Structural, magnetic and electrical properties of Al substituted Ni-Zn ferrite nanoparticles

Nanocrystalline ferrite materials having the general formula Ni_0.7Zn_0.3Fe_2−xAl_xO₄ (0.0 ≤ x ≤ 0.5) have been synthesized by citrate-gel auto combustion method and characterized using X-ray diffraction (XRD), energy dispersive X-ray (EDX), field emission scanning electron microscopy (FE-SEM), dc magnetization, dielectric and impedance spectroscopy measurements. XRD studies confirm that all the samples show single phase cubic spinel structure. The crystallite size of Ni_0.7Zn_0.3Fe_2−xAl_xO₄ (0.0 ≤ x ≤ 0.5) nanoparticles calculated using the Debye-Scherrer formula was found in the range of 13-17 nm. The value of lattice parameter ‘a’ is found to decrease with increasing Al³⁺ content. EDX patterns confirm the compositional formation of the synthesized samples. FE-SEM micrographs show that all the samples have nano-crystalline behavior and particles show spherical shape. The variation of dielectric properties ?′,?″, and tan δ with frequency shows the dispersion behavior which is explained in the light of Maxwell-Wagner type of interfacial polarization in accordance with the Koop's phenomenological theory. The dc magnetization studies infer that magnetic moment of Ni_0.7Zn_0.3Fe_2−xAl_xO₄ (0.0 ≤ x ≤ 0.5) nanoparticles was found to decrease with Al doping. Impedance spectroscopy techniques have been used to investigate the effect of grain and grain boundary on the electrical properties of the synthesized compounds.     

Structure, microstructure and electrical properties of (1 − x − y)Bi0.5Na0.5TiO3–xBi0.5K0.5TiO3–yBi0.5Li0.5TiO3 lead-free piezoelectric ceramics

The ternary system (1 − x − y)Bi_0.5Na_0.5TiO₃–xBi_0.5K_0.5TiO₃–yBi_0.5Li_0.5TiO₃ (abbreviated to BNKLT-x/y) was synthesized by conventional oxide-mixed method. The phase structure, microstructure, and dielectric, ferroelectric and piezoelectric properties of the ceramics were investigated. The X-ray diffraction patterns showed that pure perovskite phase with rhombohedral structure can be obtained in all the ceramics. The grain size varied with x and y. The temperature dependence of dielectric constant and dielectric loss revealed there were two phase transitions which were from ferroelectric (tetragonal) to anti-ferroelectric (rhombohedral) and anti-ferroelectric to paraelectric (cubic). Either increasing x or y content can make T_m (the temperature at which dielectric constant _r reaches the maximum) increase. With the addition of Bi_0.5K_0.5TiO₃, the remanent polarization P_r increased but the coercive field E_c decreased. With the addition of Bi_0.5Li_0.5TiO₃, P_r increased obviously and E_c increased slightly. Due to the stronger ferroelectricity by modifying Bi_0.5K_0.5TiO₃ and Bi_0.5Li_0.5TiO₃, the piezoelectric properties were enhanced at x = 0.22 and y = 0.10, which were as follows: P_r = 31.92 μC/cm², E_c = 32.40 kV/cm, _r = 1118, tan δ = 0.041, d₃₃ = 203 pC/N and K_p = 0.31. The results show that the BNKLT-x/y ceramics are promising candidates for the lead-free materials.     

Structural, magnetic and magnetotransport properties of La0.8Sr0.2MnO3/xLaMnO3 composites

The effect of LMO doping on the structure, magnetic and magnetotransport properties of La_0.8Sr_0.2MnO₃ (LSMO)/xLaMnO₃ (LMO) has been investigated. Two types of LSMO/xLMO composites, named as SL_x (low temperature sintered samples) and SH_x (high temperature sintered samples) samples, were prepared by different sintering temperature and solid-state reaction method. The presence of LMO at the grain boundaries increases the disordered states at the surface of the grains and therefore the magnetization and transition temperature decrease by increasing the amount of LMO doping level. Results show that the rate of decreasing of transition temperature is much more for high temperaure sintered samples. Also the resistivity of samples increases by the increase of LMO doping level. Results also show that the LMO doping has an effect on a low field magnetoresistance (LFMR). The value of LFMR increases for low doping level of 0 ≤ x ≤ 15, for SL_x samples and 0 ≤ x ≤ 10 for SH_x samples. Also LFMR decreases at high doping level. The spin dependent tunneling and scattering at the interfaces of the grain boundaries are responsible for the increase of LFMR at low doping level, while reduction of LFMR at high doping level may result from the grain boundary becoming too thick for electron tunneling.     

