Role of A-site (Sr), B-site (Y), and A,B sites (Sr,Y) substitution in lead-free BaTiO3 ceramic compounds: Structural,optical, microstructure,mechanical, and thermal conductivity properties

Strontium and Yttrium-doped and co-doped BaTiO₃ (BT) ceramics with the stoichiometric formulas BaTiO₃, B_1-xSr_xTiO₃, Ba_1-xY_xTiO₃, BaTi_1-xY_xO₃, Ba_1-xY_xTi_1-xY_xO₃, and Ba_1-xSr_xTi_1-xY_xO₃ (x = 0.075) noted as BT, BSrT, BYT, BTY, BYTY, and BSrTY have been synthesized through sol-gel method. X-ray diffraction (XRD) patterns of the prepared ceramics, calcined at a slightly low temperature (950 °C/3h), displayed that BT, BSrT, and BYT ceramics possess tetragonal structures and BTY, BYTY, and BSrTY have a cubic structure. The incorporation of the Ba and/or Ti sites by Sr²⁺ and Y³⁺ ions in the lattice of BaTiO₃ ceramic and the behaviors of the crystalline characteristics in terms of the Y and Sr dopant were described in detail. The scanning electron microscopy (SEM) images demonstrated that the densification and grain size were strongly related to Sr and Y elements. UV–visible spectroscopy was used to study the optical behavior of the as-prepared ceramic samples and revealed that Sr and Y dopants reduce the optical band gap energy to 2.74 eV for the BSrTY compound. The outcomes also demonstrated that the levels of Urbach energy are indicative of the created disorder following the inclusion of Yttrium. The measurements of the thermal conductivity indicated the influence of the doping mechanism on the thermal conductivity results of the synthesized samples. Indeed, the thermal conductivity of BaTiO₃ is decreased with Sr and Y dopants and found to be in the range of 085–2.23 W.m^-1. K^?1 at room temperature and decreases slightly with increasing temperature from 2.02 to 0.73-W.m^-1. K^?1. Moreover, the microstructure and grains distribution of the BT, BSrT, BYT, BTY, BYTY, and BSrTY samples impacted the compressive strength, hence; the compressive strength was minimized as the grain size decreased.     

High permittivity BaTiO3 and BaTiO3-polymer nanocomposites enabled by cold sintering with a new transient chemistry: Ba(OH)2∙8H2O

Cold sintering process (CSP) offers a promising strategy for the fabrication of innovative and advanced high permittivity dielectric nanocomposite materials. Here, we introduce Ba(OH)₂?8H₂O hydrated flux as a new transient chemistry that enables the densification of BaTiO₃ in a single step at a temperature as low as 150 °C. This remarkably low temperature is near its Curie transition of 125 °C, associated with a displacive phase transition. The cold sintered BaTiO₃ shows a relative density of 95 % and a room temperature relative permittivity over 1000. This new hydrated flux permits the fabrication of a unique dense BaTiO₃-polymer nanocomposite with a high volume fraction of ceramics ((1-x) BaTiO₃ – x PTFE, with x = 0.05). The composite exhibits a relative permittivity of approximately 800, at least an order of magnitude higher than previous reports on polymer composites with BaTiO₃ nanoparticle fillers that are typically well below 100. Unique high permittivity dielectric nanocomposites with enhanced resistivities can now be designed using polymers to engineer grain boundaries and CSP as a processing method opening up new possibilities in dielectric materials design.     

Dielectric properties of Ba1−xSrxTiO3 ceramics prepared by microwave sintering

A comparative study on the dielectric properties of Ba_1?xSr_xTiO₃ (x=0.1–0.6) ceramics prepared by microwave sintering (MS) and conventional sintering (CS) has been done. It was found that MS samples need lower temperature and much shorter time than CS samples to obtain the same degree of densification. Compared with CS samples, MS samples possessed smaller grain size, better densification and more uniform grain growth. The dielectric properties of the samples were measured as a function of temperature. It was observed that the dielectric constant was higher for MS samples compared with that of CS samples especially in the ferroelectric phase.     

