Phase decomposition of (Ti,Zr)(C,N) solid solutions prepared by spark plasma sintering

(Ti, Zr)(C, N) solid solutions with 10–90 mol% of ZrC were prepared by spark plasma sintering (SPS) using TiCN and ZrC powders as starting materials. The decomposition behavior of the (Ti, Zr)(C, N) solid solutions as a function of heat treatment temperature (1273–2173 K) was investigated. (Ti, Zr)(C, N) solid solutions with 20–80 mol% of ZrC were decomposed into TiCN-rich (Ti, Zr)(C, N) and ZrCN-rich (Zr, Ti)(C, N) phases when heat-treated in the temperature ranged from 1373 to 2173 K for 3.6 ks, respectively. After heat treatment, lamellar microstructure was formed with an orientation relationship of TiCN-rich (Ti, Zr)(C, N) {100} // ZrCN-rich (Zr, Ti)(C, N) {100}. The Vickers hardness and fracture toughness simultaneously increased with increasing heat-treatment temperature and showed the maximum values of 25.0 GPa and 2.5 MPa m^1/2, respectively, for Ti_0.5Zr_0.5C_0.75N_0.25 at the heat-treatment temperature of 1873 K.     

Mechanisms responsible for enhancing low-temperature oxidation resistance of nonstoichiometric (Zr,Ti)C

A series of (Zr,Ti)C_x (x = 0.7–1.0) samples were fabricated by a modified spark plasma sintering apparatus to investigate the effects of carbon concentration and Ti substitutions on the oxidation behavior. Crushed powders of (Zr,Ti)C_x were oxidized in lab air (N₂–20-vol.% O₂) from room temperature to 900°C. The results indicated that Zr_0.8Ti_0.2C_0.8, with a nominal carbon concentration x = 0.8, displayed good oxidation resistance, which was attributed to the formation of dense t-(Zr,Ti)O₂ oxide solid solution. During the oxidation of (Zr,Ti)C_x, Ti substitutions for Zr enhanced the outward diffusion of carbon, enabling a uniform carbon layer and a Zr–Ti–C–O layer on the surface of carbides. The formed carbon layer improved the oxidation resistance of (Zr,Ti)C_x below 550°C, where carbon is relatively oxidation resistant. Increasing the Ti concentration was found to enhance the oxidation resistance of (Zr,Ti)C_x with an increased oxidation onset temperature (672 ± 2°C for Zr_0.8Ti_0.2C_0.8).     

Novel (Zr,Ti)(C,N)–SiC ceramics via reactive hot-pressing at low temperature

Novel (Zr, Ti)(C, N)–SiC ceramics were fabricated by reactive hot-pressing at 1500–1700 °C using ZrC, TiC_0.5N_0.5, and Si powders as raw materials for the first time. The effects of Si addition on the microstructures and mechanical properties were investigated. The reaction completely proceeded to generate SiC with an Si addition of 5 mol%. The grain refinement by SiC and solid solution strengthening of (Zr, Ti)(C, N) improve the mechanical properties. A high flexural strength of 522 ± 20 MPa was obtained in the Z5T5S ceramics (ZrC with 4.75 mol% TiC_0.5N_0.5 and 5 mol% Si additional). When the Si addition increases to 10 mol%, the residual Ti-stabilized β-ZrSi phase appears, which significantly reduces the flexural strength. The Vickers hardness and fracture toughness monotonically increase with increasing Si addition. The fine-grained microstructure without a residual phase and abundant intrinsic lattice defects in the Z5T5S composite endow it with the potential to obtain excellent radiation resistance.     

