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1.
Effects of magnesium substitution on the magnetic properties of Nd0.7Sr0.3MnO3 have been investigated by neutron powder diffraction and magnetization measurements on polycrystalline samples of composition Nd0.7Sr0.3MnO3, Nd0.6Mg0.1Sr0.3MnO3, Nd0.6Mg0.1Sr0.3Mn0.9Mg0.1O3, and Nd0.6Mg0.1Sr0.3Mn0.8Mg0.2O3. The pristine compound Nd0.7Sr0.3MnO3 is ferromagnetic with a transition temperature occurring at about 210 K. Increasing the Mg-substitution causes weakened ferromagnetic interaction and a great reduction in the magnetic moment of Mn. The Rietveld analyses of the neutron powder diffraction (NPD) data at 1.5 K for the samples with Mg concentration, y=0.0 and 0.1, show ferromagnetic Mn moments of 3.44(4) and 3.14(4) μB, respectively, which order along the [001] direction. Below 20 K the Mn moments of these samples become canted giving an antiferromagnetic component along the [010] direction of about 0.4 μB at 1.5 K. The analyses also show ferromagnetic polarization along [001] of the Nd moments below 50 K, with a magnitude of almost 1 μB at 1.5 K for both samples. In the samples with Mg substitution of 0.2 and 0.3 only short range magnetic order occurs and the magnitude of the ferromagnetic Mn moments is about 1.6 μB at 1.5 K for both samples. Furthermore, the low-temperature NPD patterns show an additional very broad and diffuse feature resulting from short range antiferromagnetic ordering of the Nd moments.  相似文献   

2.
Crystal structures and magnetic properties of metal telluromolybdates Co1−xZnxTeMoO6 (x=0.0, 0.1,…,0.9) are reported. All the compounds have an orthorhombic structure with space group P21212 and a charge configuration of M2+Te4+Mo6+O6. In this structure, M ions form a pseudo-two-dimensional lattice in the ab plane. Their magnetic susceptibility measurements have been performed in the temperature range between 1.8 and 300 K. The end member CoTeMoO6 shows a magnetic transition at 24.4 K. The transition temperature for solid solutions rapidly decreases with increasing x and this transition disappears between x=0.4 and 0.5, which is corresponding to the percolation limit for the square-planer lattice. From the magnetization, specific heat, and powder neutron diffraction measurements, it is found that the magnetic transition observed in the CoTeMoO6 is a canted antiferromagnetic ordering of Co2+ ions. The antiferromagnetic component of the ordered magnetic moment (3.12(3)μB at 10 K) is along the b-axis. In addition, there exists a small ferromagnetic component (0.28(3)μB) along the a-axis.  相似文献   

3.
Oxides in the system PrCo1−xMgxO3 (x=0.0, 0.05, 0.10, 0.15, 0.20, 0.25) were synthesized by citrate technique and characterized by powder X-ray diffraction and scanning electron microscope. All compounds have a cubic perovskite structure (space group ). The maximum ratio of doped Mg in the system PrCo1−xMgxO3 is x=0.2. Further doping leads to the segregation of Pr6O11 in PrCo1−xMgxO3. The substitution of Mg for Co improves the performance of PrCoO3 as compared to the electrical conductivity measured by a four-probe electrical conductivity analyzer in the temperature range from 298 to 1073 K. The substitution of Mg for Co on the B site may be compensated by the formations of Co4+ and oxygen vacancies. The electrical conductivity of PrCo1−xMgxO3 oxides increases with increasing x in the range of 0.0-0.2. The increase in conductivity becomes considerable at the temperatures ?673 K especially for x?0.1; it reaches a maximum at x=0.2 and 1073 K. From x>0.2 the conductivity of PrCo1−xMgxO3 starts getting lower. This is probably a result of the segregation of Pr6O11 in PrCo1−xMgxO3 , which blocks oxygen transport, and association of oxygen vacancies. A change in activation energy for all PrCo1−xMgxO3 compounds (x=0-0.25) was observed, with a higher activation energy above 573 K and a lower activation energy below 573 K. The reasons for such a change are probably due to the change of dominant charge carriers from Co4+ to Vö in PrCo1−xMgxO3 oxides and a phase transition mainly starting at 573 K.  相似文献   

