首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 31 毫秒
1.
R. Jimenez  A. Rivera  A. Varez  J. Sanz   《Solid State Ionics》2009,180(26-27):1362-1371
The dependence of Li mobility on structure and composition of Li0.5 − xNaxLa0.5TiO3 perovskites (0 ≤ x ≤  0.5) has been investigated by means of neutron diffraction, nuclear magnetic resonance and impedance spectroscopy. At 300 K, all samples display a rhombohedral superstructure (R-3c S.G.), where octahedra are out of phase tilted along [111] direction of the ideal cubic cell. The elimination of the octahedral tilting is responsible for the rhombohedral–cubic transformation, detected near 1000 K. In these perovskites, La and Na cations are randomly distributed in A sites, but Li ions are fourfold coordinated at unit cell faces of the cubic perovskite. Lithium conductivity, σ300 K, decreases with the sodium content, decreasing from values typical of fast ionic conductors, 10− 3 S/cm, to those of good insulators, 10− 10 S/cm, when the interconnectivity between vacant A sites is lost (x > 0.3). In samples with x < 0.3, dc conductivity displays a non-Arrhenius behaviour, decreasing activation energy from ~ 0.37 to 0.25 eV when the sample is heated between 77 and 500 K. The temperature dependence of BLi factors shows the existence of two regimes for Li motion. Below 373 K, Li ions remain partially located near square oxygen windows that connect contiguous A sites, but above 400 K, extended Li motions become dominant. The additional decrease of activation energy from 0.25 to 0.16 eV (low-temperature 7Li NMR value), should require the full elimination of octahedral tilting which is only produced above 1000 °C.  相似文献   

2.
Magnetic and EPR data have been collected for complex [Cu(L-Arg)2](NO3)2·3H2O (Arg=arginine). Magnetic susceptibility χ in the temperature range 2-160 K, and a magnetization isotherm at T=2.29(1) K with magnetic fields between 0 and 9 T were measured. The observed variation of χT with T indicates predominant antiferromagnetic interactions between Cu(II) ions coupled in 1D chains along the b axis. Fitting a molecular field model to the susceptibility data allows to evaluate g=2.10(1) for the average g-factor and J=−0.42(6) cm−1 for the nearest neighbor exchange coupling (defined as Hex=-∑JijSi·Sj). This coupling is assigned to syn-anti equatorial-apical carboxylate bridges connecting Cu(II) ion neighbors at 5.682 Å, with a total bond length of 6.989 Å and is consistent with the magnetization isotherm results. It is discussed and compared with couplings observed in other compounds with similar exchange bridges. EPR spectra at 9.77 were obtained in powder samples and at 9.77 and at 34.1 GHz in the three orthogonal planes of single crystals. At both microwave frequencies, and for all magnetic field orientations a single signal arising from the collapse due to exchange interaction of resonances corresponding to two rotated Cu(II) sites is observed. From the EPR results the molecular g-tensors corresponding to the two copper sites in the unit cell were evaluated, allowing an estimated lower limit |J |>0.1 cm−1 for the exchange interaction between Cu(II) neighbors, consistent with the magnetic measurements. The observed angular variation of the line width is attributed to dipolar coupling between Cu(II) ions in the lattice.  相似文献   

3.
Magnetization and susceptibility were investigated as a function of temperature and magnetic field in polycrystalline Mn[Cr0.5Ga1.5]S4 spinel. The dc susceptibility measurements at 919 Oe showed a disordered ferrimagnetic behaviour with a Curie-Weiss temperature θCW=−55 K and an effective magnetic moment of 5.96 μB close to the spin-only value of 6.52 μB for Cr3+ and Mn2+ ions in the 3d3 and 3d5 configurations, respectively. The magnetization measured at 100 Oe revealed the multiple magnetic transitions with a sharp maximum at the Néel temperature TN=3.9 K, a minimum at the Yafet-Kittel temperature TYK=5 K, a broad maximum at the freezing temperature Tf=7.9 K, and an inflection point at the Curie temperature TC=48 K indicating a transition to paramagnetic phase. A large splitting between the zero-field-cooled (ZFC) and field-cooled (FC) magnetizations at a temperature smaller than TC suggests the presence of spin-glass-like behaviour. This behaviour is considered in a framework of competing interactions between the antiferromagnetic ordering of the A(Mn) sublattice and the ferromagnetic ordering of the B(Cr) sublattice.  相似文献   

