Influence of fabrication processing on phase transition and electrical properties of 0.8Pb(Zr1/2Ti1/2)O3–0.2Pb(Ni1/3Nb2/3)O3 ceramics

The binary system of 0.8Pb(Zr_1/2Ti_1/2)O₃–0.2Pb(Ni_1/3Nb_2/3)O₃ ceramics were synthesized by conventional mixed oxide and columbite method. X-ray diffraction analysis demonstrated the coexistence of both the rhombohedral and tetragonal phases for the columbite prepared sample. Rhombohedral to tetragonal phase transition for columbite method was different compared with those of the mixed oxide method. The permittivity shows a shoulder at the rhombohedral to tetragonal phase transition temperature T_Rho–Tetra = 195 °C, and then a maximum permittivity (36,000 at 10 kHz) at the transition temperature T_m = 277 °C on ceramics prepared with the columbite method. However, piezoelectric coefficient (d₃₃) was measured to be 282 pC/N for the conventional method and higher than the columbite method. The results were related to the phase compositions and porosity of the ceramics.     

Structural,ferroelectric, optical properties of A-site-modified Bi0.5(Na0.78K0.22)0.5Ti0.97Zr0.03O3 lead-free piezoceramics

We reported the role of A-site modification on the structural, ferroelectric, optical and electrical field-induced strain properties of Bi_0.5(Na_0.78K_0.22)_0.5Ti_0.97Zr_0.03O₃ lead-free piezoceramics. The Li⁺ ions with concentration from 0 to 5 mol% were used to substitute at A-site. There was no phase transition when Li⁺ ions was added up to 5 mol%. The electric field-induced strain (S_max/E_max) values increased from 600 to 643 pm/V for 2 mol% Li⁺-added which results from distortion both rhombohedral and tetragonal phase structures. The band gap reduced from 2.88 to 2.68 eV and the saturation polarization decreased from 46.2 to 26.1 μC/cm² when Li⁺ ions concentration increased from 0 to 5 mol% respectively. We expect that this work could be helpful for further understanding the role of A-site dopants in comparison with B-site modification in lead-free Bi_0.5(Na,K)_0.5TiO₃-based ceramics.     

Lu2O3:Tb,Hf storage phosphor

Lu₂O₃:Tb,Hf ceramics containing 0.1% of Tb and 0–1.5% of Hf were prepared in reducing atmosphere at 1700 °C and their thermoluminescence properties were systematically studied. For comparison Tb,Ca co-doped specimen was also fabricated and investigated. The Tb,Hf ceramics shows basically a single TL band located around 180 °C as found with heating rate of 15 °C/min. Ceramics singly doped with Tb show complex TL glow curves indicating the presence of traps of very different depths. On the other hand Tb,Ca co-doping is beneficial for the development of shallow traps with the main TL band around 70 °C. Hence, the aliovalent impurities, Ca²⁺ and Hf⁴⁺, strongly influenced the traps structure in Lu₂O₃:Tb ceramics, each of them in its own specific way. Isothermal decay of Lu₂O₃:Tb,Hf at 185 °C was recorded and its shape suggest that multiple hole trapping occurs in the Lu₂O₃:Tb,Hf ceramics. Due to the different traps depths the Lu₂O₃:Tb,Hf ceramics possess properties typical for storage phosphors, while Lu₂O₃:Tb,Ca is a persistent luminescent material rather.     

Dielectric,ferroelectric and piezoelectric properties of (1−x)[K0.5Na0.5NbO3]−x[LiSbO3] ceramics

Lead-free (1?x)[K_0.5Na_0.5NbO₃]?x[LiSbO₃] (x=0, 0.04, 0.05 and 0.06)/(KNN-LS) ceramics were prepared by conventional solid-state reaction route (CSSR). For dense morphology pure KNN ceramic was sintered at 1120 °C and LS modified KNN ceramics were sintered at 1080 °C for 4 h, respectively. The structural study at room temperature (RT) revealed the transformation of pure orthorhombic to tetragonal structure with the increase in LS content in KNN-LS ceramics. Temperature dependent dielectric study confirmed the increase of diffuse phase transition nature with the increase in LS content in KNN-LS ceramics. The presence of orthorhombic to tetragonal (T_O?T) polymorphic phase transition temperature (PPT) ～43 °C confirmed the presence of two ferroelectric (orthorhombic and tetragonal) phases in 0.95KNN-0.05LS ceramics at RT. 0.95KNN-0.05LS ceramics showed better ferroelectric and piezoelectric properties i.e., remnant polarization (P_r)～18.7 μC/cm², coercive field (E_c)～11.8 kV/cm, piezoelectric coefficient (d₃₃)～215 pC/N, coupling coefficient (k_p)～0.415 and remnant strain ～0.07% were obtained.     

