类钙钛矿化合物Ca(Mn2 Cu1)Mn4 O12的磁性与磁电阻效应

利用固相反应法制备了名义成分为Ca(Mn2 Cu1 )Mn4 O1 2 的类钙钛矿锰氧化物 .x射线衍射表明 ,为了获得较为致密的样品和减小杂相含量 ,可以采用高温烧结再在 10 73K长时间空气中退火的制备方法 .样品在低温下同时存在铁磁相和反铁磁相 ,由于反铁磁相的存在导致样品在 4 5K时的磁化强度显著降低 ,并在 8T的高磁场下仍未达到饱和 .样品呈半导体导电性质 ,在 85K和 6T磁场下磁电阻比的最大值可达 - 4 6 % .     

Reverse micellar synthesis and properties of nanocrystalline GMR materials (LaMnO3, La0.67Sr0.33MnO3 and La0.67Ca0.33MnO3): Ramifications of size considerations

Nanoparticles of complex manganites (viz. LaMnO₃, La_0.67Sr_0.33MnO₃ and La_0.67Ca{0.33}MnO₃) have been synthesized using the reverse micellar route. These manganites are prepared at 800‡C and the monophasic nature of all the oxides has been established by powder X-ray diffraction studies. TEM studies show an average grain size of 68, 80 and 50 nm for LaMnO₃, La_0.67Sr_0.33MnO₃ and La_0.67Ca{0.33}MnO₃respectively. Ferromagnetic ordering is observed at around 250 K for LaMnO₃, 350 K for La_0.67Sr_0.33MnO₃ and 200 K for La_0.67Ca{0.33}MnO₃. These Curie temperatures correspond well with those reported for bulk materials with similar composition.     

Photo-induced effect in the layered perovskite manganite La<Subscript>1.2</Subscript>Sr<Subscript>1.8</Subscript>Mn<Subscript>1.8</Subscript>Co<Subscript>0.2</Subscript>O<Subscript>7</Subscript>

It is helpful to study the photo-induced effect in the perovskite manganites not only for elucidating the mechanism of colossal magnetoresistance (CMR) effect but also for potential applications in technology. The laser-induced effect in the Co doping layered perovskite manganites La_1.2Sr_1.8Mn_1.8Co_0.2O₇, is studied in this paper and the obtained results are also compared with that gained in the Nd-doping manganites with cubic perovskite structure.     

Effect of Ga doping on magneto-transport properties in colossal magnetoresistive La0.7Ca0.3Mn1−xGaxO3 (0<x<0.1)

Samples of La_0.7Ca_0.3Mn_1−xGa_xO₃ with x=0, 0.025, 0.05 and 0.10 were prepared by standard solid-state reaction. They were first characterized chemically, including the microstructure. The magnetic properties and various transport properties, i.e. the electrical resistivity, magnetoresistivity (for a field below 8 T), thermoelectric power and thermal conductivity measured each time on the same sample, are reported. The markedly different behaviour of the x=0.1 sample from those with a smaller Ga content, is discussed. The dilution of the Mn³⁺/Mn⁴⁺ interactions with Ga doping considerably reduces the ferromagnetic double exchange interaction within the manganese lattice leading to a decrease of the Curie temperature. The polaron binding energy varies from 224 to 243 meV with increased Ga doping.     

Strained Structure in Ho0.5Sr0.5MnO3

The Ho_0.5Sr_0.5MnO₃ perovskite, synthesized in air, has been studied by combining neutron powder and electron diffraction techniques. The Pnma-type structure exhibits a strong tilting of the MnO₆ octahedra. This octahedra tilting and microtwinning involve a complex strained structure. No structural transition is observed down to 1.4 K, but short-range A-type antiferromagnetism running over only a few perovskite subcells is evidenced below ≈90 K. The different behavior of this perovskite compared to other Ln_0.5Sr_0.5MnO₃ perovskites is discussed in terms of A-site cationic mismatch.     

Synthesis and characterization of Mn-, La-Mn- and La-Ca-Mn-citrates as precursors for LaMnO<Subscript>3</Subscript> and La<Subscript>1−x</Subscript>Ca<Subscript>x</Subscript>MnO<Subscript>3</Subscript>

Mn-, LaMn- and LaCaMn-citrates were synthesized at 60–120°C in ethylene glycol medium using chlorides or nitrates as metal sources. Their composition, IR spectra and thermal decomposition were studied. Equimolar La/Mn ratio has been established in the complex, prepared from chloride solution with the same initial composition of the metals. In the isolated three-metallic complex the molar ratio of the metals deviates from the composition in the initial solution. The final products of the heating of Mn- and mixed-metal LaMn-citrates at 1000°C are phase-homogeneous Mn₃O₄ (hausmannite) and LaMnO₃ respectively. Parasitic phase(s) are observed in La_xCa_1−xMn_yO₃, produced from LaCaMn-citrate.     

Catalytic properties of manganites in the oxidation of CO and hydrocarbon

Manganites with a spinel structure MMn₂O₄ (M = Co, Cu, Zn, Mo) and M¹ _0.5M² _0.5 Mn₂O₄ (M = Co, Cu, Zn, Mg) have been synthesized and tested in the catalytic oxidation of CO, C₃H₆, and ethylbenzene. The dependence of the catalytic activity of the manganites on the nature of the cation has been established. The spinels containing transition metal ions (Cu, Co) are more active. A relation between catalytic and adsorption properties of manganites has been established. The participation of the lattice oxygen in the oxidation of CO to CO₂ has been found. The mechanism of the oxidation is discussed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No, 11, pp, 2686–2669. November, 1996.     

Magnesium substitution in Nd0.7Sr0.3MnO3

Magnesium substitution in Nd_0.7Sr_0.3MnO₃ has been studied by neutron powder diffraction. Polycrystalline samples of nominal compositions Nd_0.7Sr_0.3Mn_1−yMg_yO₃ with y=0.0, 0.1, 0.2 and 0.3 were synthesized by the standard solid-state reaction method. Rietveld refinements of the neutron powder diffraction data showed that all samples had distorted perovskite structure of orthorhombic symmetry. Mg initially preferred to substitute for Nd and only at Mg concentration greater than 0.1, a substantial substitution for Mn occurred. Our study also showed that Mg-substitution did not change the crystal structure of Nd_0.7Sr_0.3MnO₃.     

Ln0.5A0.5MnO3 (Ln=Lanthanide,A= Ca,Sr) Perovskites Exhibiting Remarkable Performance in the Thermochemical Generation of CO and H2 from CO2 and H2O

Perovskite oxides of the Ln_0.5A_0.5MnO₃ (Ln=lanthanide, A=Sr, Ca) family have been investigated for the thermochemical splitting of H₂O and CO₂ to produce H₂ and CO respectively. The amounts of O₂ and CO produced strongly depend on the size of the rare earth ions and alkaline earth ions. The manganite with the smallest rare earth possessing the highest distortion and size disorder as well as the smallest tolerance factor, gives out the maximum amount of O₂, and, hence, the maximum amount of CO. Thus, the best results are found with Y_0.5Sr_0.5MnO₃, which possesses the highest distortion and size disorder. Y_0.5Sr_0.5MnO₃ shows remarkable fuel production activity even at the reduction and oxidation temperatures as low as 1200 °C and 900 °C, respectively.