Effects of hafnium content on microstructures and properties of newly developed (Ti,Hf)(C,N) ceramics

In this study, novel (Ti,Hf)(C,N) ceramics with varying hafnium contents were fabricated via carbothermal reduction–nitridation and subsequent spark plasma sintering. The influence of Hf addition on the mechanical properties, wear properties, and corrosion resistance of the (Ti,Hf)(C,N) ceramics was systematically studied. The introduction of Hf promoted the sintering densification of the ceramics in the sintering process. The prepared (Ti,Hf)(C,N) ceramics exhibited excellent mechanical and wear properties owing to refinement and solution-strengthening mechanisms. The (Ti_0.9,Hf_0.1)(C_0.5,N_0.5) ceramic demonstrated higher Vickers hardness and fracture toughness, measuring 1997 HV5 and 4.28 MPa m^1/2, respectively, compared to the pure Ti(C_0.5,N_0.5) ceramic which exhibited values of 1635 HV5 and 3.94 MPa MPa m^1/2. The wear scar depth of the (Ti_0.9,Hf_0.1)(C_0.5,N_0.5) ceramic sample was 57.36% to that of the Ti(C_0.5,N_0.5) ceramic. Additionally, the addition of Hf improved the corrosion resistance of (Ti,Hf)(C,N) ceramics in a 0.5 M NaOH solution. The potential applications of (Ti,Hf)(C,N) ceramics include machining tools and wear-resistant parts.     

Microstructure and ablation behavior of carbon/carbon composites infiltrated with Zr–Ti

Carbon/carbon(C/C) composites infiltrated with Zr–Ti were prepared by chemical vapor infiltration and reactive melt infiltration. Their microstructure and ablation behavior at different temperatures and time were investigated. The results show that C/C composites infiltrated with Zr–Ti have good interface cohesion between carbon fibers, pyrocarbon and carbide. Compared with C/C composites and C/C–ZrC composites, the synthesized sample with Zr_0.83Ti_0.17C_0.92 and Ti_0.82Zr_0.18C_0.92 exhibits better ablation resistance at 2500 °C due to the newly formed protective layer composed of ZrTiO₂ pinned by ZrO₂ grains after ablation. The ablation resistance of the sample with Zr_0.57Ti_0.43C_1.01 increased gradually with the decrease of temperature from 3000 °C to 2000 °C, whereas the ablation resistance of the sample with Zr_0.83Ti_0.17C_0.92 and Ti_0.82Zr_0.18C_0.92 first increased obviously and then decreased slightly. In addition, the work indicates that surplus particles or liquid phases of oxides cannot protect the matrix, and that the liquid oxides may even cause severe ablation. Furthermore, a protective layer of oxides tends to be formed with the increase of ablation time.     

Enhanced high-temperature strength in textured (Ti1/3Zr1/3Hf1/3)B2 medium-entropy ceramics via strong magnetic field

This study prepared textured (Ti_1/3Zr_1/3Hf_1/3)B₂ medium-entropy ceramics for the first time that maintain enhanced flexural strength up to 1800°C using single-phase (Ti_1/3Zr_1/3Hf_1/3)B₂ powders, slip casting under a strong magnetic field, and hot-pressed sintering methods. Effects of WC additive and strong magnetic field direction on the phase compositions, orientation degree, microstructure evolution, and high-temperature flexural strength of (Ti_1/3Zr_1/3Hf_1/3)B₂ were investigated. (Ti_1/3Zr_1/3Hf_1/3)B₂ grain grows along the a,b-axes, resulting in a platelet-like morphology. Pressure parallel and perpendicular to the magnetic field direction can promote the orientation degree and hinder the texture structure formation, respectively. Reaction products of W(B,C) and (Ti,Zr,Hf)C between (Ti_1/3Zr_1/3Hf_1/3)B₂ and WC additive can efficiently refine the (Ti_1/3Zr_1/3Hf_1/3)B₂ grain size and promote grain orientation. (Ti_1/3Zr_1/3Hf_1/3)B₂ ceramics doped with 5 vol.% WC yielded a Lotgering orientation factor of 0.74 through slip casting under a strong magnetic field (12 T) and hot-pressed sintering at 1900°C. Furthermore, cleaning the boundary by W(B,C) and introducing texture can enhance the grain-boundary strength and improve its high-temperature flexural strength. The four-point flexural strength of textured (Ti_1/3Zr_1/3Hf_1/3)B₂-5 vol.% WC ceramics was 770 ± 59 MPa at 1600°C and 638 ± 117 MPa at 1800°C.     