Kirkendall porosity in barium titanate–strontium titanate diffusion couple

Inter-diffusion between perovskites BaTiO₃ and SrTiO₃ diffusion couple has been studied by determining the crystalline phases and analyzing the microchemistry and microstructure of undoped BaTiO₃–SrTiO₃ stacks sintered at 1250 °C in air. The Kirkendall effect manifested by: (1) an inter-diffusion zone containing (Ba_1−xSr_x)TiO₃ and (Sr_1−xBa_x)TiO₃ solid solutions, (2) the migration of the initial BaTiO₃–SrTiO₃ interface, and (3) the Kirkendall porosity was observed. The inter-diffused regions on both sides of the initial interface contain grains exhibiting the characteristic core–shell structure with distinctive solute contents between core and shell. TiO₂-rich polytitanates, notably Ba₄Ti₁₃O₃₀ and Ba₆Ti₁₇O₄₀ containing a minor amount of Sr from inter-diffusion, have been detected at the BaTiO₃ side near the initial BaTiO₃–SrTiO₃ interface. An analogy between the BaTiO₃–SrTiO₃ diffusion couple and Kirkendall's original α-brass-Cu couple is presented.     

Chemical composition and temperature dependence of the energy storage properties of Ba1‐xSrxTiO3 ferroelectrics

Dielectric materials with high power and energy densities are desirable for potential applications in advanced pulsed capacitors. Computational material designs based on first‐principles calculations provide a “bottom‐up” method to design novel materials. Here, we present a first‐principles effective Hamiltonian simulation of perovskite ferroelectrics, Ba_1‐xSr_xTiO₃, for energy storage applications. The effects of different chemical compositions, temperatures, and external electric fields on the ferroelectric hysteresis and energy storage density of Ba_1‐xSr_xTiO₃ were investigated. The Curie temperature was tuned from 400 to 100 K by doping Sr in the BaTiO₃ lattice. At a constant temperature, the ferroelectric hysteresis became slimmer as the Sr content increased, and the energy storage efficiency increased. For the same chemical composition, the energy storage density increased as the temperature increased. For the composition x = 0.4, a discharged energy density of ~2.8 J/cm³ with a 95% efficiency was obtained in an external electric field of 350 kV/cm, and a discharged energy density of 30 J/cm³ with a 92% efficiency was obtained in an external electric field of 2750 kV/cm. The energy storage property predictions and new material designs have potential to create experimental and industrial products with higher energy storage densities.     

Investigation of a new lead-free Bi<Subscript>0.5</Subscript>(Na<Subscript>0.40</Subscript>K<Subscript>0.10</Subscript>)TiO<Subscript>3</Subscript>-(Ba<Subscript>0.7</Subscript>Sr<Subscript>0.3</Subscript>)TiO<Subscript>3</Subscript> piezoelectric ceramic

Lead-free piezoelectric compositions of the (1-x)Bi_0.5(Na_0.40K_0.10)TiO₃-x(Ba_0.7Sr_0.3)TiO₃ system (when x = 0, 0.05, 0.10, 0.15, and 0.20) were fabricated using a solid-state mixed oxide method and sintered between 1,050°C and 1,175°C for 2 h. The effect of (Ba_0.7Sr_0.3)TiO₃ [BST] content on phase, microstructure, and electrical properties was investigated. The optimum sintering temperature was 1,125°C at which all compositions had densities of at least 98% of their theoretical values. X-ray diffraction patterns that showed tetragonality were increased with the increasing BST. Scanning electron micrographs showed a slight reduction of grain size when BST was added. The addition of BST was also found to improve the dielectric and piezoelectric properties of the BNKT ceramic. A large room-temperature dielectric constant, ε _r (1,609), and piezoelectric coefficient, d ₃₃ (214 pC/N), were obtained at an optimal composition of x = 0.10.     

