Microstructure and electrical properties of Bi0.5Na0.5TiO3–Bi0.5K0.5TiO3–LiNbO3 lead-free piezoelectric ceramics

Lead-free piezoelectric ceramics of (1?x?y)Bi_0.5Na_0.5TiO₃–xBi_0.5K_0.5TiO₃–yLiNbO₃ (BNT–BKT–LN-x/y) have been fabricated by a conventional solid-state reaction method, and their microstructure and electrical properties have been investigated. The results of X-ray diffraction (XRD) measurement show that K⁺, Li⁺ and Nb⁵⁺ diffuse into the Bi_0.5Na_0.5TiO₃ lattices to form a solid solution with a pure perovskite structure. The BKT and LN addition has no remarkable effect on the crystal structure. However, a significant change in grain size took place. Simultaneously, with increasing amount of LN, the temperature for a ferroelectric–antiferroelectric phase transition is clearly reduced. The temperature dependence of dielectric properties suggests that the ceramics have diffuse-type phase transition characteristics. The piezoelectric constant d₃₃ and the electromechanical coupling factor k_p of the ceramics attain maximum values of 195 pC/N and 0.336 at x=0.18 and y=0.01.     

Phase diagram of (1−x%)(0.89Bi0.5Na0.5TiO3–0.06BaTiO3–0.05K0.5Na0.5NbO3)–x%MnO2 lead-free anti-ferroelectric ceramics

A phase diagram for the lead-free ceramics in the (1?x%)(0.89Bi_0.5Na_0.5TiO₃–0.06BaTiO₃–0.05K_0.5Na_0.5NbO₃)–x%MnO₂ (BNBKN-x%Mn) binary system is constructed for the first time based on the ferroelectric and dielectric measurements. The ferroelectric behaviors under different temperatures suggest that the ceramics are basically of relaxor anti-ferroelectric nature near room temperature. The temperature dependent dielectric properties show that when the addition of MnO₂ increases, the relaxor anti-ferroelectric phase can be stabilized to be close to the Curie point, which corresponds to a relaxor anti-ferroelectric to paraelectric phase transition.     

Dielectric,structural and specific heat properties of lead-free [(1−x)(Na0.5Bi0.5)−xBa]Zr1−yTiyO3 ceramics (x = 0.06, 0.085, 0.09, 0.1 and y = 0.97)

Lead-free [(1?x)(Na_0.5Bi_0.5)?xBa]Zr_1?yTi_yO₃ ceramics (x = 0.06, 0.085, 0.09, 0.1 and y = 0.97) have been prepared by solid-state hot-pressing sintering process. The obtained samples reveal perovskite structure. Structural, thermal expansion, heat capacity, ferroelectric and dielectric measurements have been carried out on these samples in a wide temperature range. The broad anomalies were observed in thermal expansion and heat capacity, which approximately correspond to a structural, ferroelectric and dielectric properties anomaly. These anomalies can be related to temperature features of polar regions and a formation of long-range-order ferroelectric phase. The determined Burns temperature was found to increase with increasing Ba content. The obtained results are discussed in terms of local electric and strain fields caused by a difference in the ionic radii of (Na,Bi) and Ba, and Ti and Zr ions. The NBT–BTZ system is expected to be a new promising candidate for lead-free electronic ceramics.     

Modified structure and electrical properties of BSZT doped KNN hybrid ceramic

Lead free (1?x)(K_0.5Na_0.5)NbO₃–x(Ba_0.9Sr_0.1)(Zr_0.1Ti_0.9)O₃ [(1?x)KNN–xBSZT] (x=0,0.02,0.04 and 0.06) ceramic were synthesized by a solid-state reaction method and the effects of BSZT doping on the electrical properties of KNN have been studied. X-ray diffraction (XRD) indicates that all the samples have single-phase perovskite structure and addition of BSZT forms a morphotropic phase boundary (MPB) i.e. the coexistence of orthorhombic and tetragonal phase in the region 0.02≤x≤0.04. Field emission scanning electron microscopy (FESEM) indicates the reduction in the grain size with the addition of BSZT. Small broadening in the dielectric peak arises at higher concentration of BSZT. The value of remnant polarization at x=0.04 is found to be higher than any other value of x except x=0 and also results in enhancement of dielectric constant at room temperature. Thereby it makes it useful for application at room temperature.     