Structural, electrical and magnetic properties of Cu1−xZnxFe2O4 ferrites (0 ≤ x ≤ 1)

Copper–zinc ferrites bearing chemical formula Cu_1−xZn_xFe₂O₄ for x ranging from 0.0 to 1.0 with the step increment of 0.2 were prepared by the standard solid-state technique. The variation of Zn substitution has a significant effect on the structural, electrical and magnetic properties. Lattice parameters ‘a’ increased from 8.370 to 8.520 Å. Dielectric constant decreased up to 311 with the increase in frequency from 80 Hz to 1 MHz at room temperature. All the samples follow the Maxwell–Wagner's interfacial polarization. Saturation magnetization, magnetic moment and Yafet–Kittel angles were also determined. The possible reasons responsible for the change in density related, electrical and magnetic properties with the increase in Zn concentration are undertaken.     

Structural, magnetic and electrical properties of (La0.70−xNdx)Sr0.30Mn0.70Cr0.30O3 with 0 ≤ x ≤ 0.30

The structural, magnetic and electrical properties of (La_0.70−xNd_x)Sr_0.30Mn_0.70Cr_0.30O₃ perovskites (0 ≤ x ≤ 0.30) prepared by the usual ceramic procedure were investigated. Structural Rietveld refinement revealed that these compounds crystallize in a rhombohedral perovskite structure when x = 0, 0.10 and 0.20, while for x = 0.30 the structure becomes orthorhombic (Pbnm). It was found that the substitution of La by Nd reduces the Curie temperature (T_C). The FC, ZFC, M(H) and AC susceptibility measurements show typical canted-antiferromagnetism for the Nd-doped samples, in which a ferromagnetic component coexists with predominant antiferromagnetic interactions. The values of the magnetization (M(H)) decrease very slightly when increasing the Nd content, compared to the undoped sample (M_S values at 5 T and 2 K are, respectively, 47.9, 47.3 and 47.5 emu/g for x = 0.10, 0.20 and 0.30, compared to 48.2 emu/g for x = 0), indicating that the Nd³⁺ contribution is negligible compared to the total moment of the ferromagnetic (Mn/Cr) network. The resistivity increases by several orders of magnitude with Nd-doping and the semi-conducting behaviour persists in the whole temperature range. The interaction between Mn⁴⁺–O–Cr³⁺and Cr³⁺–O–Cr³⁺ is responsible for the semi-conducting state.     

Investigation of structural and electrical properties of (1 − x) Bi0.5Mg0.5TiO3–(x) PbTiO3 ceramic system

A 3 V cathode material for lithium ion batteries, Li_0.33MnO₂, was synthesized by solid-state reaction. Two Mn crystallographic positions, Mn₍₁₎ and Mn₍₂₎, were determined by X-ray diffraction analysis. The [Mn₍₂₎O₆] octahedron had a lower symmetrical degree than that of [Mn₍₁₎O₆], which was attributed to the geometrical effects of the non-symmetrical environment around Mn₍₂₎. Li_0.33MnO₂ delivered a reversible discharge capacity 140 mA h g⁻¹. In situ synchrotron diffraction clearly showed a reversible phase transition of Li_0.33MnO₂ during electrochemical process. The analysis of X-ray absorption near edge spectroscopy observed the conversion of Mn⁴⁺ to Mn³⁺ with Li⁺ intercalation into Li_0.33MnO₂, accompanied by the formation of more severely distorted [MnO₆] octahedron.     