4.
Antiferromagnetic phase transition in two vanadium garnets AgCa2Co2V3O12 and AgCa2Ni2V3O12 has been found and investigated extensively. The heat capacity exhibits sharp peak due to the antiferromagnetic order with the Néel temperature TN=6.39 K for AgCa2Co2V3O12 and 7.21 K for AgCa2Ni2V3O12, respectively. The magnetic susceptibilities exhibit broad maximum, and these TN correspond to the inflection points of the magnetic susceptibility χ a little lower than T(χmax). The magnetic entropy changes from zero to 20 K per mol Co2+ and Ni2+ ions are 5.31 J K−1 mol-Co2+-ion−1 and 6.85 J K−1 mol-Ni2+-ion−1, indicating S=1/2 for Co2+ ion and S=1 for Ni2+ ion. The magnetic susceptibility of AgCa2Ni2V3O12 shows the Curie-Weiss behavior between 20 and 350 K with the effective magnetic moment μeff=3.23 μB Ni2+-ion−1 and the Weiss constant θ=−16.4 K (antiferromagnetic sign). Nevertheless, the simple Curie-Weiss law cannot be applicable for AgCa2Co2V3O12. The complex temperature dependence of magnetic susceptibility has been interpreted within the framework of Tanabe-Sugano energy diagram, which is analyzed on the basis of crystalline electric field. The ground state is the spin doublet state 2E(t26e) and the first excited state is spin quartet state 4T1(t25e2) which locates extremely close to the ground state. The low spin state S=1/2 for Co2+ ion is verified experimentally at least below 20 K which is in agreement with the result of the heat capacity.  相似文献   

5.
Nuclear magnetic resonance (NMR) on 63Cu nuclei was performed in a pressure-induced superconductor Sr2Ca12Cu24O41 at an optimum pressure of 3.8 GPa. A pressure of 3.8 GPa was achieved by improving a piston-cylinder-type pressure cell and developing a NMR probe with a steady-load control system. We found that the spin gap still exists even at the optimum pressure. The spin gap was almost the same at pressures below 3.5 GPa on the pressure-temperature phase diagram, whereas it decreased rather drastically above 3.5 GPa.  相似文献   

6.
A study of the half-metallic character of the semi Heusler alloys Co1−xCuxMnSb (0?x?0.9) is presented. We investigated the saturation magnetization MS at temperatures from 5 K to room temperature and the temperature dependence of the DC magnetic susceptibility χ above Curie temperature TC. The magnetic moments at 5 K, for most compositions are very close to the quantized value of 4 μB for Mn3+ ion, the compound with 90% Co substituted by Cu is still ferromagnetic with MS (5 K)=3.78 μB/f.u. These results emphasize the role of Co atoms in maintaining the ferromagnetic order in the material. The Curie temperature is decreased from 476 K to about 300 K as the Cu content increases from 0% to 90%. Above TC, the χ−1 vs T curves follow very well the Curie–Weiss law. The effective moment μeff and paramagnetic Curie temperature θ are derived. A comparison between the values of MS at 5 K and μeff shows a transition from localized to itinerant spin system in these compounds.  相似文献   

7.
The thermomagnetic behaviour (within the temperature range 553-300 K) for the bulk composite Nd60Fe30Al10 alloy is described in terms of a transition from paramagnetic to superferromagnetic state at T=553 K, followed by a ferromagnetic ordering for T<473 K. For the superferromagnetic regime, the alloy thermomagnetic response was associated to a homogeneous distribution of magnetic clusters with mean magnetic moment and size of 1072 μB and 2.5 nm, respectively. For T<473 K, a pinning model of domain walls described properly the alloy coercivity dependence with temperature, from which the domain wall width and the magnetic anisotropy constant were estimated as being of ≈8 nm and ≈105 J/m3, typical values of hard magnetic phases. Results are supported by microstructural and magnetic domain observations.  相似文献   