4.
The effect of Fe doping on the ferromagnetic Nd0.7Pb0.3Mn1−xFexO3 (x=0, 0.025, 0.05, 0.075, 0.1) phases has been studied in order to analyze the double-exchange interaction. The structural and magnetic study has been carried out by neutron powder diffraction and susceptibility measurements between 1.7 and 300 K. The substitution of Fe at the Mn site results in reductions in both the Curie temperature Tc and the magnetic moment per Mn ion without appreciable differences in the crystal structures. All the compounds crystallize in Pnma space group. The thermal evolution of the lattice parameters of the Nd0.7Pb0.3Mn1−xFexO3 (x=0.025, 0.05, 0.075) compounds shows discontinuities in volume and lattice parameters close to the magnetic transition temperature. Increasing amounts of Fe3+ reduces the double exchange interactions and no magnetic contribution for x=0.1 is observed. The magnetic structures of Nd0.7Pb0.3Mn1−xFexO3 (x=0, 0.025, 0.05, 0.075) compounds show that the Nd and Mn ions are ferromagnetically ordered.  相似文献   

5.
Structural, electrical and magnetic properties of Cd-doped La0.7(Ca0.3−xCdx)MnO3 (0?x?0.3) manganites are presented. All compositions were indexed in the orthorhombic (Pnma) space group, except the Cd0.3 sample, indexed as a combination of trigonal and orthorhombic (Pnma) space groups. Substitution of Ca by Cd has a strong influence on the magnetic and magnetoresistive properties of these compounds, continuously decreasing both the magnetic moment and the Curie temperature (from 3.5 μB and 270 K for the x=0 composition to 1.59 μB and 90 K for the fully doped x=0.3 one). Samples corresponding to x=0 and 0.1 show a semiconductor-metal transition at temperatures close to the Curie ones. The measured magnetoresistance change is about 49% at 270 K and 95% at 165 K for those samples, respectively. However, the x=0.2 and 0.3 compositions show insulating behaviour in the whole temperature range studied, with values of the magnetoresistance about 85% at 105 K and 74% at 90 K, respectively. The observed weakening of the double-exchange mechanism as the Cd doping level in these samples increases is discussed in terms of structural properties, cationic disorder and Mn3+/Mn4+content ratio.  相似文献   

6.
A structural, magnetic and electronic study of the cobaltocuprate CoSr2Y2−xCexCu2Oδ (x=0.5-0.8) has been performed. All materials crystallise in the orthorhombic Cmcm symmetry space group in which chains of corner linked CoO4 tetrahedra run parallel to the 1 1 0 direction. An antiferromagnetic transition is observed for x=0.5-0.8; TM increases with x. A change in the dimensionality of the magnetic order occurs at x=0.8 as the interchain distance increases to a critical value. There is charge transfer between the cuprate planes and cobaltate layer as Ce doping increases, so that Co3+ is partially oxidised to Co4+ with a concomitant reduction in the valence of Cu. Superconductivity is not observed in any of the samples and a crossover from Mott to Efros and Shklovskii variable range hopping behaviour is evidenced as x increases from 0.5 to 0.8.  相似文献   