Tunable BaxSr1-xTiO3 nanoparticles induced high energy storage density in layer-structured asymmetric polymer-based nanocomposites

In order to solve the problem of low charging and discharging energy density of dielectric capacitors, the structure design of layered polymer matrix composites is carried out in this paper. Ba_0.7Sr_0.3TiO₃, Ba_0.8Sr_0.2TiO₃ and Ba_0.9Sr_0.1TiO₃ nanoparticles were successfully prepared by the oxalate coprecipitation method. The surface of Ba_xSr_1-xTiO₃ was successfully coated with dopamine, which promoted the dispersion of the polymer matrix of the ceramic powder. Monolayer Ba_xSr_1-xTiO₃/PVDF composites containing Ba_xSr_1-xTiO₃ with different Ba/Sr ratios were successfully prepared by the casting method. Three-layer asymmetric composites with different fillers were successfully prepared by layer-by-layer casting. The phase and microstructure of the as-prepared materials were analyzed by XRD and SEM. The dielectric, electrical conductivity, ferroelectric and energy storage properties of the composites were tested. The effects and laws of the design of the three-layer asymmetric structure on the dielectric properties and energy storage properties of the layered composites are mainly studied. When the structure of the three-layer asymmetric composite is 1-2-3, the breakdown field strength reaches 330 kV/mm, the discharge energy density reaches 8.51 J/cm³, and the charge-discharge efficiency is 67%. This work demonstrates that layered composites with asymmetric properties can facilitate the development of electrical energy storage.     

Electrical properties and phase of BaTiO3–SrTiO3 solid solution

It has been known that ABO₃ type perovskite ferroelectrics, such as BaTiO₃ (BTO) and SrTiO₃ (STO), form a complete solid solution. In this study, Ba_1?xSr_xTiO₃ (BST, x=0.0–1.0) solid solution were sintered by a solid-state reaction method using BTO and STO raw powders with appropriate chemical composition. The crystal structure was investigated by a Rietveld refinement method; Fullprof, using X-ray diffraction data. Within the reasonable goodness of fit, tetragonal symmetry was found in BST with x≤0.2, while BST with x≥0.4 were found to be cubic symmetry. However, Ba_0.7Sr_0.3TiO₃ was difficult to decide whether it is cubic or tetragonal because of large uncertainties after final fitting. The composition ratios calculated from the fitted occupancies match well with those measured by EDS within experimental uncertainties. Remnant polarizations of BST with x<0.3 decrease with increasing Sr concentration. Furthermore, measured phase transition temperatures and maximum dielectric constant decrease as increasing Sr concentration. Measured electrical properties of BST were match well with the structural refinement investigations.     

Influence of reactant type on the Sr incorporation grade and structural characteristics of Ba1−xSrxTiO3 (x=0−1) grown by sol–gel-hydrothermal synthesis

The influence of barium and strontium starting reactants used in different mole ratios, BaCl₂ and Ba(OH)₂, SrCl₂ and Sr(OH)₂, on the chemical and structural properties of Ba_1?xSr_xTiO₃ (x=0?1) (BST) nanoparticles prepared via sol–gel-hydrothermal synthesis in an oxygen atmosphere is discussed. The effect of the type of reactant on the relative amount of Sr incorporated in BST compound was also analysed. The synthesised BST nanoparticles showed differences in their structural and chemical characteristics, which were attributed to the presence of Cl^? or OH^? anions during the synthesis of the compound. The structure, morphology and oxidation state of the samples were studied by X-ray diffraction, transmission electron microscopy and X-ray photoelectron spectroscopy, respectively. In addition, theoretical calculations using cluster models were carried out to understand the possible phases formed of BST, the effect of the Sr incorporation and the possible presence of oxygen vacancies inside the BST structure.     

Mono and co-substitution of Sr2+ and Ca2+ on the structural,electrical and optical properties of barium titanate ceramics

In this work, Ba_0.9Sr_0.1TiO₃, Ba_0.7Sr_0.3TiO₃, Ba_0.5Sr_0.5TiO₃, Ba_0.5Ca_0.25Sr_0.25TiO₃ and Ba_0.5Ca_0.5TiO₃ have been synthesized to evaluate the influence of mono and co-substitution of A-site dopants (Sr²⁺ and Ca²⁺) on the structural, electrical and optical properties of BaTiO₃ ceramics. Sr²⁺ added samples showed a tetragonal structure which became slightly distorted with increasing Sr²⁺ concentration and finally achieved a cubic structure for x?=?0.50. Ba_0.5Ca_0.5TiO₃ also retained their tetragonality with limited solubility. Presence of second phase, CaTiO₃ demonstrated the fact of restricted solubility. The concurrent effect of Sr²⁺ and Ca²⁺ didn't alter the tetragonal structure. Sr²⁺ substitution enhanced the apparent density as well as grain size which stimulated the domain wall motion and improved dielectric properties. However, the ferroelectric nature of Ba_1-xSr_xTiO₃ was poor due to the redistribution of point defect at grain boundary. The optical band gap was found to be reduced from 3.48?eV to 3.28?eV with increasing Sr²⁺ content. Co-substitution of cations improved the electrical property significantly. The highest value of dielectric constant was found to be ～547 for Ba_0.5Ca_0.25Sr_0.25TiO₃ ceramics. Both Ba_0.5Ca_0.25Sr_0.25TiO₃ and Ba_0.5Ca_0.5TiO₃ had developed P-E loop having lower coercive field and moderate optical band gap energy. Co-doping with Sr²⁺ and Ca²⁺ was a good approach enhancing materials electrical as well as optical property.     