Enhancement microwave dielectric properties of La(Mg0.5Sn0.5)O3 ceramics by substituting La3+ with Sm3+

The microwave dielectric properties of La_1?xSm_x(Mg_0.5Sn_0.5)O₃ ceramics were examined with a view to their exploitation for mobile communication. The La_1?xSm_x(Mg_0.5Sn_0.5)O₃ ceramics were prepared by the conventional solid-state method with various sintering temperatures. The X-ray diffraction patterns of the La_0.97Sm_0.03(Mg_0.5Sn_0.5)O₃ ceramics revealed no significant variation of phase with sintering temperatures. Apparent density of 6.59 g/cm³, dielectric constant (ε_r) of 19.9, quality factor (Q×f) of 70,200 GHz, and temperature coefficient of resonant frequency (τ_f) of ?77 ppm/°C were obtained for La_0.97Sm_0.03(Mg_0.5Sn_0.5)O₃ ceramics that were sintered at 1500 °C for 4 h. The dielectric constant, and τ_f of La_0.97Sm_0.03(Mg_0.5Sn_0.5)O₃ ceramics were almost independent with the sintering temperature as the sintering temperature varied from 1450 to 1600 °C.     

Effects of alumina nano-particulates addition on mechanical and electrical properties of barium titanate ceramics

Ferroelectric BaTiO₃/xAl₂O₃ nanocomposite ceramics (when x = 0, 0.5, 1, 3 and 5 vol%) were fabricated from an in-house prepared BaTiO₃ powder and nano-sized Al₂O₃ powder by a solid state mixed-oxide method. Densities and grain sizes of the ceramics were found to gradually decrease with increasing content of Al₂O₃ addition. Mechanical properties such as Knoop hardness and Young’s modulus of BaTiO₃ were found to be improved with only 0.5 vol% of Al₂O₃ addition. Dielectric and piezoelectric properties of the nanocomposites with <1 vol% Al₂O₃ addition could be maintained and were comparable to the values of the monolithic BaTiO₃. Within the range of the BaTiO₃/Al₂O₃ nanocomposites investigated, this study suggested materials with acceptable electrical properties and better structural stability.     

Ferroelectric properties of Pb(Zr1/2Ti1/2)O3–Pb(Zn1/3Nb2/3)O3 ceramics under compressive stress

Effects of compressive stress on the ferroelectric properties of ceramics in PZT–PZN system were investigated. The ceramics with a formula (1−x)Pb(Zr_1/2Ti_1/2)O₃–xPb(Zn_1/3Nb_2/3)O₃ or (1−x)PZT–(x)PZN (x = 0.1–0.5) were prepared by a conventional mixed-oxide method. The ferroelectric properties under the compressive stress of the PZT–PZN ceramics were observed at the stress levels up to 170 MPa using a compressometer in conjunction with a modified Sawyer–Tower circuit. It was found that with increasing compressive stress the area of the ferroelectric hysteresis (P–E) loops, the saturation polarization (P_sat), the remnant polarization (P_r), and the coercive field (E_c) decreased. These results were interpreted through the non-180° ferroelastic domain switching processes.     

