Novel strategy for the enhancement of anti-counterfeiting ability of photochromic ceramics: Sm3+ doped KSr2Nb5O15 textured ceramics with anisotropic luminescence modulation behavior

Sm³⁺ doped KSr₂Nb₅O₁₅ (KSN-Sm) textured ceramics with anisotropic photochromic and luminescence modulation behaviors provided a new strategy for the enhancement of anti-counterfeiting ability. The KSN-Sm textured ceramics were fabricated by the tape casting technology, which exhibited obvious grain-orientation, with Lotgering factor f_(00l) of 0.62. The textured sample possessed evident difference of reflectivity, photochromic, luminescent and luminescence modulation properties among various grain-orientated directions. The difference of luminescent emission intensity was over than 30 % and the luminescence modulation ratios △R_t are 75.3 % and 63.3 % along paralleled and vertical [00l] orientations, respectively. These optical anisotropies were attributed to the different refractive indexes, distributions of photochromic centers and energy transfer rates at various orientations. This work is hopeful to achieve the multidirectional data recording and enhancement of anti-counterfeiting ability of photochromic ceramics by the anisotropic properties of textured ceramics.     

Piezoelectricity,thermal stability,and fatigue resistance in Nb and Ta-doped Bi4Ti3O12 high-temperature piezoceramics

The effect of Nb/Ta donor doping on the piezoelectricity, thermal stability, and fatigue resistance of bismuth titanate Bi₄Ti₃O₁₂ (BIT) ceramics was investigated in relation to their structural and oxygen vacancy-related electrical properties. As the Nb/Ta doping amount increased, the activation energy of oxygen vacancy conduction increased, indicating a reduction in the concentration of oxygen vacancies. The improved electrical insulating properties of the Nb/Ta-doped Bi₄Ti₃O₁₂ ceramics (BTNT) with fewer oxygen vacancies, contributed to their effective poling and strong piezoelectricity. Outstanding piezoelectric performance with high piezoelectric constant (39 pC/N) and Curie temperature (690 °C) could be achieved in the 0.005 mol Nb/Ta-doped BTNT ceramic with high density and anisotropic grain growth. The BTNT ceramics exhibited superior thermal aging stability and fatigue resistance compared to the BIT ceramic, suggesting that the reduction of oxygen vacancy defects plays a decisive role in enhancing elevated-temperature-induced and electric-field-induced degradation stabilities.     

BNT-based relaxor/ferroelectric systems: Improved field-induced strain property in the layered composite ceramics

Both high strain and low driving electric-field are important characteristics of the piezoelectric actuators for industrial applications, but they are difficult to achieve together in a single material system. In this work, the layered and inlay-onlay structures of relaxor/ferroelectric composites were prepared by selecting relaxor phase (0.94Bi_0.5(Na_0.82K_0.18)_0.5TiO₃-0.06NaNbO₃, BNKT-6NN) and ferroelectric phase (0.9Bi_0.5Na_0.5TiO₃-0.1Bi_0.2Sr_0.7TiO₃, BNT-10BST) with the volume ratio of 1:1. By comparing the field-induced strains under same electric-field, the S₃₃ of the BNKT-6NN/BNT-10BST layered composites (0.17%) was greater than that of the inlay-onlay composites (0.08%) and exhibited excellent temperature stability. The superiority in field-induced strain for the layered composite ceramic was originated from the inhomogeneous distribution of internal electric-field between relaxor and ferroelectric phase and thereby could modulate the polar nanoregions to ferroelectric phase transition. In addition, the restricted phase boundary between relaxor and ferroelectric phase enhanced the potential barrier energy (E_a = 1.47 eV) and hindered the jump of defective ions (mainly oxygen vacancies) of the BNKT-6NN/BNT-10BST layered composites. The outstanding electrical properties of layered composite ceramics provide a new idea for further improving field-induced strain performance.     