7.
We report the synthesis of SrMn1−xGaxO3−δ perovskite compounds and describe the dependence of their phase stability and structural and physical properties over extended cation and oxygen composition ranges. Using special synthesis techniques derived from thermogravimetric measurements, we have extended the solubility limit of random substitution of Ga3+ for Mn in the cubic perovskite phase to x=0.5. In the cubic perovskite phase the maximum oxygen content is close to 3−x/2, which corresponds to 100% Mn4+. Maximally oxygenated solid solution compounds are found to order antiferromagnetically for x=0-0.4, with the transition temperature linearly decreasing as Ga content increases. Increasing the Ga content introduces frustration into the magnetic system and a spin-glass state is observed for SrMn0.5Ga0.5O2.67(3) below 12 K. These properties are markedly different from the long-range antiferromagnetic order below 180 K observed for the layer-ordered compound Sr2MnGaO5.50 with nominally identical chemical composition.  相似文献   

8.
Five series of perovskite-type compounds in the system La1−xCaxCr1−yTiyO3 with the nominal compositions y=0, x=0-0.5; y=0.2, x=0.2-0.8; y=0.5, x=0.5-1.0; y=0.8, x=0.6-1.0 and y=1, x=0.8-1 were synthesized by a ceramic technique in air (final heating 1350 °C). On the basis of the X-ray analysis of the samples with (Ca/Ti)?1, the phase diagram of the CaTiO3-LaCrIIIO3-CaCrIVO3 quasi-ternary system was constructed. Extended solid solution with a wide homogeneity range is formed in the quasi-ternary system CaCrIVO3-CaTiO3-LaCrIIIO3. The solid solution La(1−x′−y)Ca(x′+y)CrIVxCrIII(1−x′−y)TiyO3 exists by up to 0.6-0.7 mol fractions of CaCrIVO3 (x<0.6-0.7) at the experimental conditions. The crystal structure of the compounds is orthorhombic in the space group Pbnm at room temperature. The lattice parameters and the average interatomic distances of the samples within the solid solution ranges decrease uniformly with increasing Ca content. Outside the quasi-ternary system, the nominal compositions La0.1Ca0.9TiO3, La0.2Ca0.8TiO3, La0.4Ca0.6Cr0.2Ti0.8O3 and La0.3Ca0.7Cr0.2Ti0.8O3 in the system La1−xCaxCr1−yTiyO3 were found as single phases with an orthorhombic structure. In the temperature range between 850 and 1000 °C, the synthesized single-phase compositions are stable at pO2=6×10−16-0.21×105 Pa. Oxygen stoichiometry and electrical conductivity of the separate compounds were investigated as functions of temperature and oxygen partial pressure. The chemical stability of these oxides with respect to oxygen release during thermal dissociation decreases with increasing Ca-content. At 900 °C and oxygen partial pressure 1×10−15-0.21×105 Pa, the compounds with x>y (acceptor doped) are p-type semiconductors and those with x<y (donor doped) and x=y are n-type semiconductors. The type and level of electrical conductivity are functions of the concentration ratios of cations occupying the B-sites of the perovskite structures: [Cr3+]/[Cr4+] and [Ti4+]/[Ti3+]. The maximum electrical conductivity at 900 °C and pO2=10−15 Pa was found for the composition La0.1Ca0.9TiO3 (near 50 S/cm) and in air at 900 °C for La0.5Ca0.5CrO3 (close to 100 S/cm).  相似文献   

9.
Thermoelectric properties of polycrystalline La1−xSrxCoO3, where Sr2+ is substituted in La3+ site in perovskite-type LaCoO3, have been investigated. Sr-doping increases the electrical conductivity (σ) of La1−xSrxCoO3, and also decreases the Seebeck coefficient (S) for 0.01?x?0.40. A Hall coefficient measurement reveals that the increase in electrical conductivity arises from increases in both carrier concentration and the Hall mobility. The decrease in the Seebeck coefficient is caused by a decrease in carrier effective mass as well as increase in carrier concentration. The highest power factor (σS2) is 3.7×10−4 W m−1 K−2 at 250 K for x=0.10. The thermal conductivity (κ) is about 2 W m−1 K−1 at 300 K for 0?x?0.04, and increases for x?0.05 because of an increase in heat transport by conductive carrier. The thermoelectric properties of La1−xSrxCoO3 are improved by Sr-doping, and the figure of merit (Z=σS2 κ−1) reaches 1.6×10−4 K−1 for x=0.06 at 300 K (ZT=0.048). For heavily Sr-doped samples, the thermoelectric properties diminish mainly because of the decrease in the Seebeck coefficient and the increase in thermal conductivity.  相似文献   