Ferroelectric phase transition and optical performance of PLZnNZT transparent ceramics

Lead-based Pb_0.97La_0.02(Zn_1/3Nb_2/3)_0.3(Zr_0.53Ti_0.47)_0.7O₃ (PLZnNZT) transparent ceramics with the addition of 2 wt% excess PbO were prepared by hot-pressing sintering method. The hot-pressing sintered PLZnNZT ceramics exhibit dense and large-grained microstructure, and perovskite structure with distorted cubic-like symmetry. The ceramics exhibit normal ferroelectric-like dielectric behavior with slightly diffused ferroelectric phase transition characteristic. The PLZnNZT ceramics exhibit fully developed, symmetric and saturated P–E hysteresis loop and large piezoelectric constant d₃₃, being 468 pC/N. The ceramics with 120 μm thickness exhibit maximum transmittance of 53% at 850 nm when Fresnel losses was not included, almost totally transparent in the mid IR region (2500–5600 nm), and low-lying optical band gap energy E_g of 3.23 eV. Three diffused Raman bands centering around 240 cm⁻¹, 560 cm⁻¹ and 750 cm⁻¹ are observed by micro-Raman spectroscopy, which can be attributed to F2g [BO₆] bending vibration, A1g [BO₆] stretching vibration and “soft mode” mixed by the bending and stretching vibrations, respectively, confirming the normal ferroelectric-like characteristic.     

Antiferromagnetic phase transition in garnet-type AgCa2Mn2V3O12 and NaPb2Mn2V3O12

Ferrimagnetism has been extensively studied in garnets, whereas it is rare to find the antiferromagnet. Present work will demonstrate antiferromagnetism in the two Mn–V-garnets. Antiferromagnetic phase transition in AgCa₂Mn₂V₃O₁₂ and NaPb₂Mn₂V₃O₁₂ has been found, where the magnetic Mn²⁺ ions locate only on octahedral A site. The heat capacity shows sharp peak due to antiferromagnetic order with the Néel temperature T_N=23.8 K for AgCa₂Mn₂V₃O₁₂ and T_N=14.2 K for NaPb₂Mn₂V₃O₁₂. The magnetic entropy change over a temperature range 0–50 K is 13.9 J K^?1 mol-Mn²⁺-ions^?1 for AgCa₂Mn₂V₃O₁₂ and 13.6 J K^?1 mol-Mn²⁺-ions^?1 for NaPb₂Mn₂V₃O₁₂, which are in good agreement with calculated value of Mn²⁺ ion with spin S=5/2. The magnetic susceptibility shows the Curie–Weiss behavior over the range 29–350 K. The effective magnetic moment μ_eff and the Weiss constant θ are μ_eff=6.20 μ_B Mn²⁺-ion^?1 and θ=?34.1 K (antiferromagnetic sign) for AgCa₂Mn₂V₃O₁₂ and μ_eff=6.02 μ_B Mn²⁺-ion^?1 and θ=?20.8 K for NaPb₂Mn₂V₃O₁₂.     

Effect of Li2CO3 addition on the structural,optical, ferroelectric,and electric-field-induced strain of lead-free BNKT-based ceramics

In this work, we reported the effect of Li₂CO₃ addition on the structural, optical, ferroelectric properties and electric-field-induced strain of Bi_0.5(Na,K)_0.5TiO₃ (BNKT) solid solution with CaZrO₃ ceramics. Both rhombohedral and tetragonal structures were distorted after adding Lithium (Li). The band gap values decreased from 2.91 to 2.69 eV for 5 mol% Li-addition. The maximum polarization and remanent polarization decreased from 49.66 μC/cm² to 27.11 μC/cm² and from 22.93 μC/cm² to 5.35 μC/cm² for un-doped and 5 mol% Li- addition BNKT ceramics, respectively. The maximum S_max/E_max value was 567 pm/V at 2 mol% Li₂CO₃ access. We expected this work will help to understand the role of A-site dopant in lead-free ferroelectric BNKT materials.     

Phase formation and electrical properties of BNLT–BZT lead-free piezoelectric ceramic system

Phase formation study in lead-free piezoelectric ceramics based on lanthanum doped bismuth sodium titanate (Bi_0.4871Na_0.4871La_0.0172TiO₃:BNLT) and zirconium doped barium titanate (BaZr_0.05Ti_0.95O₃:BZT), has been carried out in the system of (1−x)BNLT–xBZT where x = 0.0–1.0, by two-step mixed oxide method. It was observed that the addition of BZT in the BNLT ceramics developed the dielectric and piezoelectric properties of the ceramics with the optimum piezoelectric constant (d₃₃) and dielectric constant (ε_r) at room temperature of about 138 pC/N and 1651, respectively, from the 0.2 BNLT to 0.8 BZT ceramic sample. The Curie temperature (T_C) of this ceramic was found at 295 °C which is 195 °C higher than that of pure BZT ceramics, promising the use of this ceramic in a higher range of temperature.     