8.
We have investigated the magnetic, electrical transport and electron spin resonance (ESR) properties of polycrystalline Fe-doped manganite LaMn0.7Fe0.3O3+δ prepared by sol–gel method. A typical cluster-glass feature is presented by DC magnetization and AC susceptibility measurements and a sharp but shallow memory effect was observed. Symmetrical Lorentzian lines of the Mn/Fe spectra were detected above 120 K, where the sample is a paramagnetic (PM) insulator. When the temperature decreases from 120 K, magnetic clusters contributed from ferromagnetic (FM) interaction between Mn3+ and Mn3+/Fe3+ ions develop and coexist with PM phase. At lower temperature, these FM clusters compete with antiferromagnetic (AFM) ones between Fe3+ ions, which are associated with a distinct field-cooled (FC) effect in characteristic of cluster-glass state.  相似文献   

9.
Solid solutions of (CsHSO4)1 − x(CsH2PO4)x (x = 0.25-0.75) were synthesized by mechanical milling method over a wide range of compositions. Superprotonic cubic phase was confirmed for all these samples between 293 and 420 K depending on its composition. These superprotonic phases have primitive cubic structure similar to that of CsH2PO4. The kinetic stability of the supercooled cubic phase depends both on the composition x and the humidity of surrounding atmosphere. The most stable composition of the cubic phase was found around x = 0.67 and could be maintained for several days even under ambient atmosphere. The ionic conductivities of these superprotonic phases reached 10− 2–10− 3 S∙cm− 1 at 450 K. With increasing x the ionic conductivity at the superprotonic phase decreased continuously associated with the increase of the activation energy. These findings suggest that the average number of the hydrogen bonds between XO4 (X = S, P) units plays an important role on the stability of the cubic phase and also on the conductivity.  相似文献   

10.
The redox behaviour of a CuO-CeO2/Al2O3 catalyst is studied under propane reduction and re-oxidation. The evolution of the local Cu and Ce structure is studied with in-situ transmission X-ray absorption spectroscopy (XAS) at the Cu K and Ce L3 absorption edges.CuO and CeO2 structures are present in the catalyst as such. No structural effect on the local Cu structure is observed upon heating in He up to 873 K or after pre-oxidation at 423 K.Exposure to propane at reaction temperature (600-763 K) fully reduces the Cu2+ cations towards metallic Cu0. Quick EXAFS spectra taken during reduction show a small amount of intermediate Cu1+ species. Parallel to the CuO reduction, CeO2 is also reduced in the same temperature range. About 25% of the Ce4+ reduces rapidly to Ce3+ in the 610-640 K temperature interval, while beyond 640 K a further slower reduction of Ce4+ to Ce3+ occurs. At 763 K, Ce reduction is still incomplete with 32% of Ce3+.Re-oxidation of Cu and Ce is fast and brings back the original oxides.The propane reduction of the CuO-CeO2/Al2O3 catalyst involves both CuO and CeO2 reduction at similar temperatures, which is ascribed to an interaction between the two compounds.  相似文献   