Ferroelectric phase transitions in ionic conductors based on bismuth vadanate

Ceramic solid solutions (Bi_{1 ? x} La _x )₄V₂O_{11 ? z} (I), Bi₄(V_{1 ? x} Fe _x )₂O_{11 ? y} (II), and (Bi_{1 ? x} La _x )₄(V_0.96Fe_0.04)₂O_{11 ? y} (III) (x = 0–0.3, step Δx = 0.02) are prepared using solid-phase synthesis. The concentration and temperature ranges of stabilization of different polymorphic modifications, including the ranges of concentrations x corresponding to the stabilization of the ferroelectric phase, are established. It is revealed that an increase in the concentration x in the region of existence of the pseudoorthorhombic phase α of the solid solutions studied leads to a decrease in the transition temperature, smearing of the transition, and an increase in the width of the thermal hysteresis of the ferroelectric phase transition. The effect of compressing of the domain walls by oxygen vacancies was revealed in the samples from the region of existence of the ferroelectric α phase, and the effect of dielectric relaxation was detected in the samples from the region of existence of the orthorhombic phase β.     

Raman scattering studies of the effects of a symmetry-breaking impurity on the ferroelectric phase transition in K1−xLixTa1−yNbyO3

Raman scattering and optical depolarization measurements on K_1?xLi_xTa_1?yNB_yO₃ with y ? 0.028 and x ? 0.06 show that lithium impurities destabilize the niobium-induced rhombohedral ferroelectric phase. With increasing x the phase transition is altered from a soft-mode dominated transition to a disorder-order transition into a tetragonal phase. The dependence of T_c on x disagrees with the predictions of classical mean-field theory.     

Effects of uniaxial stress on dielectric properties of lithium modified potassium sodium niobate ceramics

In this work, the solid solution of ((K_0.5Na_0.5)_1−xLi_x)NbO₃ ceramics with x=0.03, 0.04, 0.05, 0.06 and 0.07 was prepared by a conventional mixed-oxide and solid-state sintering method. The structural phase formation and microstructure were characterized by X-ray diffraction technique and scanning electron microscopy. The ceramics were identified by XRD as a single-phase perovskite structure with symmetry gradually changing from orthorhombic to tetragonal. The grain size and the optimum density of the sintered ceramics were noticeably compositional-dependent. The dielectric properties of the ((K_0.5Na_0.5)_1−xLi_x)NbO₃ ceramics under the uniaxial compressive stress were observed at stress up to 180 MPa. The results showed that the dielectric constant and the dielectric loss tangent increased with applied stress. The change in the dielectric properties with stress was seen to depend on the composition and grain size. The observations were interpreted in terms of the intrinsic and extrinsic contributions to the changes in dielectric properties upon the applied compressive stress.     

Spontaneous phase transition from relaxor to macrodomain ferroelectric state in single-crystal PbSc0.5Nb0.5O3-BaSc0.5Nb0.5O3 solid solutions

The cooling of Pb_1?x Ba_xSc_0.5Nb_0.5O₃ solid solutions with x≤0.04 leads to a spontaneous transition from a relaxor to a macrodomain ferroelectric state, accompanied by anomalous variation of the dielectric and optical properties of the material. As the barium content in the system increases, the relaxor state becomes more stable and eventually “freezes” at x≈0.05. The crystals with x=0.06 exhibited the appearance of a macrodomain ferroelectric phase induced both by an external electric field with a strength of 1.5 kV/cm and by an internal electric field formed in the course of dielectric aging.     

X-ray and dielectric characterization of Co doped tetragonal BaTiO3 ceramics

ABSTRACT

The crystal structure modifications of BaTiO₃ induced by cobalt doping were studied. The polycrystalline (1 ? x)BaTiO₃ + xCo₂O₃ samples, with x ≤ 10 wt.%, were prepared by high temperature sintering conventional method. According to X-ray phase and structural characterization, performed by full-profile Rietveld refinement technique, all synthesized samples showed tetragonal symmetry perovskite structure with minor amount of parasitic phases. Pure single-phase composition has been detected only in the low level of doping BaTiO₃. It was indicated that substitution of Co for the Ti sites in the (1 ? x)BaTiO₃ + xCo₂O₃ series led to decrease of tetragonality (c/a) of the BaTiO₃ perovskite structure. This effect almost vanished in the (1 ? x)BaTiO₃ + xCo₂O₃ samples with nominal Co content higher than ～1 wt.%, in which precipitation of parasitic Co-containing phases CoO and Co₂TiO₄ has been observed. Based on the results, the solubility limit of Co in Ti sub-lattice in the (1 ? x)BaTiO₃ + xCo₂O₃ series is estimated as x = 0.75 wt.%.     