High-pressure dielectric studies of a novel hydrogen-bonded ferroelectric (NH4)2H2P2O6

The hydrostatic pressure effect on the dielectric properties of (NH₄)₂H₂P₂O₆ ferroelectric crystal was studied for pressures from 0.1 MPa to 360 MPa and for temperatures from 100 to 190 K. The pressure–temperature phase diagram obtained is linear with increasing pressure. The paraelectric–ferroelectric phase transition temperature decreases with increasing pressure with the pressure coefficient dT_c/dp=?5.16×10^?2 K MPa^?1. Additionally, the pressure dependences of Curie–Weiss constants for the crystal in paraelectric (C₊) and ferroelectric (C_?) phases are evaluated and discussed. The possible mechanism of paraelectric–ferroelectric phase transition is also discussed.     

Phase stability and oxygen non-stoichiometry of SrCo0.8Fe0.2O3−δ measured by in situ neutron diffraction

The phase stability, oxygen stoichiometry and expansion properties of SrCo_0.8Fe_0.2O_3−δ (SCF) were determined by in situ neutron diffraction between 873 and 1173 K and oxygen partial pressures of 5 × 10^− 4 to 1 atm. At a pO₂ of 1 atm, SCF adopts a cubic perovskite structure, space group Pm3¯m, across the whole temperature range investigated. At a pO₂ of 10^− 1 atm, a two-phase region exists below 922 K, where the cubic perovskite phase coexists with a vacancy ordered brownmillerite phase, Sr₂Co_1.6Fe_0.4O₅, space group Icmm. A pure brownmillerite phase is present at pO₂ of 10^− 2 and 5 × 10^− 4 atm below 1020 K. Above 1020 K, the brownmillerite phase transforms to cubic perovskite through a two-phase region with no brownmillerite structure observed above 1064 K. Large distortion of the BO₆ (B = Co, Fe) octahedra is present in the brownmillerite structure with apical bond lengths of 2.2974(4) Å and equatorial bond lengths of 1.9737(3) Å at 1021 K and a pO₂ of 10^− 2 atm. SCF is highly oxygen deficient with a maximum oxygen stoichiometry, 3 − δ, measured in this study of 2.58(2) at 873 K and a pO₂ of 1 atm and a minimum of 2.33(2) at 1173 K and a pO₂ of 5 × 10^− 4 atm. Significant differences in lattice volume and expansion behavior between the brownmillerite and cubic perovskite phases suggest potential difficulties in thermal cycling of SrCo_0.8Fe_0.2O_3−δ membranes.     

High temperature protonic conduction in Sr-doped LaP3O9

Electrical conduction of Sr-doped LaP₃O₉ ([Sr]/{[La] + [Sr]} = 2–10 mol%) was investigated under 0.4–5 kPa of p(H₂O) and 0.01–100 kPa of p(O₂) or 0.3–3 kPa of p(H₂) at 573–973 K. Sr-doped LaP₃O₉ showed apparent H/D isotope effect on conductivity regardless of the Sr-doping level under both H₂O/O₂ oxidizing and H₂/H₂O reducing conditions at investigated temperatures. Conductivities of the material were almost independent of p(O₂) and p(H₂O). These results demonstrated that the Sr-doped LaP₃O₉ exhibited protonic conduction under wide ranges of p(O₂), p(H₂O) and temperature. The conductivity of the Sr-doped LaP₃O₉ increased with increasing Sr concentration up to its solubility limit, ca. 3 mol%, while the further Sr-doping slightly degraded the conductivity. These indicate that Sr²⁺ substitution for La³⁺ leads to proton dissolution into the material and induced protonic conduction. Conductivities of the 3 mol% Sr-doped sample were 2 × 10^- 6–5 × 10^− 4 S cm^− 1 at 573–973 K.     

