Structural,microstructural, ferroelectric and photoluminescent properties of praseodymium modified Ba0.98Ca0.02Zr0.02Ti0.98O3 ceramics

The ‘x’ wt% (x = 0, 0.02, 0.04 and 0.06) Pr₆O₁₁ modified Ba_0.98Ca_0.02Zr_0.02Ti_0.98O₃ (BCZT – x Pr) piezoelectric ceramics have been fabricated by the solid state reaction method with sintering at 1450 °C (x = 0) and 1350 °C (0.02 ≤ x ≤ 0.06) for 2 h. The impact of Pr concentration on the structural, microstructural, photoluminescence and ferroelectric properties has been systematically investigated. The x-ray diffraction (XRD) patterns revealed the co-existence of tetragonal and orthorhombic phases at room temperature upto x = 0.04 Pr concentration. The grain size was found to decrease upto x = 0.04 Pr content. Room temperature Raman spectroscopy results were consistent with the XRD results. The photoluminescence (PL) spectra showed significant emissions consisting of strong blue (489 nm), green (528 nm) and red (649 nm) wavelengths. The emission intensities of PL spectrum were strongly Pr concentration dependent and a maximum value was obtained for 0.04 Pr modified BCZT ceramic. Further, a large remnant polarization (2P_r ~ 13 µC/cm²) and low coercive field (E_C ~ 22 V/cm) were obtained for BCZT – 0.04 Pr ceramic. The crystal structure and microstructure affect the photoluminescence and ferroelectric properties. Such properties of 0.04 Pr modified BCZT ceramic make it the potential candidate for novel integrated and multifunctional devices.     

Preparation and mid-infrared 2.7 µm luminescence property of high content Er3+-doped (Y0.9La0.1)2O3 transparent ceramics pumped at 980 nm

High content Er³⁺ doped (Y_0.9La_0.1)₂O₃ transparent ceramics have been prepared by conventional ceramic process. Absorption spectra, mid-infrared, up-conversion and near-infrared emission spectra of Er³⁺ pumped at 980 nm have been investigated. The mechanisms of energy transfer processes have been discussed. Large values of Judd–Ofelt parameter Ω₂ (5.73 × 10^–20 cm²) and spectral quality factor X (3.71) have been obtained. The greatly enhanced green up-conversion emission in the high Er³⁺ doped sample is considered important for the applications in up-converters. The much enhanced mid-infrared 2.7 µm and up-conversion emissions, as well as the depressed near-infrared 1.5 µm emission demonstrate the efficient population inversion of Er³⁺:⁴I_11/2 → ⁴I_13/2 in high Er³⁺-doped ceramics for the 2.7 µm emission. These results suggest that high Er³⁺-doped (Y_0.9La_0.1)₂O₃ transparent ceramics are promising host materials for the applications of mid-infrared lasers and infrared-to-visible up-converters.     

A novel ((Bi0.5Na0.5)0.94Ba0.06)1-x (K0.5Nd0.5)xTiO3 lead-free relaxor ferroelectric ceramic with large electrostrains at wide temperature ranges

Novel ((Bi_0.5Na_0.5)_0.94Ba_0.06)_1-x(K_0.5Nd_0.5)_xTiO₃(x = 0.0, 0.02, 0.04, 0.06) lead-free ceramics (BNBT–xKN) were prepared by the solid-state reaction method. The effects of A-site (K_0.5Nd_0.5)²⁺ complex-ion substitution on their phase structure, dielectric, piezoelectric, and electromechanical properties were studied. The X-ray diffraction results indicate that all compositions are located in the morphotropic phase boundary (MPB) region where the tetragonal phase coexists with the rhombohedral phase. In addition, as the KN content increases, the ferroelectric order transform to relaxor order, which is characterized by a degeneration of maximum polarization, remnant polarization and correspondingly adjusts the ferroelectric-relaxor transformation temperature (T_F-R) to room temperature. Interestingly, the disruption of ferroelectric phase caused a significant improvement of strains. A maximum strain of ~ 0.52% corresponding to normalized strain of ~ 612 pm/V appeared at 85 kv/cm for the x = 0.04 composition. Particularly, the composition of x = 0.04 exhibited high electrostrains of temperature insensitivity, which remained above 0.4% and kept within 10% from ambient temperature up to 110 °C. It can be ascribed to the coexistence of non-ergodic and ergodic states in the relaxor region. As a result, the systematic investigations on the BNBT–xKN ceramics can benefit the developments of temperature-insensitive “on-off” actuators.     

