke Hoechst für die zur Verfügung gestellten Polypropylenproben, der Deutschen Forschungsgemeinschaft für die Bereitstellung des Rechenautomaten und HerrnG. Günther für die Hilfe beim Programmieren.  相似文献   

3.
Abstract

The one-pot synthesis of tetrasubstituted imidazoles by use of a series of LaxSr1 ? xFeyCo1 ? yO3 perovskites as catalysts is described. The La0.8Sr0.2Fe0.34Co0.66O3 nanocatalyst had the greatest activity in the heterogeneous cyclocondensation of an aldehyde, benzil, ammonium acetate, and a primary aromatic amine in water under ultrasonic irradiation. Some of the derivatives generated during this work were utilized as substrates for the synthesis in good yields of novel multifunctional tetrasubstituted imidazoles with Me3Si, C=S, and SH groups, via nucleophilic attack of tris(trimethylsilyl)methyllithium (TsiLi) at the carbon of carbon disulphide.  相似文献   

4.
Vacancy ordering is observed in the compound Gd0.88Se. The symmetry is reduced fromFm3m¯ for stoichiometric GdSe toPm3m¯ and the cubic cell edge is 5.7669(4)A˚. The Gd occupancies become of Cu3Au type, whereas no vacancies or distortions were observed for the Se sublattice.  相似文献   

5.
Nanocrystals of Ce1?xPbxO2?δ (x = 0.00, 0.05, 0.10, 0.15, 0.20, 0.25, 0.30, and 0.35) were prepared by a hydrothermal reaction route. During the formation reaction, buffer solutions were explored as an effective additive to retain the initial molar ratio. With increasing the Pb2+ content, the average crystallite size was slightly retarded. Morphologies observed by transmission electron microscope indicated that the particles were spherical-like and highly uniformed. Pb2+ ions are homogenously distributed in the solid solutions. Analyses using X-ray diffraction, Raman and UV spectroscopies showed that the solid solubility limit of Pb2+ in CeO2 was about x = 0.20. For x < 0.20, with increasing the Pb2+ content, the bulk conductivity increased, and the oxygen storage capacity was enhanced as followed by a decrease in reduction temperature.  相似文献   

6.
Bi1?xSrxFeO3?δ perovskites synthesised by solid-state reaction in ambient atmosphere or in a closed vessel were analysed by X-ray diffraction and Mössbauer spectroscopy. The evolution of the valence state of iron with both Bi/Sr ratio and oxygen content has been more particularly discussed. The samples are single phase and homogeneous for x ≤ 0.5 (Bi-rich) and x > 0.8 (Sr-rich). For intermediate Sr contents, the samples are less homogeneous and tend to contain both Bi-rich and Sr-rich phases. The appearance of Sr-rich phases for x > 0.5 corresponds to the appearance of Fe4+, to compensate for the lack of positive charges due to the replacement of Bi3+ by Sr2+.  相似文献   

7.
Various compositions (1−x)BaTiO3 + xPbF2 + xLiF were prepared, shaped to pellets then sintered at 900°C for 2 h in gold sealed tubes. The purity and the symmetry of the obtained samples were checked by X-ray diffraction. A new solid solution with Ba1−x Pb x (Ti1−x Li x ) O3−3x F3x formula occurs in the composition range 0 ≤ x ≤ 0.20. SEM observations were performed on polished and fractured ceramics. The complex permittivity was measured as a function of temperature (−120°C ≤ T ≤ 250°C) and frequency (50 Hz ≤ f ≤ 4 × 107 Hz). The dielectric performances are the best for ceramic Ba0.97Pb0.03(Ti0.97Li0.03)O2.91F0.09. The real component ε′, exhibits a maximum of approximately 7500 at the ferroelectric Curie temperature T C ≈ -18°C, the dielectric losses tan δ value being 0.012. At room temperature, the relaxation frequency f r is around 40 MHz for this ceramic. This novel ferroelectric oxifluoride is a promising material for applications, in particular in the field of Z5U multilayer capacitors.   相似文献   

8.
The paper presents a thermodynamic analysis of the formation of equilibrium defects in perovskitelike La1?x SrxCo1?y MeyO3?δ oxides, where Me = Cu or Mn, x = 0.0 or 0.3, and y = 0.0, 0.25, or 0.3, at high temperatures (873 K ≤ T ≤ 1373 K) depending on the composition and oxygen pressure (10?8 atm ≤ $p_{O_2 } $ ≤ 1 atm). The results were used to study the nature of charge transfer. Small-radius polarons were shown to be responsible for the electric properties of the cobaltites under consideration; their concentrations and mobilities were calculated.  相似文献   