High-temperature complex impedance and modulus spectroscopic studies of doped Na<Subscript>0.5</Subscript>Bi<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript>-BaTiO<Subscript>3</Subscript> ferroelectric ceramics

Lead-free Na_0.5Bi_0.5TiO₃ (NBT) and (1 ? x)Na_0.5Bi_0.5TiO₃ + xBaTiO₃ with x = 0.1 and 0.2 (where x = 0.1 and 0.2 are named as NBT1 and NBT2, respectively), (1 ? y)Na_0.5Bi_0.5TiO₃ + yBa_0.925Nd_0.05TiO₃ with y = 0.1 and 0.2 (where y = 0.1 and 0.2 are named as NBT3 and NBT4, respectively)-based relaxor ferroelectric ceramics were prepared using the sol-gel method. The crystal structure was investigated by X-ray diffraction (XRD) at room temperature (RT). The XRD patterns confirmed the presence of the rhombohedral phase in all the samples. The electrical properties of the present NBT-based samples were investigated by complex impedance and the modulus spectroscopy technique in the temperature range of RT–600 °C. The AC conductivity was found to increase with the substitution of Ba²⁺ ions to the NBT sample whereas it significantly decreased with the addition of Nd³⁺ ions. The more anion vacancies in Ba-added samples and the lower anion vacancies in Nd-added samples were found to be responsible for higher and lower conductivities, respectively.     

Dielectric and ferroelectric properties of NBT-BT systems

ABSTRACT

The (1-x)Na_0.5Bi_0.5TiO₃- xBaTiO₃ ceramics (x = 0.1, 0.135 and 0.17) were fabricated by a conventional solid phase sintering process. The bulk density of the obtained samples exceeded 95% of the theoretical relative density as determined by Archimedes method. Dielectric and ferroelectric measurements of these ceramics were performed. Measurements of the ferroelectric properties show that, above the depolarization temperature T_d, the shape of the hysteresis loops approaches that of linear dielectrics. The dielectric study results correlate with the hysteresis loops measurements. The relaxor-like behavior of the investigated materials was revealed.     

Microscopic magnetic properties of nonstoichiometric V2O3+x—NMR and inelastic spin-flip neutron scattering measurements

The local magnetic properties of the V sites in the nonstoichiometric V₂O_3+x (0 ? x <0.08) have been examined by nuclear magnetic resonance and inelastic spin-flip neutron scattering techniques. The samples with x = 0.01 and 0.02 show a paramagnetic metal (PM)-antiferromagnetic insulator (AFI) transition. In the AFI phase, two distinct ⁵¹V NMR signals with hyperfine fields H_n = 184.9±0.5 kOe and 71±1 kOe were observed at 1.8 K, which were assigned as due to V³⁺ and V³⁺ sites, respectively. On the other hand, the samples with x = 0.04 and 0.06 were metallic down to 1.4K, and showed a paramagnetic (PM)-antiferromagnetic (AFM) transition at about 10 K. In these samples, a ⁵¹V NMR signal with H_n = 58±2 k0e and one with 〈H_n〉 = 9kOe were observed at 1.8 K, which were assigned as due to V³⁺-like sites and the matrix V sites, respectively. These results are entirely consistent with those obtained from the neutron experiment. We propose that in the metallic phase (0.04 ? x < 0.08) the minority V⁴⁺-like sites are magnetically localized in the delocalized V matrix and may be responsible for the antiferromagnetic long range order below 10 K.     