Giant electrocaloric effect of free-standing Pb0.85La0.1(Zr0.65Ti0.35)O3 thick films fabricated by the self-lift-off screen printing method

Free-standing Pb_0.85La_0.1(Zr_0.65Ti_0.35)O₃ (PLZT) ceramic thick films have been prepared via a facile and low-cost self-separating screen printing method for electrocaloric cooling, and the relation among the fabrication processes, phase composition, microstructure, dielectric characteristics, ferroelectric properties and electrocaloric effect (ECE) has been systematically investigated. Compared to the conventional ceramic thick films supported by substrates, the free-standing feature enables the EC cooling of the free-standing PLZT thick films to be fully used for cooling down different thermal loads rather than be futilely absorbed by the substrates. Furthermore, without the mechanical restriction of the substrates, the free-standing PLZT thick films can freely shrink during the high-temperature densification process, leading to their high density and favorable microstructures. Additionally, by introducing an adequate amount of excess PbO, the pyrochlore phase can be removed from the samples to yield high-purity perovskite PLZTs. With the comprehensive improvement in phase composition, microstructure and the elimination of mechanical strain between the active materials and substrates, the free-standing PLZT thick films exhibited an optimized ECE including changes of temperature and entropy of 1.95 °C and 2.09 J kg^?1 K^?1, which are almost 3 times that of the samples deposited on the Al₂O₃ substrates without excess PbO. This work would contribute to the development of ferroelectric ceramics, especially thick films, for practical EC cooling.     

Effects of TiO2 addition on dielectric and energy storage properties of BaO-K2O-Nb2O5-SiO2 glass ceramics

In this work, 25.6BaO-6.4K₂O-32Nb₂O₅-36SiO₂-xTiO₂ (0 ≤ x ≤10 mol%) (BKNST) glass ceramics were synthesized by conventional melts and controllable crystallization method. The effects of different TiO₂ addition on the phase composition, dielectric and energy storage properties of BKNS glass ceramics were systematically evaluated. With the TiO₂ concentration increasing, a growing content of Ba₂TiO₄ phase was observed in the glass ceramics. The microstructures appeared to be homogenous and uniform with very low porosity through the addition of TiO₂, for which the maximal breakdown strength of 2112 kV/cm and the corresponding energy storage density of 9.48 J/cm³ were obtained with x = 7.5. The extremely low dielectric loss of less than 1‰ (25 °C, 100 kHz) and the obviously improved microstructure contributed to the increased breakdown strength. In addition, the discharge power density of the glass-ceramic capacitor (x = 7.5) was investigated using the RLC charge-discharge circuit and a relatively high value of 16 MW/cm³ at 300 kV/cm was obtained.     

Enhanced dielectric and energy-storage properties in ZnO-doped 0.9(0.94Na0.5Bi0.5TiO3−0.06BaTiO3)−0.1NaNbO3 ceramics