Enhanced piezoelectricity and high-temperature sensitivity of Zn-modified BF-BT ceramics by in situ and ex situ measuring

Effect of Zn addition on microstructure, electrical properties and temperature stability and sensitivity of piezoelectric properties for 0.7Bi_1-xZn_xFeO₃ −0.3BaTiO₃ (abbreviated as BZxF–BT) ceramics was investigated. The improved piezoelectric properties, high-temperature stability and high-temperature sensitivity by in situ and ex situ measuring were obtained by moderate Zn addition. It was demonstrated that the enhancement piezoelectric properties can be attributed to poling induced texturization degree of ferroelectric domains and increased rhombohedral structural distortions. It was proposed that the depoling temperature where the induced small signal piezoelectricity disappears stemmed from the detexturization of preferred orientation domains. The improved piezoelectric responses and high-temperature sensitivity could be attributed to the thermally activated preferred orientation domains. The good piezoelectric properties together with high-temperature stability suggest that BZxF–BT system is a promising material for high temperature piezoelectric applications.     

The anisotropic conductivity of ferroelectric La2Ti2O7 ceramics

Ferroelectric ceramics with perovskite-like layered structure (PLS) have good potential for high temperature piezoelectric applications due to their high Curie point (T_c). The electrical conduction behaviour of these materials is a critical parameter to consider for practical applications. In this study, we prepared textured ceramics of the typical PLS ferroelectric La₂Ti₂O₇ using spark plasma sintering and investigated the electrical properties using impedance spectroscopy and Seebeck measurements. The results reveal that the bulk resistivity along the parallel direction is much higher than that along the perpendicular direction. The activation energy for conduction (E_a) along the parallel direction is 1.45 eV, which is close to half of the optical band gap and much higher than the 0.67 eV along the perpendicular direction. Electrical conduction along both the directions is dominated by p-type hole conduction. No appreciable contribution of oxide ion conduction to the measured conductivity is observed.     

Fabrication and electrical properties of textured (Na,K)0.5Bi0.5TiO3 ceramics by reactive-templated grain growth

Textured (Na_0.85K_0.15)_0.5Bi_0.5TiO₃ (NKBT) ceramics with a relative density of >94% were fabricated by reactive-templated grain growth. Plated-like Bi₄Ti₃O₁₂ template particles synthesized by the NaCl–KCl molten salt process were aligned by tape casting in a mixture of original oxide powders. The effect of sintering temperature on the grain orientation and electrical properties of textured NKBT ceramics were investigated. The results show that the textured ceramics have a microstructure with plated-like grains aligning in the direction parallel to the casting plane. The degree of grain orientation increased at increasing sintering temperature. The textured ceramics show anisotropic electrical properties in the directions parallel and perpendicular to the casting plane. The dielectric constant parallel to {h 0 0} plane is three times higher than that of the perpendicular direction in textured NKBT ceramics. The optimized sintering temperature is 1150 °C where the maximum dielectric constant is 2041, the remnant polarization is 68.7 μC/cm², the electromechanical coupling factor (k₃₁) and the piezoelectric constant (d₃₃) amount to 0.31 and 134 pC/N, respectively.     

Electromechanical properties of [0 0 1]-textured Mn–PMN–PZT ceramics under uniaxial pressure

Dielectric, ferroelectric, and piezoelectric properties of both random and textured Mn–PMN–PZT ceramics were characterized under uniaxial stress. Textured ceramics exhibit a large piezoelectric response under uniaxial pressure; the bias field piezoelectric constant is higher than 700 pC/N when pressure is below 50 MPa. Moreover, textured ceramics also show better depolarization resistance under uniaxial stress fields; overall, 30% of the origin performance will remain when stress approaches 200 MPa, but for random ceramics, it is only 10%. The ferroelectricity of both random and textured ceramics is suppressed by uniaxial compression. E_c, P_r, E_i, and dissipation energy all decrease with increasing uniaxial stress. In addition, phase-field simulation was used to better understand the polarization-changing effects on piezoelectric and dielectric performance. The uniaxial stress causes polarization rotation and increases the angle between polarization and the electric field, which is an important factor leading to the increase of the dielectric constant.     