11.
Magnetic nanoparticles of La0.67Sr0.33MnO3 (LSMO) manganite were prepared by sol-gel method. Phase formation and crystal structure of the synthesized powder were examined by the X-ray diffraction (XRD) using the Rietveld analysis. The mean particle size was determined by the transmission electron microscopy (TEM). Infrared transmission spectroscopy revealed that stretching and bending modes are influenced by calcinations temperature. The temperature dependence of the ac magnetic susceptibility was measured at different frequencies and ac magnetic fields in the selected ranges of 40-1000 Hz and 80-800 A/m, respectively. The temperature dependence of ac susceptibility shows a characteristic maxima corresponding to the blocking temperature near room temperature. The frequency dependence of the blocking temperature is well described by the Vogel-Fulcher law. By fitting the experimental data with this law, the relaxation time τ0=1.7×10−12 s, characteristic temperature T0=262±3 K, anisotropy energy Ea/k=684±15 K and effective magnetic anisotropy constant keff=2.25×104 erg/cm3 have been obtained. dc Magnetization measurement versus magnetic field shows that some of LSMO nanoparticles are blocked at 293 K. The role of magnetic interparticle interactions on the magnetic behavior is also investigated.  相似文献   

12.
La0.8Sr0.2Co1−xFexO3 (x=0.15, 0.2, 0.3) samples were studied by means of AC magnetic susceptibility, magnetization, magnetoresistance and 57Fe Mössbauer spectrometry. Iron was found to take on a high spin 3d5−α electronic state in each of the samples, where α refers to a partly delocalized 3d electron. The compounds were found to exhibit a spin-cluster glass transition with a common transition temperature of ∼53 K. The spin-cluster glass transition is visualized in the 57Fe Mössbauer spectra as the slowing down of magnetic relaxation below ∼70 K, thereby showing that iron takes part in the formation of the glassy magnetic phase. The paramagnetic-like phase found at higher temperatures is identified below Tc≈195 K as being composed of weakly interacting, magnetically ordered nanosized clusters of magnetic ions in part with a magnetic moment oriented opposite to the net magnetic moment of the cluster. For each of the samples a considerable low-temperature negative magnetoresistance was found, whose magnitude in the studied range decreases with increasing iron concentration. The observed results obtained on the present compounds are qualitatively explained assuming that the absolute strengths of magnetic exchange interactions are subject to the relation ∣JCo–Co∣<∣JFe–Co∣<∣JFe–Fe∣.  相似文献   

13.
Raman spectroscopy studies are reported for the RuSr2Eu1.5Ce0.5Cu2O10 (Ru-1222) compound at various temperatures of 300, 250, 200 and 90 K. Three distinct vibrational bands: the first at 110, 140, and 160 cm−1, the second at 295 and 347 cm−1, and third one at 651 cm−1 are seen in Raman spectra of the compound at room temperature. These bands are attached to the Cu atoms’ c-direction, the Ru atoms’ ab-plane stretching and Ru atoms’ c-direction anti-stretching modes. Below 200 K, an extra vibrational mode is also seen at 260 cm−1. Also, with a decrease in temperature, though the Cu vibrational modes remain intact, the Ru atoms’ ab-plane stretching (295 cm−1) and c-direction anti-stretching (651 cm−1) modes shift gradually to higher wave number positions. The frequencies of modes at 260 and 651 cm−1 showed anomalous softening and line-width broadening below 100 K that corroborates well with the spin ordering seen in susceptibility studies. The studied compound is a ferromagnetic superconductor with magnetic ordering of the Ru spins at 200 K and superconductivity below 30 K. A magnetic and electrical transport characterization of the compound is also presented briefly.  相似文献   

14.
Thermo-gravimetric, differential scanning calorimetry and comprehensive 57Fe Mössbauer spectroscopy studies of amorphous and crystalline ferromagnetic glass coated (Co0.2Fe0.8)72.5Si12.5B15 micro-wires have been recorded. The Curie temperature of the amorphous phase is TC(amorp) ∼730 K. The analysis of the Mössbauer spectra reveals that below 623 K the easy axis of the magnetization is axial-along the wires, and that a tangential or/and radial orientation occurs at higher temperatures. At 770 K, in the first 4 hours the Mössbauer spectrum exhibits a pure paramagnetic doublet. Crystallization and decomposition to predominantly α-Fe(Si) and Fe2B occurs either by raising the temperature above 835 K or isothermally in time at lower temperatures. Annealing for a day at 770 K, leads to crystallization. In the crystalline material the magnetic moments have a complete random orientation. After cooling back to ambient temperature, both α-Fe(Si) and Fe2B in the glass coated wire show pure axial magnetic orientation like in the original amorphous state. The observed spin reorientations are associated with changes in the stress induced by the glass coating.  相似文献   