Effects of Zr/Ti ratio on dielectric and ferroelectric properties of 0.8Pb(ZrxTi1−x)O3–0.2Pb(Co1/3Nb2/3)O3 ceramics

The influences of Zr/Ti ratio on electrical properties of the 0.8Pb(Zr_xTi_1−x)O₃–0.2Pb(Co_1/3Nb_2/3)O₃ ceramics prepared by a mixed-oxide method (with x = 0.46, 0.48, 0.50, 0.52, and 0.54) have been investigated in order to identify the morphotropic phase boundary composition in this system. With XRD analysis, the crystal structure of dense specimens appeared to change gradually from tetragonal to rhombohedral with increasing Zr content. The dielectric properties measurements showed a maximum dielectric constant at x = 0.50, while the transition temperature decreased with increasing Zr content in the system. Moreover, all ceramics showed diffused phase transition behaviors with a minimum diffusivity at x = 0.50. In addition, the Polarization–Electric field (P–E) hysteresis loops of the ceramic systems also changed significantly with the Zr content. Interestingly, the loop squareness parameter reached maximum around x = 0.50. Other ferroelectric hysteresis parameters showed noticeable change at x = 0.50. These results clearly showed the significance of Zr/Ti ratio in controlling the electrical properties of the PZT–PCN ceramic systems.     

Dielectric and ferroelectric properties of 0.8PZT–0.2PCN ceramics under sintering conditions variation

The influences of sintering conditions on electrical properties of the 0.8Pb(Zr_1/2Ti_1/2)O₃–0.2Pb(Co_1/3Nb_2/3)O₃ ceramics have been investigated with sintering temperatures of 1175, 1200, 1225, and 1250 °C and dwell times for 2, 6, and 10 h. The crystal structure of dense specimens showed coexistence between tetragonal, rhombohedral and pseudo cubic phases in all sintering temperatures, while tetragonal-rich phase appeared with increasing dwell times. A maximum dielectric constant was observed at sintering condition of 1200 °C for 2 h, while the transition temperature slightly increased with increasing dwell time. All ceramics also showed diffused phase transition behaviors with a minimum diffusivity at sintering condition of 1200 °C for 2 h. In addition, the polarization–electric field (P–E) hysteresis loops of the ceramic systems also changed significantly with sintering conditions. Interestingly, the ferroelectric parameters; remnant polarization (P_r) and loop squareness (R_sq) tended to increase with increasing sintering temperatures and dwell times.     

Enhanced mangnetoelectric voltage in multiferroic particulate Ni0.83Co0.15Cu0.02Fe1.9O4−δ/PbZr0.52Ti0.48O3 composites – dielectric,piezoelectric and magnetic properties

Multiferroic particulate composites of Ni_0.83Co_0.15Cu_0.02Fe_1.9O_4−δ– NCCF and lead zirconate titanate (PZT) were prepared conventional ceramic method. The generic formulae x NCCF + (1−x) PZT where x = 0.1, 0.2, 0.3, 0.4, 0.5 and 0.6 mole fractions. The presence of two phases in multiferroic was confirmed with XRD technique. The dielectric constant and loss tangent were studied as a function of frequency (100 Hz to 1 M Hz) and temperature (30–500 °C). The piezoelectric coefficient d₃₃ were also studied on these particulate composites. The hysteresis behaviour was studied to understand the magnetic properties such as saturation magnetization (Ms) and magnetic moment (μ_B). The static magnetoelectric (ME) voltage coefficient was measured as a function of dc magnetic bias field. A high value of ME output (3151 mV/Oe.cm) was obtained in the composite containing 50% highly magnetostrictive ferrite component NCCF – 50% highly piezoelectric ferroelectric component PZT. These multiferroic particulate composites are used as phase shifters, magnetic sensors, cables etc.     