The influence of mechanical activation on the structure and phase formation of an electro-thermal explosion in the Ti–Zr–C system

The Ti_xZr_1-xC solid solutions were synthesized by electro-thermal explosion under pressure in the (Ti + Zr + C) blends mechanically activated in hexane (MA-ETE). The effect of mechanical activation (MA) duration on reaction blend characteristics, ETE parameters, phase composition, and microstructure formation in solid solutions was investigated. At MA, the Ti + Zr blend deforms metal crystal lattices for 20 min, complete amorphization occurs for 40 min, and the carbide grains form a cubic structure for 90 min. The single-phase Zr_0.50Ti_0.50C solid solution with a grain size of 3–5 μm and a submicron composite with a grain size of 0.1–0.2 μm containing the Ti_0.86Zr_0.14C and Zr_0.74Ti_0.26C solid solutions were synthesized in a one-stage process for the first time without any additional thermotreatment. The influence of mechanical activation on diffusional mass transfer of reactants, structure, and phase formation is discussed.     

Enhancing high power performances of Pb(Mn1/3Nb2/3)O3–Pb(Zr,Ti)O3 ceramics by Bi(Ni1/2Ti1/2)O3 modification

High power piezoelectric ceramics 0.04Bi(Ni_1/2Ti_1/2)O₃-xPb(Mn_1/3Nb_2/3)O₃-(0.96-x)Pb(Zr_yTi_1-y)O₃ (BNT-xPMnN-PZ_yT) with various contents of PMnN from 0 to 12 mol% (keep y = 0.50) and Zr/Ti ratio gradually increasing from 48/52 to 52/48 (keep x = 0.06) were prepared by solid-state method. X-ray diffraction (XRD) results show a single phase of polycrystalline perovskite and indicate that the phase structure transforms from tetragonal phase to rhombohedral with x and y increasing. The optimal comprehensive properties of BNT-xPMnN-PZ_yT ceramic, d₃₃ (355 pC/N), k_p (0.58), ε_r (1512), tanδ (0.40%), T_c (336 °C) and Q_m (2010), are obtained at x = 0.06 and y = 0.50, which are apparently superior to typical or commercial Pb(Zr,Ti)O₃ (PZT) based power ceramics. Within the range from room temperature to 200 °C, the variation of electric-field induced strains is less than 8.3%, indicating its good temperature stability. The maximum vibration velocity of the ceramic at temperature rise of 20 °C is measured to be 0.92 m/s, which is about 2 times higher than that of commercial hard PZT ceramics, suggesting the BNT-xPMnN-PZ_yT ceramic is a competitive and potential candidate for power piezoelectric transduction and actuation applications.     

Fabrication and characterization of medium-entropy carbide ceramics in low temperature sintering

The medium-entropy carbide (W,Ti,V)C_0.8 ceramics were prepared by sparking plasma sintering at temperatures between 1400 and 1700°C. The effects of sintering temperature on the microstructure and mechanical properties of the medium-entropy carbide (W,Ti,V)C_0.8 ceramics were investigated. X-ray diffraction, scanning electron microscope, and energy dispersive spectrometer were used to confirm the formation of single-phase face-centered cubic (FCC) solid solution of the medium-entropy carbide (W,Ti,V)C_0.8 ceramics prepared at a sintering temperature of 1600°C. It was found that the mechanical properties of the material were improved by solid solution strengthening during the formation of single-phase FCC solid solution, and the best overall performance of the medium-entropy carbide (W,Ti,V)C_0.8 ceramics was achieved at 1600°C, when the hardness value was 22.3 ± 1.8 GPa, the fracture toughness was 5.7 ± 0.8 MPa·m^1/2, the flexural strength was 605 ± 4 MPa, and the compressive strength was 1.84 GPa. Most importantly, the addition of TiC_0.4 promoted the diffusion among the elements of the medium-entropy carbide (W,Ti,V)C_0.8 ceramics, which contributed to the formation of single-phase FCC solid solution and significantly reduced the sintering temperature of the medium-entropy carbide (W,Ti,V)C_0.8 ceramics due to the effect of vacancies. This study provides a new idea for the preparation of medium-entropy carbide ceramics.     