Direct writing of textured ceramics using anisotropic nozzles

Direct writing is a unique means to align anisotropic particles for the fabrication of textured ceramics by templated grain growth (TGG). We show that alignment of tabular barium titanate (BT) template particles (20–40 μm width and 0.5–2 μm thickness) in a PIN-PMN-PT matrix powder (d₅₀ = 280 nm) is significantly improved during direct writing using anisotropic nozzles at high printing rates. The particle orientation distribution in as-printed filaments, and the texture orientation distribution in sintered ceramic filaments are shown to directly correlate with COMSOL Multiphysics-predicted torque distributions for direct writing with aspect ratio 2, 3 and 5 oval nozzles. Electromechanical strain properties of the textured piezoelectric ceramics significantly improved relative to random ceramics when printed with anisotropic nozzles. Simulations of aspect ratio 20 nozzles and nozzles with interior baffles demonstrate significantly increased torque and near elimination of constant shear stress cores (i.e. plug flow).     

Magnetocrystalline anisotropy in the Co/Fe codoped Aurivillius oxide with different perovskite layer number

Perpendicular magnetic anisotropic materials are of great interest for their huge potential to realize high‐density nonvolatile memory and logic chips. Designing such materials with lower cost and better magnetoelectric coupling still remains major challenges. In this work, aurivillius oxide ceramics with highly [00l]‐oriented grains were prepared by a facile pressureless sintering method, and the perovskite layer number was modified by varying the cobalt content. Afterwards, the unique perpendicular magnetic anisotropy and the intriguing anisotropic ferroelectric properties have been observed. The magnetic properties of the Aurivillius oxides with different layer numbers have been carefully investigated by field cooling, zero field cooling, and the magnetization with a varying field. The magnetic anisotropy in the oriented ceramics is demonstrated to be caused by the magnetocrystalline anisotropy with the easy magnetization direction along the c‐axis, which possibly arises from the unquenched 3d orbitals combined with the special layered crystal structures. The magnetocrystalline anisotropy becomes weaker in the ceramics with lower numbered perovskite layers, whereas the orientation degree of the ceramics and the ferroelectric anisotropy show quite opposite trends. Furthermore, the weak magnetoelectric coupling is also observed in the ceramics. This special anisotropic multiferroic properties may open up a new window for the Aurivillius materials.     

Achievement of high electric performances for bismuth titanate-based piezoceramics via hot press sintering

Bi₄Ti₃O₁₂ (BIT) ceramic has great potential in high-temperature environment due to its high Curie temperature T_C ~ 675 °C. In this work, hot press sintering (HPS) is applied on the 0.01 mol Ce and Nb/Cr co-doped BIT (BCTNC) ceramics to enhancing the low piezoelectric coefficient (d₃₃ < 7 pC/N) and resistivity. Extremely high d₃₃ (~39 pC/N) together with high T_C (~672 °C) and high dc resistivity ρ (~1.49 ×10⁷ Ω?cm at 500 °C) are obtained in HPS samples. The enhancement of piezoelectricity benefits from high density of domain and high poling electric field. Moreover, outstanding thermal stability of piezoelectric constant (d₃₃ ~ 35 pC/N after annealing at 650 °C) and low dielectric loss (tanδ ~ 3.8% at 500 °C) are observed as well. These findings are instrumental in understanding HPS and provide a possible manipulation of crystallized mechanism and domains growing kinetics to enhance piezoelectric performances of BIT based ceramics.     