Dielectric and piezoelectric properties of (Bi1−x−yNdxNa1−y)0.5BayTiO3 lead-free ceramics

New lead-free (Bi_1−x−yNd_xNa_1−y)_0.5Ba_yTiO₃ ceramics were prepared by a conventional ceramic technique and their dielectric and piezoelectric properties were studied. X-ray diffraction studies reveal that Nd³⁺ and Ba²⁺ diffuse into the Bi_0.5Na_0.5TiO₃ lattices to form a new solid solution with a pure perovskite structure, and a morphotropic phase boundary (MPB) of rhombohedral and tetragonal phases is formed at 0.04 < y < 0.10. The partial substitutions of Nd³⁺ and Ba²⁺ decrease effectively the coercive field E_c and increase significantly the remanent polarization P_r. Because of lower E_c, larger P_r and the formation of the MPB, the piezoelectric properties of the ceramics are significantly enhanced at x/y = 0.02/0.06: d₃₃ = 150 pC/N and k_p = 30.5%. The ceramics exhibit relaxor characteristic, which is probably resulted from the cation disordering in the 12-fold coordination sites. The depolarization temperature T_d shows a strong compositional dependence and reaches a minimum value at the MPB. The temperature dependences of the ferroelectric and dielectric properties suggest that the ceramics may contain both the polar and non-polar regions near the depolarization temperature T_d, which cause the polarization hysteresis loop become deformed near/above T_d.     

Low-temperature investigations of the open-framework material HfMgMo3O12

The A₂Mo₃O₁₂ family, where A³⁺ is a large trivalent cation, can show interesting thermal properties such as negative thermal expansion. One member of this family, HfMgMo₃O₁₂, where the two A³⁺ cations have been replaced by Hf⁴⁺ and Mg²⁺, has been shown to have a low positive coefficient of thermal expansion above room temperature. This property makes HfMgMo₃O₁₂ an attractive candidate as a component for solid solutions with near-zero thermal expansion. However, its properties below room temperature were unexplored. In this work we report the phase transition from orthorhombic Pnma to monoclinic P2₁/a at T～175 K with an enthalpy change of 0.27 kJ mol^?1. Relaxation calorimetry, from 5 K to 300 K, show only the small anomaly associated with this transition. The thermal conductivity, determined from 2 K to 300 K, was low, but not as low as some other materials exhibiting negative thermal expansion. Analysis of the low-temperature heat capacity indicates the presence of low-energy phonon modes in HfMgMo₃O₁₂, consistent with the low thermal conductivity. The upper bound of the Young's modulus, estimated from the effective Debye temperature derived from the low-temperature heat capacity, is 20 GPa, a relatively low value due to the flexibility of the framework structure.     

Mixed conductivity,stability and thermomechanical properties of Ni-doped La(Ga,Mg)O3−δ

Perovskite-type LaGa_0.65Mg_0.15Ni_0.20O_3−δ exhibiting oxygen transport comparable to that in K₂NiF₄-type nickelates was characterized as a model material for ceramic membrane reactors, employing mechanical tests, dilatometry, oxygen permeability and faradaic efficiency measurements, thermogravimetry (TG), and determination of the total conductivity and Seebeck coefficient in the oxygen partial pressure range from 10^− 15 Pa to 40 kPa. Within the phase stability domain which is similar to La₂NiO_4+δ, the defect chemistry of LaGa_0.65Mg_0.15Ni_0.20O_3−δ can be adequately described by the ideal solution model with oxygen vacancies and electron holes to be the only mobile defects, assuming that Ni²⁺ may provide two energetically equivalent sites for hole location. This assumption is in agreement with the density of states, estimated from thermopower, and the coulometric titration and TG data suggesting Ni⁴⁺ formation in air at T < 1150 K. The hole conductivity prevailing under oxidizing conditions occurs via small-polaron mechanism as indicated by relatively low, temperature-activated mobility. The ionic transport increases with vacancy concentration on reducing p(O₂) and becomes dominant at oxygen pressures below 10^− 7–10^− 5 Pa. The average thermal expansion coefficients in air are 11.9 × 10^− 6 and 18.4 × 10^− 6 K^− 1 at 370–850 and 850–1270 K, respectively. The chemical strain of LaGa_0.65Mg_0.15Ni_0.20O_3−δ ceramics at 1073–1123 K, induced by the oxygen partial pressure variations, is substantially lower compared to perovskite ferrites. The flexural strength determined by 3-point and 4-point bending tests is 167–189 MPa at room temperature and 85–97 MPa at 773–1173 K. The mechanical properties are almost independent of temperature and oxygen pressure at p(O₂) = 1–2.1 × 10⁴ Pa and 773–1173 K.