Structural, magnetic and electrical transport properties for a series of La1−xSrxFe1−xMnxO3 (0.3 ≤ x ≤ 0.7) compounds

The structural, electrical transport and magnetic properties have been studied for compounds: La_1−xSr_xFe_1−xMn_xO₃ (0.3 ≤ x ≤ 0.7). The lattice parameter, a, first decreases with x, and followed by an increase when Sr²⁺ and Mn⁴⁺ was continuously doped. The cell parameters, b and c, slightly decrease with coupled substitution of Sr²⁺ for La³⁺ and Mn⁴⁺ for Fe³⁺. In the paramagnetic temperature range, formation of magnetic clusters is suggested; the sizes of clusters decrease with x up to 0.5, following that they increase sharply with continuing doping. The electrical behaviors of all specimens demonstrate insulators and the electrical resistivity increases with content of Mn⁴⁺ and Sr²⁺ ions doped. A variable range hopping model is suitable to describe electrical transport process for the compounds at low temperature. At high temperature the electrical transport process can be described by bipolaron model for all compounds.     

Ba4In2−x(CO3)1+xO6−2.5x and Ba4In0.8Cu1.6(CO3)0.6O6.2—new indium oxycarbonates closely related to n=3 Ruddlesden–Popper phases

Investigations of phase relations in the Ba-rich part of the In₂O₃–BaO(CO₂)–CuO pseudo-ternary system at 900 °C have revealed the existence of new indium–copper oxycarbonate – Ba₄In_0.8Cu_1.6(CO₃)_0.6O_6.2. Rietveld refinement of the X-ray powder diffraction data combined with infrared studies gives evidence that this phase is a oxycarbonate crystallising in the tetragonal structure (space group I4/mmm) with unit cell parameters: a=4.0349(1) Å and c=29.8408(15) Å. In the binary part of the In₂O₃–BaO(CO₂) system we have identified the occurrence of Ba₄In_2−x(CO₃)_1+xO_6−2.5x oxycarbonate solid solution showing a crystal structure also described by I4/mmm space group, but with the unit cell parameters: a=4.1669(1) Å and c=29.3841(11) Å for x=1. The existence range of this phase, −0.153<x<0.4, includes chemical compositions of earlier found phases: Ba₅In_2+xO_8+0.5x with 0≤x≤0.45 (known as the -solid solution), as well as the binary Ba₄In₂O₇ phase. The crystal structures of both new oxycarbonates are isomorphic and related to n=3 member of the Ruddlesden–Popper family.     

Structural, magnetic and magnetocaloric effect in double perovskite Ba2CrMo1−xWxO6

Magnetic refrigeration, an emerging new technology for cooling and gas liquefaction, needs magnetic materials with specific thermomagnetic behavior. Depending on the thermodynamic cycle selected, the isothermal magnetic entropy change or the adiabatic temperature change upon field application needs to be a preselected function of temperature. In double perovskite Ba₂CrMo_1−xW_xO₆ (x = 0, 0.2 and 0.5) prepared by the sol–gel method, the experimental results show the observation of a large magnetocaloric effect (MCE) near the Curie temperature T_C which decreases with the increasing of the substitution of Mo by W. The maximum of the magnetic entropy change peaks at the magnetic ordering temperature T_C, and a large magnetic entropy change (|ΔS_M| ≈ 1.6 J kg⁻¹ K⁻¹) is obtained at 285 K in the sample Ba₂CrMo_0.5W_0.5O₆ under an applied magnetic field of 10 kOe.     

Microstructural, Raman and dielectric properties of (1−x)NaNbO3–xBiCrO3 biphase ceramics

The phase, microstructural and dielectric properties of (1−x)NaNbO₃–xBiCrO₃ (x = 0.1, 0.2, 0.3, 0.4 and 0.5) ceramics with perovskite–pyrochlore mixed-phase were investigated. A single-phase solid solution in the sintered specimens was identified as observed perovskite phase for x = 0.1 and pyrochlore for x = 0.5. The results indicate that the microstructure has mixed large and small grains. Dielectric constants and dielectric loss were measured as functions of temperatures (−15 to 200 °C) at 1 kHz. Complex impedance spectroscopy shows the presence of barrier layers in biphase ceramics. The Raman spectra and porosity percentage in the biphase system were also measured.     

Dielectric properties and current–voltage nonlinear behavior of Ca1−xSrxCu3Ti4O12 ceramics

The effects of Sr doping on the dielectric properties and current–voltage nonlinear behavior of CCTO were investigated. By combining the observations of dielectric properties, current–voltage nonlinearity and impedance spectroscopy, we have found that Sr doping has influenced the electrical properties by adjusting the impedance characteristics of the grain and grain boundary. Among the Sr-CCTO specimens in this work, as Sr doping concentration is 10%, the specimen (Sr-CCTO-2) has the highest permittivity and lowest nonlinear coefficient.     