Defect dipoles induced high-energy storage density in Mn-doped BST ceramics prepared by spark plasma sintering

Ba_0.5Sr_0.5TiO₃ ceramics with different Mn-doping amount (Ba_0.5Sr_0.5Ti_1-xMn_xO₃, x = 0, 0.1%, 0.3%, 0.5%) were prepared by spark plasma sintering method. The single phase with cubic structure symmetry was confirmed and a gradual increase in lattice parameter with increasing x was observed. Fine grains with dense microstructure were revealed from the SEM images, while an obvious increase in grain size was detected when x = 0.5%. An optimized doping amount of 0.3% was determined, showing high dielectric constant (ε_r ≈ 2190), low dielectric loss (tanδ ≈ 2.78 × 10⁻³), enhanced breakdown strength (290 kV/cm), and high-energy storage density (1.69 J/cm³) at room temperature. A possible mechanism, namely defect dipoles formation mechanism, was employed to explain the optimization of energy storage performance, and further confirmed from the variation in AC conductivity.     

Preparation and properties of (Ba0·7Sr0·3)TiO3 powders and thin films using precursor solutions formed from alkoxide-hydroxide

(Ba_0·7Sr_0·3)TiO₃ powders and thin films were prepared using alkoxide-hydroxide route. Solutions of Ba and Sr hydroxides dissolved in methanol were reacted with Ti-isopropoxide under conditions of stirring at room temperature for 15 h, and then dried under reduced pressure at ≦40°C to prepare precursors of (Ba_0·7Sr_0·3)TiO₃ powder. The amorphous precursors were hydrolyzed at 100°C by introducing nitrogen gas containing water vapor. The hydrolyzed products were crystalline nanosize powders of (Ba_0·7Sr_0·3)TiO₃. As-hydrolyzed (Ba_0·7Sr_0·3)TiO₃ powders showed a good crystallinity with cubic phase. (Ba_0·7Sr_0·3)TiO₃ thin films were also successfully prepared at 650°C on Pt/Ti/SiO₂/Si substrates from precursor solutions obtained by the reaction of alkoxide with hydroxides. The (Ba_0·7Sr_0·3)TiO₃ thin films exhibited the microstructure with fine grains as small as 20–60 nm. The dielectric constants of the thin films ranged from 600 to 800 at room temperature.     

Enhanced Electrocaloric Effects in Spark Plasma‐Sintered Ba0.65Sr0.35TiO3‐Based Ceramics at Room Temperature

Improvement of electrocaloric effect was investigated in the lead‐free undoped and Mn‐doped Ba_0.65Sr_0.35TiO₃ ceramics prepared by spark plasma sintering process. Owing to the merit of spark plasma sintering process, a fully dense undoped and Mn‐doped Ba_0.65Sr_0.35TiO₃ ceramics with fine grain sizes could be obtained. The electrocaloric (EC) effect can be significantly enhanced from 0.83 K for conventional sintered Ba_0.65Sr_0.35TiO₃ to 3.08 K for spark plasma‐sintered Mn‐doped Ba_0.65Sr_0.35TiO₃ ceramics since the dielectric strength was dramatically increased. This work indicated an effective way to achieve the significantly enhanced EC effect in a lead‐free system at room temperature.     