Prediction of solid solution characteristics of MC (M = Zr,Nb, and Ta) in TiC lattice using phase stability diagrams

Phase stability diagrams of Ti-M-O-C (M = Zr, Nb, and Ta, molar ratio of Ti and M = 1:1) systems at 1800 K were drawn as a function of the carbon activity, oxygen partial pressure, and solution formation characteristics. The solid solution characteristics were varied with the kind of M. The solid solution carbide, (Ti_0.5Zr_0.5)C, was less stable than the TiC-ZrC mixture while other solid solution carbides (Ti_0.5Nb_0.5)C and (Ti_0.5Ta_0.5)C were more stable than the mixtures of monocarbides. Thus, the (Ti_0.5Zr_0.5)C phase was not included in the phase stability diagram of the Ti-Zr-O-C system unlike the other solid solution carbides. The validity of the drawn stability diagrams was proved by experimental results. Thus, the conditions for synthesis of solid solution carbides by carbothermal reduction, or fabrication of TiC-based composites with solid solution phases, can be deduced using the phase stability diagrams.     

In situ reaction and solid solution induced hardening in (Ti,Zr)B2-(Zr,Ti)C composites

(Ti,Zr)B₂ - (Zr,Ti)C ceramics were synthesized by reactive hot-pressing and solid solution coupling effect using ZrB₂ and TiC powders as starting materials. Effects of sintering temperature on phase relations, microstructure and mechanical properties were reported. The equimolar ZrB₂ and TiC reactants ensured a complete in situ reaction to form (Ti,Zr)B₂ and (Zr,Ti)C solid solutions. The (Ti,Zr)B₂ - (Zr,Ti)C composite sintered at 1750°C was fully densified, and exhibited a high hardness of 29.1 GPa due to fine-grain hardening and solid solution hardening. The optimized comprehensive mechanical properties such as a hardness of 27.9 GPa, a strength of 705 MPa and an indentation fracture toughness of 5.3 MPa m^1/2 were achieved in (Ti,Zr)B₂ - (Zr,Ti)C composites sintered at 1800°C for 1 hour.     

High‐Strength ZrC Ceramics Doped with Aluminum

High‐strength ZrC ceramics with relative density above 98% were prepared by reactive hot pressing of ZrC and Al at 1900°C. The reaction between ZrC and Al resulted in the formation of ZrC_1?x, Zr₃Al₃C₅ and Zr–Al compound such as AlZr₃ and Al–C–Zr. The intermediate product AlZr₃ below 1600°C and remained Al–C–Zr phase could form liquid phase and promoted the first stage of densification process. The improvement in densification behavior at higher temperatures (1800°C–1900°C) could be attributed to the formation of nonstoichiometric ZrC_1?x. Adding 5 wt% and 7.5 wt% Al to ZrC, the formed ZrC_0.85–Zr₃Al₃C₅ and ZrC_0.80–Zr₃Al₃C₅ based ceramics had 3‐point bending strength as high as 757 ± 79 MPa and 967 ± 50 MPa, respectively, with hardness and fracture toughness being 16.2–18.3 GPa and 3.3–3.5 MPa m^1/2, respectively.     