Hydrothermal synthesis of single-crystal α-tristrontium phosphate particles

Anisotropic ceramic bodies can be fabricated by a reactive template grain growth method; however, template particles with suitable powder properties are required to create the ceramics with well controlled anisotropy. Therefore, we synthesized well-isolated α-tristrontium phosphate (α-TSP) particles with a hexagonal plate-like shape as template particles for anisotropic strontium apatite ceramics using α-strontium hydrogen phosphate (α-SrHPO₄) precursor particles. Three synthetic parameters were varied: (i) precursor particle size, (ii) stirring rate, and (iii) hydrothermal temperature. Well-isolated hexagonal plate-like α-TSP single-crystal particles were successfully synthesized by hydrothermal treatment at 150 °C for 3 h at a stirring rate of 150 rpm using fine α-SrHPO₄ precursor particles. The developed plane of the hexagonal plate-like α-TSP particles was determined to be the {00l} plane, and the side planes were revealed to be not {h00} planes, but inclined {h0l} planes. The resulting α-TSP particles may provide a promising template for the development of anisotropic apatite-based ceramics.     

Grain-orientation-engineered multilayer NaSr2Nb5O15 ferroelectric ceramics via templated grain growth

It is difficult to take both texture degree and density into account by the conventional method, especially when one-dimensional particles are used as templates to prepare textured ferroelectric ceramics. Here, we proposed a strategy to improve the texture degree and density of ceramics simultaneously by a grain-orientation-engineered technique. To solve the problem of directional arrangement of template particles, template layers without mixed matrix were prepared by the brushing technique. Dense textured NaSr₂Nb₅O₁₅ ceramics with grain size gradient distribution were designed by the lamination of template and matrix layers. An evaluation method of texture degree was developed. Ferroelastic and ferroelectric domains were observed simultaneously in the oriented grains, which was further confirmed that the ferroelectric-ferroelastic phase transition occurred for the NaSr₂Nb₅O₁₅ ceramics at the low temperature. The obtained textured NaSr₂Nb₅O₁₅ ceramics exhibited the high piezoelectric constant (d₃₃ =134 pC/N). The present research offers a route for designing grain-oriented ferroelectric ceramics.     

Fine-grained relaxor ferroelectric PMN-PT ceramics prepared using hot-press sintering method

Relaxor ferroelectric PbMg_1/3Nb_2/3O₃-PbTiO₃ (PMN-PT) ceramics are high-performance piezoelectric materials that are widely used in many electronic devices. However, it is extremely difficult to manufacture thin piezoelectric components dozens of micrometers in size using commercial coarse-grained PMN-PT ceramics. This limits the application of PMN-PT ceramics to high-frequency ultrasonic devices. In this work, we prepared a dense, fine-grained PMN-PT ceramic at low temperature using a hot-press sintering (HPS) method. The HPS ceramic had small grains with an average size of 1 μm and maintained high performance with a large permittivity (ε_r = 4500), piezoelectricity (d₃₃ = 650 pC/N), and electrostrain (S_E = 0.14% at 20 kV/cm). The large volume fraction of grain boundaries led to stronger relaxor behavior of the fine-grained PMN-PT ceramic than of the normal coarse-grained one. Owing to its small grains and high piezoelectric performance, this fine-grained PMN-PT ceramic meets the strict requirements of manufacturing thin piezoelectric components. Our results demonstrate that PMN-PT ceramics have great potential for developing low-cost, high-frequency ultrasonic devices by replacing expensive piezoelectric single crystals.     

3D printing orientation controlled PMN-PT piezoelectric ceramics

Piezoelectric textured ceramics have drawn increasing research and industry interests by balancing the production cost and material performances. A new approach to realize the texture in piezoelectric ceramics is developed based on 3D printing stereolithography (SL) technique and successfully applied in the preparation of < 001 > -textured 0.71(Sm_0.01Pb_0.985)(Mg_1/3Nb_2/3)O₃-0.29(Sm_0.01Pb_0.985)TiO₃ (1 %Sm-PMN-29PT) ceramics in this work. As a critical process in texture ceramic fabrication, the alignment of BaTiO₃ templates along the horizontal direction is achieved by the shear force produced from the relative motion between the resin container and the blade during SL. The textured ceramics with obvious grain orientation features are successfully obtained. The enhanced piezoelectric properties of d₃₃ ≈ 652 pC N^?1 and d₃₃* ≈ 800 pm V^?1 are achieved in the 3D printed textured ceramic, which are about 60 % and 40 %, respectively, higher than their non-textured counterparts. Moreover, the textured sample shows a significant improvement on thermal stability of d₃₃*_T, which varies by less than ± 6 % from RT to 110 °C. Furthermore, the introduction of 3D printing into the synthesis of textured piezoelectric ceramics shows great advantages over the traditional tape-casting method. This work is expected to provide a promising way for the future design of textured piezoelectric functional materials.     