9.
Polycrystalline samples of oxygen deficient perovskites SrFe1?xScxO3?δ (0  x  0.5) have been synthesized by direct solid state reactions. Each compound has been stabilized with two different oxygen stoichiometries. The structural study shows, firstly, the good cationic homogeneity of the samples and, secondly, that the Sc and Fe atoms are randomly distributed over the same crystallographic site, whatever the scandium content. This implies that no anionic order is possible. A detailed Mossbauer spectroscopy study clearly shows that the substitution of scandium for iron involves an oxygen content decrease which decreases the tetravalent iron content until its total disappearance for x = 0.5. The evolutions of the isomer shift, the quadrupolar splitting and the relative intensity versus the Sc3+ content are depicted in the present paper.  相似文献   

10.
Zusammenfassung Mit Hilfe röntgenographischer Messungen werden die Boride von Vanadin und Niob untersucht, wobei eine neue Phase der ungefähren Zusammensetzung V2B identifiziert wird, welche mit der entsprechenden Nb-Borid-Phase isotyp ist. Dieselbe Kristallart tritt auch im System: Ta–B auf. Die in der Literatur angegebene -Phase im Zweistoff: Nb–B erweist sich als NbO.Im System: V–B–Si wird wie im analogen Mo-System die Existenz einer ternärenT 2-Phase Me5(Si1/3, B2/3)3 nach-gewiesen1; ihre Gitterkonstanten werden ermittelt.Im Schnitt Ta2Si–Ta2B besteht ein geringes Lösungs-vermögen der beiden Phasen ineinander. Durch Zusatz von 20 Mol-% Ta2Si zu Ta2B erhält man die oben erwähnte neue Kristallart.Bei den Borid-Siliziden der Metalle aus der 4a-, 5a- und 6a-Gruppe werden die Stabilitätsbereiche derT 1-,T 2- undD 88-Phasen miteinander verglichen.  相似文献   

11.
The thermal behaviour of chemically deintercalated samples obtained by HCl treatment of non-stoichiometric Li/Ni mixed oxides is studied. A multi-step reduction of Ni with O2 evolution is observed between room temperature and 800C. Two cation redistribution processes are shown by the exothermal occurrence of a spinel phase at 300C and the endothermal reduction to a rock-salt phase with random distribution of Li and Ni cations in octahedral sites at 800C.The authors wish to express their acknowledgement to CICYT and PFPI for financial support.  相似文献   

12.
《Solid State Sciences》2004,6(7):647-654
The structural, thermal and magnetic properties of the perovskite-type alkaline-earth manganites of the series Sr1−xCaxMnO3−δ (0⩽x⩽1) were investigated. SrMnO3−δ forms a hexagonal perovskite lattice and shows a first-order transformation to a highly defective cubic high-temperature modification. By substituting Ca for Sr (x>0.25) the hexagonal perovskite is suppressed and a cubic (or orthorhombic) lattice becomes stabilized for all temperatures. For x=0.5 and 0.75 cubic perovskites with a large nonstoichiometry (e.g., δ=0.25 for x=0.5) are obtained at 1400 °C. The defective perovskites are prepared by either quenching from high temperature or by cooling in an inert atmosphere. The oxygen vacancies are easily filled by subsequent reoxidation at low temperature (400–600 °C) and stoichiometric samples are obtained. Orthorhombic perovskites are formed at T⩽1200 °C with the nonstoichiometry δ increasing with increasing temperature (e.g., δ=0.06 at 1000 °C and δ=0.14 at 1200 °C for x=0.5). Slow cooling in air results in almost complete reoxidation (δ=0). CaMnO3−δ is an orthorhombic perovskite with a large range of nonstoichiometry (0⩽δ⩽0.30). The cubic to hexagonal phase transformation of the Sr-rich samples is accompanied by a large expansion of the lattice that is reduced by Ca substitution. The Ca/Sr-manganites are antiferromagnets with TN of 170 K for x=0.5 and δ=0.02 and 120 K for x=1 and δ=0.05.  相似文献   