[0.9(0.94Na_0.5Bi_0.5TiO₃?0.06BaTiO₃)?0.1NaNbO₃]-xZnO (NBT-BT-NN-xZnO, x=0, 0.5 wt%, 1.0 wt%, 1.5 wt%, and 2.0 wt%) ferroelectric ceramics were fabricated using a conventional solid-state reaction method. The effects of ZnO content on dielectric, energy-storage and discharge properties were systematically investigated. Dielectric constant and difference between maximum and remanent polarization were significantly improved by ZnO doping. Dielectric constant of NBT-BT-NN-1.0-wt% ZnO was 3218 at 1 kHz and room temperature, i.e. one time bigger than that of pure NBT-BT-NN ceramic. As a consequence, a maximum energy-storage density of 1.27 J/cm³ with a corresponding efficiency of 67% was obtained in NBT-BT-NN-1.0-wt% ZnO ceramic. Moreover, its pulsed discharge energy density was 1.17 J/cm³, and 90% of which could be released in less than 300 ns. Therefore, ZnO doped NBT-BT-NN ceramic with a large energy-storage density and short release time could be a potential candidate for applications in high energy-storage capacitors.     

Low-temperature sintering of Ti1−xCux/3Nb2x/3O2 (x = 0.23) microwave dielectric ceramics with CuO and B2O3 addition

The influence of CuO and B₂O₃ addition on the sintering behavior, microstructure and microwave dielectric properties of Ti_1?xCu_x/3Nb_2x/3O₂ (TCN, x = 0.23) ceramic have been investigated. It was found that the addition of CuO and B₂O₃ successfully reduced the sintering temperature of TCN ceramics from 950 to 875 °C. X-ray diffraction studies showed that addition of CuO-B₂O₃ has no effect on the phase composition. The TCN ceramics with 0.5 wt% CuO-B₂O₃ addition showed a high dielectric constant of 95.63, τ_f value of + 329 ppm/°C and a good Q × f value of 8700 GHz after sintered at 875 °C for 5 h, cofirable with silver electrode.     

Enhanced magnetocaloric effect of Sr1.8Eu0.13Ba0.07FeMoO6 perovskite compound

Double perovskite (Sr_1.8Eu_0.13Ba_0.07)FeMoO₆ (SEBFMO) as well as Sr₂FeMoO₆ (SFMO) were prepared by the traditional solid reaction method. X-ray diffraction results show that all compounds are single phase, which belongs to I4/m space group. The magnetic hysteretic loops (M-H) and field-cooled magnetization (FC) curves indicate that all compounds have good ferromagnetic properties. The FC curves show a phase transition temperature at around 370 K. The Arrot plots (H/M-M²) of samples show that a second-order magnetic transition has occurred. An enhanced magnetocaloric effect was observed in SEBFMO. The maximum isothermal magnetic entropy change of SEBFMO reaches to 0.76 J kg^?1 K^?1 for ?H = 3 T, but that of SFMO only reaches to 0.50 J kg^?1 K^?1.     

Investigation of fracture toughness of modified (KxNa1 − x)NbO3 lead-free piezoelectric ceramics

While most of the previous studies have focused on the processing and electrical properties of KNN-based ceramics, very little research has been carried out to evaluate their mechanical behavior. This work presents for the first time an examination of the fracture toughness, K_IC, of the most widely studied (K_xNa_1 ? x)NbO₃ (KNN)-based lead-free ceramics modified with lithium, tantalum and antimony. The samples were produced through the conventional mixed-oxide route and the K_IC values were measured using the single edge V-notched beam (SEVNB) method under four-point bending. The mean K_IC values were determined to be 0.48 ± 0.18 MPa m^1/2 for (K_0.48Na_0.48Li_0.04)NbO₃, 0.8 ± 0.18 MPa m^1/2 for (K_0.5Na_0.5)(Nb_0.9Ta_0.1)O₃, 0.86 ± 0.04 MPa m^1/2 for (K_0.48Na_0.48Li_0.04)(Nb_0.9Ta_0.1)O₃ and 1.06 ± 0.21 MPa m^1/2 for (K_0.48Na_0.48Li_0.04)(Nb_0.86Ta_0.1Sb_0.04)O₃ compositions. The microstructure, phase structure and dielectric constant values of the samples have been used to correlate the results of the K_IC values.     