Phase evolution and <110>-orientation mechanism in RTGG-processed BaTiO3 ceramics with electrical properties

The <110>-oriented BaTiO₃ ceramics were fabricated using BaCO₃ matrix and H_1.08Ti_1.73O₄.nH₂O (HTO) template particles, and the mechanism of BaTiO₃ phase formation was investigated. The dielectric, ferroelectric, and piezoelectric properties were also investigated. The transformation of the HTO phase into the TiO₂ bronze or TiO₂ (B) phase was observed at 600°C, where the BaTiO₃ nucleation was accompanied by the formation of a Ba₂TiO₄ phase. The TiO₂ phase reacted with the Ba₂TiO₄ phase at 800°C to give a BaTiO₃ phase, whereas its reaction with the BaTiO₃ resulted in the formation of BaTi₂O₅ phase that got decomposed into BaTiO₃ and Ba₆Ti₁₇O₄₀ phase at sintering temperature ≥1300°C. Sintering with samples’ embedding in BaTiO₃ powders prevented the formation of the Ba₆Ti₁₇O₄₀ secondary phase. The crystallographic orientation along the <110> direction (F₁₁₀) was developed by the epitaxial grain growth mechanism. In addition to the contribution of the grain-size increment for enhancing the F₁₁₀, the preservation of the platelike structure was also found to have a significant impact. The ceramics prepared by the embedded sintering (grain size ≈12.4 µm and F₁₁₀ = 83%) exhibited the room-temperature dielectric constant of 1708 and piezoelectric strain constant of 445 pm/V, which are higher than those of the BaTiO₃ ceramics with randomly oriented grains.     

Effect of Mn-doping on the morphological and electrical properties of (Ba0·7Sr0.3) (MnxTi1−x)O3 materials for energy storage application

Lead-free (Ba_0·7Sr_0.3) (Mn_xTi_1?x)O₃ (x = 0.0, 1.0, 2.0, 4.0, 6.0, and 8.0%) ceramics were effectively synthesized by the sol-gel process. XRD and Raman spectroscopy confirm the single-phase perovskite structure with tetragonal symmetry, for all compositions. An in-depth analysis of the chemical composition and thermochemistry of the ceramics was carried out via FT-IR and TG-DTG. Morphological analyses of the samples revealed that doping Mn at higher concentrations suppresses the grain size and grain growth rate. The dielectric properties increased first and then decreased with increasing Mn content. The ferroelectric properties represented similar trend in polarization and energy storage efficiency as showed in dielectric properties. 2% Mn-doped sample exhibits the best dielectric and energy storage performance which is attributed to increased densification and grain size effects. Dielectric anomaly caused by defect dipole polarization was observed in temperature-dependent dielectric constant curves, for 6% and 8% Mn-doped samples. This study is helpful to establish the relationship between the structure, morphology, dielectric and ferroelectric properties of Mn substituted Ba_0·7Sr_0·3TiO₃ ceramics.     

Effect of strontium doping on structural and dielectric behaviour of barium titanate nanoceramics

ABSTRACT

Barium strontium titanate (Ba_(1?x)Sr_xTiO₃ where, x?=?0.0, 0.2, 0.3, 0.4 and 0.5) nanoparticles have been successfully synthesised by sol–gel method and characterised thoroughly. With the increase in Sr concentration (x?>?0.3), the symmetry of the crystal structure changed from tetragonal to cubic phase. The dielectric behaviour of the ceramic nanoparticles was evaluated using impedance analyser with an operating frequency of 1?Hz to 1?MHz. A very high dielectric constant 4915 was obtained for Ba_0.7Sr_0.3TiO₃ at 1?Hz frequency with low dielectric loss of 1.91, which showed very good value than the one previously reported. The density of the material was found to be >98% of theoretical density. Dielectric constants were measured by varying the temperature from 35 to 150°C and the Curie temperatures were also evaluated. The small amount of Sr doping was beneficial for obtaining high dielectric constant material which can be used in various electronic applications.     