13.
Barium cerate doped by trivalent rare earth metal ions is a potentially huge component of materials for electrochemical industry due to its high protonic conductivity. However, the poor chemical stability especially in the presence of CO2, SO2 or H2O, resulting in decreasing the mechanical durability of obtained materials, limits their possible applications. The new approach towards stable ceramic protonic conductors with high electrical conductivity is presented. Thermal stability of yttrium doped (10 mol%) of BaCeO3 was enhanced by forming the composite material BaCe0.9Y0.1O3–BaWO4 (10 mol% of BaWO4). The synthesis was performed by solid-state reaction method. The detailed study of thermal decomposition of starting powders mixture was performed using thermogravimetry and differential thermal analysis (TG/DTA) techniques combined with Evolved Gas Analysis (EGA—mass spectrometry). Structure, phase composition and microstructure together with thermal stability of sintered materials were determined. The exposition tests were performed to characterise the stability of composites in carbon dioxide and water vapour-rich atmospheres. The samples were exposed to atmosphere containing CO2/H2O (7 % of CO2 in air, 100 % RH) at temperature of 25 °C for 300 h. Thermal analysis supplied with mass spectrometry was applied to analyse the materials after the test. The results of this experiment showed better chemical resistance of composite material—BaCe0.9Y0.1O3 with 10 mol% of BaWO4 compared to single phase material.  相似文献   

14.
Zusammenfassung Der Schnitt: Me3Si (Me=Cr, W bzw. Mo, W) wird an Hand heißgepreßter und in Argon homogenisierter Legierungen untersucht; es läßt sich weder das metastabile W3Si, noch eine W-reiche Mischphase von diesem Typ beobachten. Cr3Si nimmt bei 1500°C etwa 20 Mol%, W3Si auf, während Mo3Si selbst bei 1900°C praktisch kein W3Si löst (ev. wenige Mol%). Dagegen bestehen lückenlose Mischreihen zwischen den Me5Si3-Phasen mit W5Si3-Typ. Die grundsätzliche Aufteilung der Phasenfelder ist damit möglich.Mit 2 Abbildungen  相似文献   

15.
An electron diffraction and microscopy study of the CaFexMn1−xO3−y system treated at 1100°C in air has been performed. An increase of y is accompanied by an increase of the cubic perovskite substructure parameter, the nonstoichiometry being accommodated in several ways. The system contains two solid solutions of the perovskite-type (P) and of the brownmillerite-type (B) and also an intermediate phase (x = 0.6) which makes disordered intergrowth with the B-type solid solution. These results are discussed in terms of multitwinning, randomly dispersed oxygen deficiency, and ordered and disordered intergrowth formation.  相似文献   

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17.
A family of novel highly π-extended tetracyano-substituted acene diimides, named as tetracyanodiacenaphthoanthracene diimides (TCDADIs), have been synthesized using a facile four-fold Knoevenagel condensation strategy. Unlike conventional cyano substitution reactions, our approach enables access to a large π-conjugated backbone with the in-situ formation of four cyano substitutents at room temperature while avoiding extra cyano-functionalization reactions. TCDADIs decorated with different N-alkyl substituents present good solubility, near-coplanar backbones, good crystallinity, and low-lying lowest unoccupied molecular orbital energies of −4.33 eV, all of which contribute to desirable electron-transport performance when applied in organic field-effect transistors (OFET). The highest electron mobility of an OFET based on a 2-hexyldecyl-substituted TCDADI single crystal reaches 12.6 cm2 V−1 s−1, which is not only among the highest values for the reported n-type organic semiconductor materials (OSMs) but also exceeds that of most n-type OSMs decorated with imide units.  相似文献   

18.
(LFN, 0<x<0.6) perovskites were synthesised by a solid-state route and were characterised by powder XRD, dilatometry, four-point DC conductivity measurements and electro-chemical impedance spectroscopy (EIS) on cone-shaped electrodes using a Ce1.9Gd0.1O1.95 (CGO10) electrolyte. All the compounds were of single phase, and they belong to either the cubic or the hexagonal crystal system. The thermal expansion coefficient (TEC) was in the range 10.7*10−6 K−1 to 13.4*10−6 K−1, which continued to increase with increasing nickel content. The highest electronic conductivity was measured for the composition giving a value of 670 S/cm at 380 °C. The highest electro-chemical performance was measured for the composition giving an area specific resistance as low as 5.5 Ωcm2 at 600 °C based on EIS measurements on a cone-shaped electrode. Composite cathodes made from and CGO10 revealed a rather low performance due to an un-optimised micro-structure.
K. KammerEmail: Phone: +45-46775835Fax: +45-46775858
  相似文献   

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