A novel aerogels/porous Si3N4 ceramics composite with high strength and improved thermal insulation property

A novel ZrO₂-SiO₂ aerogels/porous Si₃N₄ ceramics composite with high strength, low density, good dielectric properties and low thermal conductivity was synthesized by filling ZrO₂-SiO₂ aerogels into the porous Si₃N₄ ceramics through vacuum sol-impregnating. The effects of aerogels on the microstructure and properties of composite were discussed. The results show that aerogels could form a mesoporous structure and significantly decrease the thermal conductivity from 9.8 to 7.3 W m^?1 K^?1. Meanwhile, the density, mechanical and dielectric properties of the porous Si₃N₄ ceramics could not be affected after introducing ZrO₂-SiO₂ aerogels. The composite exhibits high porosity (62.6%), high flexural strength (53.86 MPa) and low dielectric constant (2.86). The ZrO₂-SiO₂ aerogels/porous Si₃N₄ ceramics composite shows great potential as radome materials applied in the fields of aerospace.     

Investigation on the anti-reduction mechanism of Ti4+ in high dielectric constant system Ca0.9La0.067TiO3 by doping with Al2O3

Ca_0.9La_0.067TiO₃ (abbreviated as CLT) ceramics doped with different amount of Al₂O₃ were prepared via the solid state reaction method. The anti-reduction mechanism of Ti⁴⁺ in CLT ceramics was carefully investigated. X-ray diffraction (XRD) was used to analyze the phase composition and lattice structure. Meanwhile, the Rietveld method was taken to calculate the lattice parameters. X-ray photoelectron spectroscopy (XPS) was employed to study the valence variation of Ti ions in CLT ceramics without and with Al₂O₃. The results showed that Al³⁺ substituted for Ti⁴⁺ to form solid solution and the solid solubility limit of Al³⁺ is near 1.11 mol%. Furthermore, the reduction of Ti⁴⁺ in CLT ceramics was restrained by acceptor doping process and the Q × f values of CLT ceramics were improved significantly. The CLT ceramic doped with 1.11 mol% Al₂O₃ exhibited good microwave dielectric properties: ε_r = 141, Q × f = 6848 GHz, τ_f = 576 ppm/°C.     

Processing,microstructure and performance of Al2O3/Er3Al5O12/ZrO2 ternary eutectic ceramics prepared by laser floating zone melting with ultra-high temperature gradient

Directionally solidified Al₂O₃/Er₃Al₅O₁₂(EAG)/ZrO₂ ternary eutectic/off-eutectic composite ceramics with high density, homogeneous microstructures, well-oriented growth have been prepared by laser floating zone melting at different solidification rates from 4 to 400 µm/s. Uniform and stable melting zone is obtained by optimizing temperature field distribution to keep continuous and stable eutectic growth and prevent from cracks and defects. The as-solidified composite ceramic exhibits complexly irregular eutectic structure, in which the eutectic spacing is rapidly refined but dotted ZrO₂ number inside Al₂O₃ phase is decreased as increasing the solidification rate. The formation mechanism of ZrO₂ distributed inside Al₂O₃ matrix is revealed by examining the depression of solid/liquid interface. Furthermore, after heat exposure 1500 °C for 200 h, the eutectic microstructure only shows tiny coarsening, which indicates it has excellent microstructural stability. As increasing the ZrO₂ content, the fracture toughness can be improved up to 3.5 MPa m^1/2 at 20.6 mol% ZrO₂.     

Large electric-field-induced strain in B-site complex-ion (Fe0.5Nb0.5)4+-doped Bi1/2 (Na0.82K0.12)1/2TiO3 lead-free piezoceramics