10.
Electrical conductivity, thermopower and oxygen content were measured for La1−xSrxFeO3−δ (x=0.2, 0.5, 0.9) within the oxygen partial pressure range 10−4-0.5 atm and at temperatures 750-950 °C. The dominating charge carriers under these experimental conditions are electron holes. The results of oxygen nonstoichiometry measurements are used to estimate the concentration of holes and to analyze data on conductivity and thermopower. The changes in thermopower are described by the model assuming that the number of sites accessible for migration of holes is independent on oxygen content. The mobility of electron holes is calculated, and it is found to be virtually independent on temperature in the compositions with x<0.5 while compositions with x>0.5 exhibit thermally activated mobility and mobility values about 0.1 cm2 V−1 s−1 or smaller. It is suggested that the main contribution to the composition dependent variations in electron hole mobility are associated with Coulomb interactions at small x's, whereas at high degrees of doping the mobility of holes is most strongly affected by the increasing amount of oxygen vacancies.  相似文献   

11.
Ag-doped n-type (Bi2Te3)0.9-(Bi2−xAgxSe3)0.1 (x=0-0.4) alloys were prepared by spark plasma sintering and their physical properties evaluated. When at low Ag content (x=0.05), the temperature dependence of the lattice thermal conductivity follows the trend of (Bi2Te3)0.9-(Bi2Se3)0.1; while at higher Ag content, a relatively rapid reduction above 400 K can be observed due possibly to the enhancement of scattering of phonons by the increased defects. The Seebeck coefficient increases with Ag content, with some loss of electrical conductivity, but the maximum dimensionless figure of merit ZT can be obtained to be 0.86 for the alloy with x=0.4 at 505 K, about 0.2 higher than that of the alloy (Bi2Te3)0.9-(Bi2Se3)0.1 without Ag-doping.  相似文献   

12.
The solid solution of YMn1−xFexO3 (x=0.0, 0.1, 0.2, 0.3, 0.5, 1.0) was synthesized from the citrate precursor route. The hexagonal crystal structure related to YMnO3 was stable for x?0.3. Rietveld refinement was carried out on the composition for x=0.3 and was refined to a major hexagonal phase (∼97%) with 3% of orthorhombic Y(Fe/Mn)O3 phase. The a-axis lattice constant increases and the c-axis lattice constant decreases with x for x?0.2. The increase in the c-axis lattice constant at x=0.3 could be due to the doping of significant amount of d5 ion (high spin Fe3+ ion) in a trigonal bipyramidal crystal field. The detailed structural, magnetic and dielectric properties are discussed.  相似文献   

13.
The crystal and magnetic structures of Sr2(Fe1−xVx)MoO6 (0.03?x?0.1) compounds are refined by alternately using X-ray powder diffraction (XRD) and neutron powder diffraction (NPD) data collected at room temperature. The refinement results reveal that the V atoms selectively occupy the Mo sites instead of the Fe sites for x?0.1. The 3d/4d cation ordering decreases with the increase of the V content. Slight distortions in the lattice and metal octahedra are shown at 300 K, and the distortions increase at 4 K. The magnetic structure at 4 K can be modeled equally well with the moments aligning along [001], [110] or [111] directions. The total moments derived from the NPD data for the [110] and [111] direction models agree well with the magnetic measurements, whereas the [001] model leads to a smaller total moment. Bond valence analysis indicates that Sr ions are properly located in the structure and Mo ions are compatible with both the Fe sites and the Mo sites. The electronic effects are suggested to be responsible for the selective occupation of the V on the Mo sites due to the different distortions of the FeO6 and MoO6 octahedra.  相似文献   