Concentration-phase transitions in solid solutions Li x Na1 − x Ta0.1Nb0.9O3, Li0.12Na0.88Ta y Nb1 − y O3, and NaTa y Nb1 − y O3 and their manifestations in Raman spectra

Using the Raman-spectroscopy method, we have studied concentration-phase transitions in the solid solutions Li _x Na_{1 ? x} Ta_0.1Nb_0.9O₃, Li_0.12Na_0.88Ta _y Nb_{1 ? y} O₃, and NaTa _y Nb_{1 ? y} O₃ (x = 0?0.16, y = 0–1). It has been revealed that, for the solid solutions Li _x Na_{1 ? x} Ta_0.1Nb_0.9O₃ and Li_0.12Na_0.88Ta _y Nb_{1 ? y} O₃, the concentration-phase transition is a transition between the ferroelectric and antiferroelectric states. It is accompanied by the disappearance from the spectrum of a line that corresponds to stretching bridge vibrations of oxygen atoms along the polar axis, which is forbidden by selection rules in the centrosymmetric phase, and by splitting into two components of a line that corresponds to librational vibrations of oxygen octahedra as a whole, which can be caused by doubling of the unit cell in the antiferroelectric phase. Manifestation and variation of intensities of lines with frequencies 860–873 and 900–905 cm^?1 upon variation of the concentration of tantalum for solid solutions Li_0.12Na_0.88Ta _y Nb_{1 ? y} O₃, and NaTa _y Nb_{1 ? y} O₃ is caused by the formation of polar clusters in the medium, which is centrosymmetric in general due to disordering in the sublattice of niobium and tantalum.     

Local structure and magnetic properties of Mn substituted manganites studied by EXAFS and Dc magnetic measurements

We report extended X-ray absorption fine structure (EXAFS) measurements at the Mn K edge and magnetic measurements performed on (La_1−xCa_x)(Mn_1−yM_y)O₃ samples (M=Cr or Ni; x=0.37 and 0.75 and y=0.03 or 0.08). The Mn substitution produces important effects on both the sides of the LaMnO₃-CaMnO₃ phase diagram. For x<0.5 the ferromagnetic-metallic phase maintains its main character even after Mn substitution, but both the doping species (Ni or Cr) lower T_C and broaden the magnetic transition, and the EXAFS study evidences two Mn-O distances, suggesting the presence of zones of distorted insulating phase. For x>0.5, after the doping with Cr, the charge ordered phase persists but on a shorter scale, whereas the Jahn-Teller distortion is weakened as indicated by EXAFS measurements, and the formation of ferromagnetic clusters is evidenced by magnetic measurements.EXAFS and magnetic measurements are in mutual agreement, thus confirming the correlation between the local disorder determined by charge localization and magnetic degrees of freedom.     

Intermediate valence and semiconductor-metal transition of TmS1−xSex and TmSe1−yTey

A complete series of TmS_1?xSe_x and TmSe_1?yTe_y single crystals has been prepared in order to enable a systematic investigation of the valence change of the Tm-ion between nearly +3 for metallic TmS (x = 0) and +2 for semiconducting TmTe (y = 1). A discontinuous semiconductor-metal transition (SMT) is observed at y = 0.33, associated with a lattice parameter decrease of Δa₀/a₀ = ?0.037. Using the lattice parameter as a measure for the Tm-valence results in a valence change of 0.65 at the SMT. All other physical parameters are likewise discontinuous at the SMT. For instance, the effective Bohr magneton number evaluated from the high-temperature Curie-Weiss susceptibility jumps by 16% at the SMT which gives a valence change of 0.26, just 40% of the value deduced from a₀. In the metallic state (y ? 0.33, all x) the valence number of the Tm-ion evaluated from μ_eff is systematically lower than that resulting from a₀. For TmSe a valence of +2.83 is obtained from a₀ + 2.62 from μ_eff. All metallic samples undergo a metamagnetic phase transition. The type of order changes gradually to antiferromagnetic on approaching TmS. Application of Falicov's model for the phase transition into the metallic state with intermediate valence implies that the system be close to the critical point for Δa₀/a₀ = ?0.037, in contradiction to the experimental evidence.     

Li and Nb codoping in dielectric properties and phase transitions of KTaO3: Reentrant dipolar glass and long-range dipole ordering

Abstract

The highly polarizable perovskite-type oxide, KTaO₃ doped simultaneously with Li⁺ and Nb⁵⁺ (K_1?xLi_xTa_1?yNb_yO₃, KLTN), reveals unexpected properties and ordering effects. Studies of the dielectric permittivity ?'(T, f) (10—300K, 100Hz-1 MHz) for x = 0.0014 and y = 0.024 show collective dipolar ordering effects with a transition from paraelectric into a mixed phase (coexisting dipole-glass-like and long-range ordered ferroelectric phases) taking place near 39 K. At 15 K another phase transition into a reentrant dipolar glass-like state is observed. Such a sequence of transitions and the existence of a reentrant glass state are unknown for electrical dipolar systems.     