In order to obtain a new system of (Bi_1/2Na_1/2)TiO₃ (BNT) based lead-free incipient piezoceramics with large strain for practical applications of actuators, we investigated the effect of B-site complex-ion (Fe_0.5Nb_0.5)⁴⁺ (FN)-doped Bi_1/2 (Na_0.82K_0.12)_1/2TiO₃ ceramics on the phase structure, dielectric, ferroelectric, piezoelectric and electric-field-induced strain properties. All samples exhibited single perovskite phase with pseudocubic symmetry. The room temperature electric-field-induced polarization (P-E) and strain (S-E) hysteresis loops indirectly illustrated ferroelectric-to-relaxor (FE-RE) phase transition. The increasing content of FN doping decreased the FE-RE phase transition temperature, T_F-R to below room temperature and induced the reversible FE-RE phase transition, giving rise to a large strain of 0.462% with a normalized strain, d^*₃₃ of 660 pm/V at a critical composition of x = 5. A fluctuation of the dielectric curve for BNKT-5 mol% FN ceramics in the spectra around 80 °C before and after polarization suggested that the large strain response can be induced via delicate mixing of the FE and RE phase.     

Investigation of optical,mechanical, and thermal properties of ZrO2-doped Y2O3 transparent ceramics fabricated by HIP

Highly transparent ZrO₂-doped Y₂O₃ ceramics were successfully synthesized using the hot isostatic pressing (HIP) process. The effects of the ZrO₂ content on the sintering behaviors, optical transmission spectra, Vickers hardness, grain size, size distribution, and Raman spectra were determined. The results indicated that decreased ZrO₂ content could promote increased transmittance, red-shifted infrared cutoff wavelength, increased thermal conductivity, decreased Vickers hardness, and increased lattice ordering. According to the optical transmission spectra, the optimized ZrO₂ content was 0.50 at%, at which point the ceramic exhibited a larger pre-sintering temperature range of 1650–1750 °C and the average grain size of 3.35 µm at 1750 °C. The grain size was significantly decreased at lower pre-sintering temperatures. Furthermore, a moderate Vickers hardness of 8.42 GPa and high thermal conductivity of 10.85 W/m K at room temperature were obtained for the optimized ceramic.     

Joining of dense Si3N4 ceramics with tape cast Lu-Al-Si-O-N interlayer

Lu-Al-Si-O-N tapes with different thickness were used to join gas pressure sintered Si₃N₄ ceramics. The microstructure of the joints and the influences of the joint thickness and joining temperature on the bonding strength of the as-joined Si₃N₄ ceramics have been investigated. The highest bonding strength about ~ 300 MPa of the joined specimens was achieved by using 450 µm interlayer at 1450 °C. The existence of Si₃N₄ nanowires was beneficial for the improvement of the bonding strength by interweaving the oxynitride glass matrix in the joint region.     

Structural and electrical characterization of (K0.48Na0.52)0.96Li0.04Nb0.85Ta0.15O3 synthesized by spray drying

The synthesis of lead-free ferroelectric materials with composition (K_0.48Na_0.52)_0.96Li_0.04Nb_0.85Ta_0.15O₃ has been achieved by spray drying technique. Pure perovskite phase was obtained after calcination of as-prepared powders at 800 °C for 1 h. Crystallized powders have a particle size average of 100 nm. Well sintered samples were obtained at 1120 and 1130 °C for 2 h in air with densities of 4.58 and 4.49 g/cm³, respectively. We attributed this improvement as the result of sintering process and the very small particle size in powders. Sintered samples have promising piezoelectric parameters, k_p 0.40–0.41, d₃₁ 50–55 pC/N and dielectric losses around 1%.     

Ferroelectric,upconversion emission and optical thermometric properties of color-controllable Er3+-doped Pb(Mg1/3Nb2/3)O3-PbTiO3-Pb(Yb1/2Nb1/2)O3 ferroelectrics

The (0.98-x)(0.6Pb(Mg_1/3Nb_1/3)O₃-0.4PbTiO₃)-xPb(Yb_1/3Nb_1/3)O₃-0.02Pb(Er_1/2Nb_1/2)O₃ ((0.98-x)(PMN-PT)-xPYN:Er³⁺) ceramics were prepared through a solid-state reaction method. The phase structure, piezoelectric response, ferroelectric performance and upconversion emission of the ceramics were systematically investigated. The phase structure, the electrical and optical properties are strongly related to the content of PYN. The optimized piezoelectric response and upconversion emissions of the ceramics were achieved near x = 0.12, which locates in the morphotropic phase boundary (MPB) composition. Furthermore, the temperature sensing behaviors of the resultant compounds based on the thermally coupled levels of ²H_11/2 and ⁴S_3/2 of Er³⁺ ions in the temperature range of 133–573 K were studied by utilizing the fluorescence intensity ratio technique. Additionally, the thermal effect, which is induced by the laser pump power, of the studied ceramics is also investigated and the produced temperature is enhanced from 268 to 348 K with the pump power rising from 109 to 607 mW.     