Crystal structure and electrical properties of textured Ba2Bi4Ti5O18 ceramics

Highly textured Ba₂Bi₄Ti₅O₁₈ ceramic was prepared by spark plasma sintering (SPS). X-ray diffraction of the ceramics revealed the coexistence of a major ferroelectric phase (Space group, SG: B2cb) and a minor paraelectric phase (SG: I4/mmm) at room temperature. A diffused phase transition was observed at around 240 °C. The evolution of the switching current peaks in the electric current vs. electric field (I-E) loops with increasing temperature was interpreted by the structural changes and temperature dependent polarisation reversal processes. The slim polarisation vs. electric field (P-E) loops, the extra switching current peaks in the I-E loops and the non-zero piezoelectric d₃₃ coefficient indicate that Ba₂Bi₄Ti₅O₁₈ is a relaxor ferroelectric material. The recoverable energy density (0.41 ± 0.01 J/cm³) of Ba₂Bi₄Ti₅O₁₈ ceramics in the perpendicular direction to the SPS pressing direction is close to that of Pb(Mg_1/3Nb_2/3)O₃-based ceramics. The obtained results suggest Ba₂Bi₄Ti₅O₁₈ ceramics might be promising for energy storage applications.     

Achieving large piezoelectric response and ultrahigh electrostriction in [001] textured BiScO3-PbTiO3 high-temperature piezoelectric ceramics

[001] textured 0.40BiScO₃-0.60PbTiO₃-0.125 mol%Nb⁵⁺ (BS-60PT-0.125Nb) high-temperature piezoelectric ceramics were synthesized using templated grain growth process. A high texture degree F₀₀₁ of 99% was obtained using 2 vol% BaTiO₃ (BT) templates. The piezoelectric charge constant d₃₃ and the unipolar strain under 40 kV cm⁻¹ at room temperature for the textured ceramics are 646 pC N⁻¹ and 0.36%, respectively, which is over two times as those for untextured ceramics (∼243 pC N⁻¹ and 0.17%). The electrostriction Q₃₃ value of the textured sample remarkably increased from 0.034 m⁴ C⁻² to 0.068 m⁴ C⁻² under 30 kV cm⁻¹, showing a twice higher than untextured. Compared with random ceramics, the improvement piezoelectric response of the textured ceramics is primarily attributed to the increase of the dielectric constant ε_r and electrostriction coefficient Q₃₃ along [001] orientation, which is originating from the anisotropy of piezoelectricity. The BS-60PT-0.125Nb textured ceramics have large piezoelectric response and ultrahigh electrostriction with high temperature stability (high depolarization temperature T_d of ∼360°C and high Curie temperature T_c of 421°C), showing great potential for the piezoelectric applications at high temperatures.     

Anisotropy on SrTiO3 templated textured PMN–PT monolithic ceramics

In this work, templated grain growth (TGG) and reactive templated grain growth (RTGG) texture techniques combined with uniaxial hot pressing were used for the first time to produce high dense monolithic textured 0.6PMN–0.4PT ceramics. Microstructural analysis of the textured ceramics showed that both TGG and RTGG texture methods are efficient to promote anisotropic grain nucleation around the SrTiO₃ single crystal templates. The structural data remarkably revealed that although there was no previous reaction of the powder to form the lead magnesium niobate–lead titanate (PMN–PT) compound in the RTGG samples and the ceramic phase formation was 100% perovskite indicating that RTGG texture technique is more attractive than TGG in the case of SrTiO₃ templated PMN–PT. Rather, dielectric characterizations performed in the RTGG samples parallel and perpendicular to the template axis revealed a high anisotropy in the electrical permittivity for RTGG samples (1.48) that were comparable to an estimated value for 0.62PMN–0.38PT single crystals. Piezoelectric characterization of RTGG samples resulted in strain levels up to 0.34% and the highest d₃₃ coefficient was 1100 pC/N, which showed significant increase compared to random ceramic.     