Characterization of hydrothermally prepared BaTi1−xZrxO3

BaTiO₃ (BTO) and BaTi_0.8Zr_0.2O₃ (BZT) powders were prepared using the hydrothermal method, starting from BaO, TiO₂ and Zr(NO₃)₂, 7H₂O. X-ray diffraction analysis showed that the cubic phase is stable at room-temperature and the pure perovskite phase is obtained after heating the powders for 2 h at 1280 °C. The temperature dependence of the dielectric constant points to ferroelectric behavior. This ferroelectric behavior can likely be due to the presence of a possible quadraticity gradient in the grains since the cubic phase may not be ferroelectric. The diffuse character of the transition is attributed to this quadraticity gradient, to grain size distribution and (for BZT) to spatial fluctuations in the concentrations of the substituted ion (Zr) leading to the coexistence of regions of different Curie temperatures.     

Study of the electrical conduction behaviour of the Ba1−xLaxTi1−xNixO3 (x 0.10) system

The electrical conduction behaviour of the Ba_1−xLa_xTi_1−xNi_xO₃ (x 0.10) system has been studied by complex plane impedance analysis and measurements of a.c. conductivity in the temperature range 400–575 K. The values of the bulk resistance for these samples are obtained from a circular arc passing through the origin in their impedance plots. A.c. conductivity obeys the relation σ_a.c.αω⁸ in the temperature range of measurements. These results indicate that conduction occurs in this system because of hopping of charge carriers between localized nickel sites.     

Dielectric and magnetic properties of 0.7Bi(Fe1−xCrx)O3–0.1BaTiO3–0.2PbTiO3 solid solutions

0.7Bi(Fe_1−xCr_x)O₃–0.1BaTiO₃–0.2PbTiO₃ (x = 0, 0.1, 0.2, 0.3) solid solutions were prepared by the traditional ceramic process. X-ray diffraction results revealed that the samples with x = 0–0.3 showed pure perovskite structure. Frequency and temperature dependences of dielectric constants and dielectric loss of the samples were investigated. Both dielectric constant and the loss tangent increased at given frequencies (100 Hz–1 MHz), while the Curie temperature of the solid solutions decreased with increasing Cr content. Room temperature magnetic hysteresis loops indicated that an appropriate amount of Cr could improve magnetization of the solid solutions.     

Study of (1 − x)(Mg0.6Zn0.4)0.95Co0.05TiO3–xCa0.61Nd0.26TiO3 microwave dielectrics

The microwave dielectric properties and the microstructures of the (1 − x)(Mg_0.6Zn_0.4)_0.95Co_0.05TiO₃–xCa_0.61Nd_0.26TiO₃ ceramic system were investigated. In order to achieve a temperature-stable material, we studied a method of combining a positive temperature coefficient material with a negative one. Ca_0.61Nd_0.26TiO₃ has a large positive temperature coefficient of resonant frequency. (Mg_0.6Zn_0.4)_0.95Co_0.05TiO₃ possesses a negative temperature coefficient of resonant frequency. By appropriately adjusting the x value in the (1 − x)(Mg_0.6Zn_0.4)_0.95Co_0.05TiO₃–xCa_0.61Nd_0.26TiO₃ ceramic system, a near-zero τ_f value can be obtained. A new microwave dielectric material of 0.8(Mg_0.6Zn_0.4)_0.95Co_0.05TiO₃–0.2Ca_0.61Nd_0.26TiO₃ possesses the excellent dielectric properties of a dielectric constant of 28.6, a Q × f value of 80,600 GHz and a temperature coefficient of resonant frequency of 4.1 ppm/°C and has a lower sintering temperature of 1250 °C.     