Dielectric relaxation properties of SrTiO3 ceramics modulated by stoichiometry

SrTiO₃ has received increasing attention duo to the fact that small perturbation can produce outstanding physical properties. Nonstoichiometric SrTiO₃ ceramics have been prepared in the range of Sr/Ti = 1.064–0.943. Their dielectric behaviors are investigated in the temperature range of 30–500 °C and in the frequency range 100 Hz to 2 MHz. It is observed that the two types of dielectric relaxation processes are caused by polar nanoregions associated with Sr non-stoichiometry and variable range hopping behavior associated with the dipolar effects for Sr/Ti>1 and Sr/Ti<1 ceramics samples, respectively. Our findings imply that the cation vacancy may be responsible for the adjusted properties in nonstoichiometric SrTiO₃.     

Composition and poling-induced modulation on photoluminescence properties for NBT-xBT: Pr3+ ceramics

In this work, the modulation of photoluminescence (PL) properties, which was realized by the composition and poling-induced structural evolution, for the Pr³⁺ doped (1-x)(Na_1/2Bi_1/2)TiO₃-xBaTiO₃ (NBT-xBT: Pr³⁺) piezoelectric ceramics was systematically investigated. Based on the Rietveld refinement structural analysis, there were two distinct composition ranges characterized by different structural features for NBT-xBT: Pr³⁺ ceramics at room temperature: (i) rhombohedral R3c + monoclinic Cc phases for the compositions of x ≤ 0.03, and (ii) tetragonal P4bm + monoclinic Cc phases for 0.04 ≤ x ≤ 0.07. It was interesting to notice that the PL emission intensity is positively correlated with the phase fraction of Cc, which is closely related to the crystal symmetry of NBT-xBT: Pr³⁺ ceramics. The compositions with x ≤ 0.06 underwent an irreversible phase transformation on the application of electric field. The dielectric and Raman measurement revealed a transition from a relaxor state to a normal ferroelectric for the x ≤ 0.06 compositions under an applied poling electric field, with not only the reduction in the in-phase octahedral tilting disorder but also the establishment of long-range ordering. These electric field-induced structural changes were responsible for poling-induced PL quenching behaviors as a result of the increased local structure symmetry around doped Pr³⁺ ions in the poled ceramics.     

Stirring speed assisted homogenization of precipitation reaction for enhanced optical performance of Y2O3 transparent ceramics

Y₂O₃ transparent ceramics were fabricated from precipitated powders prepared at different stirring speeds during the precipitation process. The influence of the stirring speed on the phase component of precursors, morphology of Y₂O₃ powders and properties of fabricated ceramics were systematically investigated. Crystalline phase precursors of (NH₄)_aY(OH)_b(CO₃)_c·H₂O were prepared from 110 rpm, 220 rpm and 550 rpm respectively. But amorphous precursors of Y(CO₃)(OH)·nH₂O (n = 1–1.5) were observed when stirring speeds were 330 rpm and 440 rpm. Y₂O₃ powders prepared from 440 rpm exhibited the lowest agglomeration and the smallest grain size, and the ceramics with the optimal transmittance was accordingly obtained. The results of computational fluid dynamics software CFX showed that a more homogeneous flow field distribution without local circulations could be produced at 440 rpm, which would be benefit for the optical quality of transparent ceramics. The study would provide a considerable reference for the controllable fabrication of well-dispersibility Y₂O₃ powders and Y₂O₃ transparent ceramics.