Indium doping effect on the magnetic properties of Y-type hexaferrite Ba0.5Sr1.5Zn2(Fe1-xInx)12O22

The effect of indium doping on structural and magnetic properties of Y-type hexaferrite Ba_0.5Sr_1.5Zn₂(Fe_1-xIn_x)₁₂O₂₂ (x = 0, 0.02, 0.04, 0.06, 0.08 and 0.1) prepared by the solid state reaction method was investigated. The Rietveld refinement method was used to analyze the X-ray diffraction patterns. The magnetic transition temperatures associated with the proper-screw spin phase to the collinear ferrimagnetic spin phase transition can be efficiently modulated by varying indium content. The magnetic transition temperature increases to a maximum with indium content x = 0.04 and then decreases with x, suggesting the possibility that electrically controlled magnetization reversal can be can be effectively tailored by varying indium content. The saturation magnetization at room temperature was decreased as increasing indium content, which can be explained as the metal ions occupation. It is worthy to note that the coercivity of In-doped samples was decreased drastically compared that of undoped sample, which is probably resulted from the reduction in anisotropy field with substitution of In³⁺ for Fe³⁺. The In-doped hexaferrite Ba_0.5Sr_1.5Zn₂(Fe_1-xIn_x)₁₂O₂₂ may be potential candidates for application in magnetoelectric devices.     

Effects of A-site disorder on magnetic,electrical and thermal properties of La0.5−xLnxCa0.5−ySryMnO3manganites

The magnetic, electrical and thermal properties in the La_0.5?xLn_xCa_0.5?ySr_yMnO₃ (Ln=Pr, Nd, Sm) bulk system were investigated. Detailed dc magnetization and linear ac susceptibility measurements reveal that the samples first undergo phase transition from paramagnetic to ferromagnetic phase and then to an antiferromagnetic phase upon further cooling. It is found that both the Curie and Neel temperatures decrease systematically with increasing A-site disorder in these manganites. The electrical resistivity exhibits semiconducting behavior throughout the temperature range investigated and the electronic conduction mechanism can be conveniently described within the framework of the variable range hopping model above T=150 K. The Seebeck coefficient (S) in the magnetically ordered regime infers that the complicated temperature dependence of S is an indication of electron–magnon scattering. Specific heat measurements depict a broadened hump in the vicinity of T_C, indicating the existence of magnetic ordering and magnetic inhomogeneity in the samples. The temperature dependence of thermal conductivity, κ(T), reveals a positive dκ/dT in the paramagnetic region, which may be related to the local anharmonic lattice distortions associated with small polarons.     

Phase stratification in the Nd1 − x BaxCoO3 − δ (0.3 ≤ x ≤ 0.54) system

Slowly cooled Nd_{1 ? x} Ba_xCoO_{3 ? δ} samples were two-phase in the concentration interval 0.3 ≤ x ≤ 0.46. One of the phases had O-orthorhombic lattice distortions (Pbnm) characteristic of ferromagnetic samples with x ≤ 0.3, and the other phase had tetragonal distortions (P4/mmm) characteristic of samples with x ≥ 0.46. Tetragonal distortions were caused by ordering of Nd³⁺ and Ba²⁺ ions. Samples with ordered neodymium and barium ions (Nd_{1 ? y} Ba_{1 + y} Co₂O_{6 ? γ} at ?0.08 ≤ y ≤ 0.08) experienced metal-dielectric and orientation magnetic phase transitions.     

Phase Formation,Structure, and Electrical Conductivity of Modified Lanthanum-Gallate Ceramics

The solid-phase synthesis method is used to prepare perovskite-like ceramic samples with the compositions (La_0.8Sr_0.2){[Ga_0.8–x(Si_0.5Mg_0.5) _x ]Mg_0.2}O_3–y (x = 0, 0.1, 0.2, 0.4, and 0.6) and investigate their phase formation, structure, microstructure, and electrical conductivity. Single-phase samples are obtained when up to 10 at % of gallium cations are replaced with silicon and magnesium cations. It is established that silicon-containing samples with the perovskite structure are characterized by a high density, optimal microstructure, dense grain packing, and large electrical conductivities at high temperatures.