15.
The effect of doping of rare earth Pr3+ ion as a replacement of Sm3+ in Sm0.5Sr0.5MnO3 is investigated. Temperature dependent dc and ac magnetic susceptibility, resistivity, magnetoresistance measurements on chemically synthesized (Sm0.5−xPrx)Sr0.5MnO3 show various unusual features with doping level x=0.15. The frequency independent ferromagnetic to paramagnetic transition at higher temperature (∼191 K) followed by a frequency dependent reentrant magnetic transition at lower temperature (∼31 K) has been observed. The nature of this frequency dependent reentrant magnetic transition is described by a critical slowing down model of spin glasses. From non-linear ac susceptibility measurements it has been confirmed that the finite size ferromagnetic clusters are formed as a consequence of intrinsic phase separation, and undergo spin glass-like freezing below a certain temperature. There is an unusual observation of a 2nd harmonic peak in the non-linear ac susceptibility around this reentrant magnetic transition at low temperature (∼31 K). Arrott plots at 10 and 30 K confirm the existence of glassy ferromagnetism below this low temperature reentrant transition. Electronic- and magneto-transport measurements show a strong magnetic field—temperature history dependence and strong irreversibility with respect to the sweeping of magnetic field. These results are attributed to the effect of phase separation and kinetic arrest of the electronic phase in this phase separated manganite at low temperatures.  相似文献   

16.
Cu(im)6 complexes in Zn(im)6Cl2·4H2O exhibit a strong Jahn-Teller effect which is static below 100 K and the complex in localized in the two low-energy potential wells. We have reinvestigated electron paramagnetic resonance (EPR) spectra in the temperature range 4.2-300 K and determined the deformation directions produced by the Jahn-Teller effect, energy difference 11 cm−1 between the wells and energy 300 cm−1 of the third potential well. The electron spin relaxation was measured by electron spin echo (ESE) method in the temperature range of 4.2-45 K for single crystal and powder samples. The spin-lattice relaxation is dominated by a local mode of vibration with energy 11 cm−1 at low temperatures. We suppose that this mode is due to reorientations (jumps) of the Cu(im)6 complex between the two lowest energy potential wells. At intermediate temperatures (15-35 K), the T1 relaxation is determined by the two-phonon Raman processes in acoustic phonon spectrum with Debye temperature ΘD=167 K, whereas at higher temperatures the relaxation is governed by the optical phonon of energy 266 cm−1. The ESE dephasing is produced by an instantaneous diffusion below 15 K with the temperature-independent phase memory time , then it grows exponentially with temperature with an activation energy of 97 cm−1. This is the energy of the first excited vibronic level. The thermal population of this level leads to a transition from anisotropic to isotropic EPR spectrum observed around 90 K. FT-ESE gives ESEEM spectrum dominated by quadrupole peaks from non-coordinating 14N atom of the imidazole rings and the peak from double quantum transition νdq. We show that the amplitude of the νdq transition can be used to determine the number of non-coordinating nitrogen atoms.  相似文献   