14.
The complex conductivity spectra of mixed alkali borate glasses of compositions y [xLi2O·(1−x)Na2O]·(1−y)B2O3 (with x=0.0, 0.2, 0.4, 0.6, 0.8, 1.0; y=0.1, 0.2, 0.3) in a frequency range between 10−2 Hz and 3 MHz and at temperatures ranging from 298 to 573 K have been studied. For each glass composition the conductivities show a transition from the dc values into a dispersive regime where the conductivity is found to increase continuously with frequency, tending towards a linear frequency dependence at sufficiently low temperatures. Mixed alkali effects (MAEs) in the dc conductivity and activation energy are identified and discussed. It has been for the first time found that the strength of the MAE in the logarithm of the dc conductivity linearly increases with the total alkali oxide content, y, and the reciprocal temperature, 1/T.  相似文献   

15.
Crystals of LixWO3 with nominal compositions, x=0.1, 0.25, 0.3, 0.35, 0.4 and 0.45 were grown by chemical vapour transport method using HgCl2 as transporting agent. A complete transport was achieved with a temperature gradient T1/T2=800/700 °C revealing bluish-black crystals of sizes up to a few 10th of a millimeter. X-ray powder diffraction and infrared (IR) absorption spectra show Perovskite tungsten bronze of cubic symmetry (PTBc) for x=0.45 and 0.4, mixed phase of PTBc and Perovskite tungsten bronze of tetragonal symmetry (PTBt) for x=0.35, 0.3 and 0.25 and of PTBt and Perovskite tungsten bronze of orthorhombic symmetry (PTBo) for x=0.1. The structure of PTBt is explained by the off centring of the W-ions along c and tilting of the WO6 octahedra around c. Crystal slices of mixed phase (i.e. PTBc and PTBt) reveal bright and dark areas on a sub-millimeter scale which are separated by sharp interfaces. Laser ablation inductively coupled plasma optical emission (LA ICP OES) analysis on small spot sizes show the separation into Li contents of x=0.18 (bright areas) and x=0.38 (dark areas) as threshold compositions of PTBt and PTBc, respectively. Polarized reflectivity using a microscope technique in the bright area of the crystals indicates strong anisotropic absorption effects with maximum between 1000 and 6000 cm−1, which are related to optical excitations of polarons. Crystals of composition x=0.4 and 0.45 appear optically homogeneous and show an effective “free carrier-type plasma frequency” (wp) of about 12,900 and 13,700 cm−1, respectively.  相似文献   

16.
Doping of manganese (Mn3+/Mn4+) into the Aurivillius phase Pb1−xBi4+xTi4−xMnxO15 was carried out using the molten salt technique for various Mn concentrations (x=0, 0.2, 0.4, 0.6, 0.8, and 1). Single phase samples could be obtained in the composition range with x up to 0.6 as confirmed by X-ray and neutron diffraction analysis. Dielectric measurements show a peak at 801, 803, 813 and 850 K for samples with x=0, 0.2, 0.4, and 0.6, respectively, related to the ferroelectric transition temperature (Tc). The main contribution of the in-plane polarization for x≤0.2 which was calculated from the atomic positions obtained by the structure analysis is the dipole moment in the Ti(1)O6 layer; however, for x≥0.4 the polarization originates from the dipole moment in the Ti(2)O6 layer. Mn doping in the Pb1−xBi4+xTi4−xMnxO15 does not show any long range magnetic ordering.  相似文献   