Synchronous improvement of piezoelectric property and temperature stability in PSN-PMN-PT ceramics by forming composites with ZnO

Relaxor ferroelectric materials with high piezoelectric properties always suffer from low phase transition temperature, making them difficult to satisfy the demands for high-temperature environment applications. In this work, we proposed a composite approach to improve the piezoelectricity and temperature stability of PSN-PMN-PT ceramics at the same time. The ZnO nanoparticles as a second phase were introduced into the PSN-PMN-PT matrix to form composite ceramics. When the ZnO content reaches 5 mol%, the piezoelectric constant d₃₃ increases from 529 pC/N for pure PSN-PMN-PT ceramic to 590 pC/N. Meanwhile, the retained d₃₃ after annealing at 200 °C keeps 92% of the value before annealing, indicating the thermal depolarization behavior is suppressed by the composite method. The synchronous improvement of the d₃₃ and thermal depolarization behavior for PSN-PMN-PT/ZnO composite ceramics is related to the local electric field and stress field caused by the addition of ZnO particles. Our results pave a simple and effective way to develop next-generation PT-based relaxor ferroelectric ceramics.     

An effective strategy to realize superior high-temperature energy storage properties in Na0.5Bi0.5TiO3 based lead-free ceramics

To develop and fabricate environmentally friendly dielectric capacitors used in high-temperature environment, in this work, we prepare La³⁺ doped 0.94Na_0.5Bi_0.5TiO₃-0.06BaTiO₃ lead-free relaxor ferroelectric ceramics with high and wide phase transition temperature. With the introduction of La³⁺, due to the enhancement of the A- and B- site cation ion disorder, the dielectric relaxation characteristics of the ceramics are more obvious. Therefore, the polarization-electric field loops become slimmer and the remnant polarization (P_r) reduces. In addition, because La³⁺ as a donor dopant has lower mobility than A-site cation ions in the ceramic matrix, the grain sizes decrease with increasing La³⁺ content, which significantly leads to an increase in the breakdown strength (E_b). As a result, both a large recoverable energy density (W_rec) of 1.92 J/cm³ and a high energy efficiency (η) of 85.7% are obtained in the ceramic with 12 mol% La³⁺ content. More importantly, even at 200 °C and a low driving electric field of 155 kV/cm, the W_rec and η of this kind of ceramic are still as high as 1.2 J/cm³ and 89.4%, indicating good temperature stability. This work provides an effective and simple way to prepare environmentally friendly dielectric capacitors that are applicable in high-temperature environment.     

Preparation and Electric Properties of Bi0.5Na0.5TiO3–Bi(Al0.5Ga0.5)O3 Lead‐Free Piezoceramics

A new lead‐free BNT‐based piezoelectric ceramics of (1 ? x)Bi_0.5Na_0.5TiO₃–xBi(Al_0.5Ga_0.5)O₃ (x = 0, 0.02, 0.03, 0.04, and 0.05) were synthesized using a conventional ceramic fabrication method. Their structures and electrical properties were investigated. All the samples show a typical ferroelectric P(E) loops and S(E) curves at room temperature. The optimal properties are obtained at the composition of the x = 0.03. The substitution of Bi(Al_0.5Ga_0.5)O₃ enhances piezoelectric constant and increases Curie temperature from 58 pC/N and 310°C of pure BNT to 93 pC/N and 325°C of the x = 0.03. The temperature‐dependent P(E) loops and S(E) curves of 0.97BNT–0.03BAG indicate that phase transition from ferroelectric to antiferroelectric takes place over a very wide temperature region from 80°C to 180°C. The results show that the introduction of BAG improves the electrical properties of BNT.