Sinterability and dielectric properties of Ba0.55Sr0.4Ca0.05TiO3-CaTiSiO5-Mg2TiO4 composite ceramics

The composite ceramics of Ba_0.55Sr_0.4Ca_0.05TiO₃-CaTiSiO₅-Mg₂TiO₄ (BSCT-CTS-MT) were prepared by the conventional solid-state route. The sintering performance, phase structures, morphologies, and dielectric properties of the composite ceramics were investigated. The BSCT-CTS-MT ceramics were sintered at 1100 °C and possessed dense microstructure. The dielectric constant was tailored from 1196 to 141 as the amount of Mg₂TiO₄ increased from 0 to 50 wt%. The dielectric constant and dielectric loss of 40 wt% Ba_0.55Sr_0.4Ca_0.05TiO₃-10 wt% CaTiSiO₅-50 wt% Mg₂TiO₄ was 141 and 0.0020, respectively, and the tunability was 8.64% under a DC electric field of 8.0 kV/cm. The Curie peaks were broadened and depressed after the addition of CaTiSiO₅. The optimistic dielectric properties made it a promising candidate for the application of tunable capacitors and phase shifters.     

Electrical, magnetic and elastic properties of La1.2(Sr1−xCax)1.8Mn2O7 (0.0 ≤ x ≤ 0.4)

Polycrystalline bulk samples of double layered manganite system La_1.2(Sr_1−xCa_x)_1.8Mn₂O₇ (0.0 ≤ x ≤ 0.4) were prepared by sol–gel method. After characterizing the samples using XRD and SEM, their electrical, magnetic and elastic properties were investigated. The lattice parameters and cell volume show a monotonous decrease with increase of Ca content, whereas the grain size is found to increase with increasing Ca content. The value of T_IM is found to decrease with Ca content up to x = 0.3 and then a slight increase of T_IM is observed. The low temperature upturn of resistivity is attributed to the spin-glass-like behavior, which is also evidenced by the irreversibility observed between ZFC and FC magnetizations. The conduction mechanism above T_IM can be explained by Mott VRH model. The present magnetization and ultrasonic studies indicate that the system shows a secondary transition at T^*, which decreases with increasing Ca content. Further, the T^* seems to be intrinsic to the present double layered manganite system.     

Phase structure and electrical properties of (0.8 − x) BaTiO3-0.2Bi0.5Na0.5TiO3-xBaZrO3 lead-free piezoceramics

Lead-free piezoelectric ceramics (0.8 − x)BaTiO₃-0.2Bi_0.5Na_0.5TiO₃-xBaZrO₃ (BT-BNT-xBZ, 0 ≤ x ≤ 0.08) doped with 0.3 wt% Li₂CO₃ were prepared by conventional solid-state reaction method. With the Li₂CO₃ doping, all the ceramics can be well sintered at 1170-1210 °C. The phase structure, dielectric, ferroelectric and piezoelectric properties of the ceramics were investigated. Results show that a morphotropic phase boundary (MPB) between tetragonal and pseudocubic phases exists at x = 0.03-0.04. The addition of Zr can improve the piezoelectric properties of BT-BNT ceramics. Furthermore, a relaxor behavior is induced and the tetragonal-cubic phase transition shifts towards lower temperatures after the addition of Zr. The ceramics with x = 0.03 possess the optimum electrical properties: d₃₃ = 72 pC/N, k_p = 15.4%, ?_r = 661, P_r = 18.5 μC/cm², E_c = 34.1 kV/cm, T_c = 150 °C.     

Nuclear structure and magnetic properties of perovskite compounds La1−xNdxFe0.5Cr0.5O3 (x = 0.1, 0.15 and 0.2)

Perovskite oxides with the composition La_1−xNd_xFe_0.5Cr_0.5O₃ (x = 0.10, 0.15 and 0.20) have been studied. The samples have been prepared using the standard solid-state reaction method in air. The X-ray and neutron diffractograms indicates that the samples crystallize in the orthorhombic perovskite structure with space group Pnma (No. 62). The Nd-substitution causes minor changes in the cell parameters and bond lengths but the nuclear structure remains orthorhombic in the whole range of substitutions and in the temperature range of 10–700 K. The magnetic structure of the samples at room temperature and below is G-type antiferromagnetic with an average magnetic moment of the Fe/Cr ions of 3.29(3) μ_B/atom at 10 K independent of the Nd content. At room temperature the average magnetic moment of the Fe/Cr ions reduces to 1.23 μ_B/atom. At temperatures below 250 K a weak but increasing uncompensated spontaneous magnetic moment develops that reaches a magnitude of about 0.5 emu/g (or 0.02 μ_B per Fe/Cr site) at 10 K. This moment saturates rather rapidly in the magnetization versus magnetic field curve and is at higher field superposed on the response of the antiferromagnetic spin system.