17.
Composite solid electrolytes in the system (1 − x)LiNO3-xAl2O3, with x = 0.0-0.5 were synthesized by sol-gel method. The synthesis carried out at low temperature resulted in voluminous and fluffy products. The obtained materials were characterized by X-ray diffraction, differential scanning calorimetry, scanning electron microscopy/energy dispersive X-ray, Fourier transform infrared spectroscopy and AC impedance spectroscopy. Structural analysis of the samples showed base centred cell type of point lattice of LiNO3 for the composite samples with x = 0.1-0.2 and body centred cell for the sample with x = 0.3. A trace amount of α-LiAlO2 crystal phase was also present in these composite samples. The thermal analysis showed that the samples were in a stable phase between 48 °C and 230-260 °C. Morphological analysis indicated the presence of amorphous phase and particles with sizes ranging from micro to nanometre scale for the composite sample with x = 0.1. The conductivities of the composites were in the order of 10−3 and 10−2 S cm−1 at room temperature and 150 °C, respectively.  相似文献   

18.
Ca2FeAl1−xMgxO5 (x=0, 0.05 and 0.1) compounds adopting the brownmillerite-type structure were prepared by a self-combustion route using two different fuels. Characterisation was performed using X-ray powder diffraction, Mössbauer spectroscopy, magnetisation measurements, chemical analysis, scanning electron microscopy and 4-point dc conductivity measurements. Global results indicate that the solubility limit was reached for x=0.1. An antiferromagnetic behaviour was detected for all studied compositions, with magnetic ordering temperatures of 340 and 290 K for x=0 and 0.05, respectively. Mg doping increases the number of iron cations in tetrahedral sites, which induces magnetisation enhancement at low temperatures through the coupling between octahedral iron cations in different octahedral planes. The compounds exhibit semiconductor behaviour and Mg2+ doping yields a significant enhancement of the total conductivity, which can be essentially attributed to the presence of Fe4+ ions.  相似文献   

19.
The 6H BaRu1−xMnxO3 with the hexagonal BaTiO3 structure was synthesized using high-pressure sintering method. It is found that the lattice parameter deviates from Vegard's law at x=0.3 for the solid solutions due to the charge transfer effects at B-site. The substitution of Mn for Ru cations gives rise to the short-range magnetic ordering, due to the disordered arrangement of Ru and Mn cations. The compounds are weak ferromagnetic in the x range 0.05-0.40, with the maximal Curie temperature Tc 175.2 K at x=0.10. They are of spin-glass-like magnetism at lower temperature at x?0.1. With Mn doping, the 6H BaRuO3 transforms to a semiconductor from the primal metal at x=0.30. The resistance as a function of temperature below about 70 K follows the two-dimensional variable-range hopping conduction mechanism in BaRu0.50Mn0.50O3.  相似文献   

20.
The non-linear thermal expansion behaviour observed in Ce1−yPryO2−δ materials can be substantially controlled by Gd substitution. Coulometric titration shows that the charge compensation mechanism changes with increasing x, in the system GdxCe0.8−xPr0.2O2−δ. For x=0.15, charge compensation is by vacancy formation and destabilises the presence of Pr4+. At x=0.2, further Gd substitution is charge compensated by additionally raising the oxidation state of Pr rather than solely the creation of further oxygen ion vacancies. Oxygen concentration cell e.m.f. measurements in an oxygen/air potential gradient show that increasing Gd content decreases ionic and electronic conductivities. Ion transference numbers measured under these conditions show a positive temperature dependence, with typical values to=0.90,0.98 and 0.80 for x=0,0.15 and 0.2, respectively, at 950 °C. These observations are discussed in terms of defect association. Oxygen permeation fluxes are limited by both bulk ambipolar conductivity and surface exchange. However, the composition dependent trends in permeability are shown to be dominated by ambipolar conductivities, and limited by the level of electronic conductivity. At the highest temperatures, oxygen permeability of composition x=0.2 approaches that of composition x=0, Ce0.8Pr0.2O2−δ, with specific oxygen permeability values approximately 2×10−9 mol s−1 cm−1 at 950 °C, but offering much better thermal expansion properties.  相似文献   

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