Effect of SrTiO3 concentration and sintering temperature on microstructure and dielectric constant of Ba1−xSrxTiO3

The Ba_1−xSr_xTiO₃ materials have received increased attention as one of the most important materials for electroceramic components, such as high dielectric ceramic capacitors, tunable phase shifters and PTCR. In this paper, the effect of SrTiO₃ concentration and sintering temperature on the microstructure and dielectric constant of Ba_1−xSr_xTiO₃ materials at the Curie temperature have been investigated. When Ba_1−xSr_xTiO₃ materials were sintered at 1350 °C, the peak value of the dielectric constant, ϵ_max, monotonically decreased with increasing SrTiO₃ concentration. At the sintering temperature of 1400 °C the dielectric constant maximum at the T_C increased with an increase in the x value, reaching the highest value at around x=0.4 and then decreased. As sintering temperature increased to 1450 °C, ϵ_max increased with increasing SrTiO₃ concentration up to x=0.6. The dielectric properties of Ba_1−xSr_xTiO₃ materials were discussed in terms of SrTiO₃ concentration and microstructure.     

Composition-dependent microstructure and electrical property of (1−x)SBN-xBNBT solid solutions

In this study, (1−x)Sr_0.75Ba_0.25Nb₂O₆-x[0.94Bi_0.5Na_0.5TiO₃-0.06BaTiO₃] solid solution ceramics were prepared and investigated. The length-diameter ratio of pillar-like grain increased with increase in x, reaching maximum value of 10.5 at average length of 1.36 μm and diameter of 0.13 μm for x = 0.20. The maximum dielectric constant, temperature corresponding to the maximum dielectric constant, and saturated polarization decreased, respectively, from 507, 36°C, and 3.2 μC/cm² for x = 0 to 365, −61°C, and 2.0 μC/cm² fort x = 0.10, and then increased to 1167, 43°C, and 5.5 μC/cm² for x = 0.20. These results indicate the competitive effects of B-site Ti⁴⁺ and A-site Ba²⁺ on ferroelectricity.     

Screen printed barium strontium titanate films for microwave applications

Powders to be used in inks for screen printing of Ba_0.5Sr_0.5TiO₃ thick films have been prepared by two different routes — calcination of BaCO₃, SrCO₃ and TiO₂ by a conventional solid-state reaction, and thorough mixing of uncalcined nano-sized BaTiO₃ and SrTiO₃. The effect of these two different production routes on the microstructural properties in terms of grain size and density has been assessed using SEM. Electrical measurements at 1 kHz indicate that both permittivity and dielectric loss are affected by the density of the films. Permittivity also appears to be affected by the grain size of the films, which increases dramatically above a particular sintering temperature. The Curie temperature also decreases as sintering temperature increases and this has been linked to observed Ba diffusion from the film into the alumina substrate.     

Reassessing cold sintering in the framework of pressure solution theory

Cold sintering densification and coarsening mechanisms are considered from the perspective of the non-equilibrium chemo-mechanical process known in Earth Sciences as pressure solution creep (or dissolution-precipitation creep). This is an important mechanism of densification and deformation in many geological rock formations in the Earth’s upper crust, and although very slow in nature, it is of direct relevance to the cold sintering process. In cold sintering, we select particulate materials and identify experimental processing parameters to significantly accelerate the kinetics of dissolution-precipitation phenomena, with appropriate consideration of chemistry, applied stress, particle size and temperatures. In the theory of pressure solution, pressure-driven densification is considered to involve the consecutive stages of dissolution at grain contact points, then diffusive transport along the grain boundaries towards open pore surfaces, and then precipitation, all driven by chemical potential gradients. In this study, it is shown that cold sintering of BaTiO₃, ZnO and KH₂PO₄ (KDP) ceramic materials proceeds by the same type of serial process, with the pressure solution creep rate being controlled by the slowest kinetic step. This is demonstrated by the values of activation energy (E_a) for densification, which are in good agreement with the existing literature on dissolution, precipitation, or coarsening. The influence of pressure on the morphology of ZnO grains also supports the pressure solution mechanism. Other characteristics that can be understood qualitatively in terms of pressure solution are observed in the in systems such as BaTiO₃ and KDP. We further consider activation energies for grain growth with respect to the precipitation process, as well as evidence for coalescence and Ostwald ripening during cold sintering. For completeness we also consider materials that show significant plastic deformation under compression. Our findings point the way for new advances in densification, microstructural control, and reductions in cold sintering pressure, via the use of appropriate transient solvents in metals and hybrid organic-inorganic systems, such as the Methylammonium lead bromide (MAPBr) perovskite.