17.
We report the results of the temperature-dependent neutron diffraction measurements on the nearly half-doped (La0.325Tb0.125)(Ca0.3Sr0.25)MnO3 manganite sample. The simultaneous doping of magnetic Tb3+ and divalent Sr2+ in the La0.7Ca0.3MnO3 system results into a large A-site size disorder. Rietveld refinement of neutron diffraction data reveal that the single phase sample crystallizes in a distorted orthorhombic structure. Increased 〈rA〉 value affects the transport behavior that results into an insulating-like behavior of the sample. Under application of 1 T field sample exhibit insulating-like behavior while insulator-metal transition (TIM) is exhibited under 5 and 8 T fields. Variable range hoping (VRH) mechanism of charge carriers is exhibited in the insulating region. Field cooled and zero field cooled magnetization measurement shows the Curie temperature (TC)~47 K. The refinement of the ND data collected at various temperatures below 300 K shows that there is no structural phase transition in the compound. Around 100 K, a magnetic peak appears at lower angle that can be ascribed to the presence of the A-type antiferromagnetic (AFM) phase. Two more peaks are observed around 50 K at lower angles that can be fitted in CE-type antiferromagnetic phase. Splitting of the peaks at lower temperatures is the signature of orbital ordering in the presently studied nearly half-doped manganite system. Results of the detailed structural analysis of the temperature-dependent ND measurements on (LaTb)0.45(CaSr)0.55MnO3 sample has been discussed in the light of coexisting A-type and CE-type antiferromagnetic phases present in the sample at low temperature.  相似文献   

18.
The magnetic property of double doped manganite Nd0.5(1+x)Ca0.5(1−x)Mn(1−x)CrxO3 with a fixed ratio of Mn3+:Mn4+=1:1 has been investigated. For the undoped sample, it undergoes one transition from charge disordering to charge ordering (CO) associated with paramagnetic (PM)-antiferromagnetic (AFM) phase transition at T<250 K. The long range AFM ordering seems to form at 35 K, rather than previously reported 150 K. At low temperature, an asymmetrical M-H hysteresis loop occurs due to weak AFM coupling. For the doped samples, the substitution of Cr3+ for Mn3+ ions causes the increase of magnetization and the rise of Tc. As the Cr3+ concentration increases, the CO domain gradually becomes smaller and the CO melting process emerges. At low temperature, the FM superexchange interaction between Mn3+ and Cr3+ ions causes a magnetic upturn, namely, the second FM phase transition.  相似文献   

19.
The magnetic, thermodynamic and electronic structure properties are discussed for the CeNi4Cr compound. The X-ray photoemission spectra (XPS) provide an evidence of a mixed valence behavior with the occupancy of the f states nf=0.89 and their hybridization with the conduction electrons Δ=30 meV. These values reproduce well the magnetic susceptibility χ(T=0), which is enhanced compared to similar CeNi4M (M=Al, B, Cu) compounds. In combination with a slightly increased electronic specific heat coefficient (up to 100 mJ mol−1 K−2), this compound can be classified as being on the border of the heavy fermion and mixed valence behavior. Using a small magnetic field in the χ(T) measurements reveals a presence of magnetically ordered impurity phase, which is easily damped by higher fields and it is shown that the contribution of this phase is minor. The question of the dependence of the electronic specific heat coefficient on the magnetic field is also addressed and the observations agree well with theoretical predictions based on the Anderson model.  相似文献   

20.
Lithium tetraborate (Li2B4O7) is a tissue equivalent material and single crystals of this material doped with Cu are promising for dosimetric applications. In the present study highly transparent single crystals of lithium tetraborate (Li2B4O7) doped with Cu (0.5 wt%) have been grown using the Czochralski technique. The Li2B4O7:Cu crystals were studied using photoluminescence, X-ray diffraction (XRD), UV-vis transmission, time resolved fluorescence and thermoluminescence (TL) techniques. The TL readout of Li2B4O7:Cu crystals showed two well-defined glow peaks at 402 K (peak-1) and 513 K (peak-2) for a 4 K/s heating rate. While the low temperature TL peak-1 fades completely within 24 h at room temperatures, the main dosimetric peak-2 remains the same. The TL sensitivity of the grown single crystal is found to be 3.3 times that of a conventional TL phosphor, TLD-100. The Li2B4O7:Cu crystals showed a linear TL dose-response in the range from 1 mGy to 1 kGy. The TL analysis using a variable dose method revealed first order kinetics for both the peaks. Trap depth and frequency factor for peak-1 were found to be 0.81 eV and 5.2×109 s−1, whereas for peak-2 the values were 1.7 eV and 1.7×1016 s−1, respectively.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号