Synthesis of MAX phase-based ceramics from early transition metal hydride powders

MAX phase ceramics are typically prepared by the reactive sintering of elemental powders that are often coarse, expensive, and prone to oxidation. The temperature-driven dehydrogenation of metal hydride powders offers an alternative synthesis approach, as the hydrides decompose into phase-pure, dimensionally fine elemental powder particles. The increased reactivity of these in situ formed, fine powder particles drastically reduces the formation temperature of the antecedent intermetallic phases, without forming excess binary carbides or facilitating powder oxidation in the Ti-Al-C and Zr-Al-C systems. This work elucidates the effect of metal hydrides on the sequence of formation reactions in MAX phase ceramics. In the Zr-Al-C system, the use of coarse, oxidation-prone elemental Zr powders prevented MAX phase formation, whereas spark plasma sintering of ZrH₂ powders at 1500 °C produced ceramics containing 60 wt% Zr₃AlC₂. Similarly, in the Ti-Al-C system, spark plasma sintering of TiH₂ powders at 1200 °C produced phase-pure Ti₃AlC₂ ceramics.     

Zirconium Incorporation into CaTiO3 Perovskite Prepared from Xerogels and Implication for the Fate of (Ca,Sr)TiO3 Nuclear Waste Ceramics

CaTiO₃ perovskite has been proposed as a ceramic waste form for immobilization of ⁹⁰Sr. Nonradioactive coprecipitated xerogel powders with nominal atomic ratios of Ca:Zr:Ti = 0.75:0.25:1.00 were synthesized to mimic the fate of (Ca_0.75⁹⁰Sr_0.25)TiO₃ solid solution after complete decay of the Sr and its intermediate product Y to stable Zr when an excess B⁴⁺ (Ti and ⁹⁰Zr) cations will present. Ca:Ti = 1.00:1.00 samples were used as a reference. The powders were heated to various conditions to explore the thermodynamic stability of its oxides. The heated Ca:Zr:Ti = 0.75:0.25:1.00 samples formed a major orthorhombic Ca(Zr_1?xTi_x)O₃ perovskite phase. The Ti/(Ti + Zr) ratio of the perovskite preserves its nominal ratio at 600°C. The Zr rejects from the Ca(Zr_1?xTi_x)O₃ with further increasing the temperature, following the formation of Ca–Ti–Zr–O secondary phases. This study indicates a tendency of the Zr to segregate from an original (Ca,Sr)TiO₃ waste form when the stoichiometry is controlled by the conversion of Sr to Zr (in normal oxidation states).     

Densification and mechanical properties of hot-pressed ZrN ceramics doped with Zr or Ti

The densification of hot-pressed ZrN ceramics doped with Zr or Ti have been investigated at 1500–1700 °C. It is shown that either Zr or Ti additive can facilitate the densification process. ZrN with 20 mol% Zr or Ti (named ZNZ and ZNT) sintered at 1700 °C can achieve above 98% relative densities whereas densification temperature up to 2000 °C is necessary for pure ZrN. The densification improvements are attributed to solid solution of Zr or Ti into ZrN to form non-stoichiometric ZrN_1?x or (Zr, Ti)N_1?x. The microstructures and mechanical properties of ZNZ and ZNT samples have been examined. Large grain size and flat fracture surface existed in ZNT sample sintered at 1700 °C, which lead to poor toughness as low as 2.3 MPa m^1/2. On the contrary, the fracture toughness of ZNZ sample sintered at 1700 °C was up to 5.9 MPa m^1/2, attributed to fine and uniform grain size distribution.     

Superhard single-phase (Ti,Cr)B2 ceramics

A nominally pure and dense (Ti_0.9Cr_0.1)B₂ ceramic was produced by spark plasma sintering of powders synthesized by boro/carbothermal reduction of oxides. The synthesized powders were a single phase and had an average particle of 0.4 ± 0.1 μm and an oxygen content of 1.2 wt%. Average Vickers hardness values of the resulting ceramics increased from 25.9 ± 0.8 GPa at a load of 9.81 N, to 46.3 ± 0.8 GPa at a load of 0.49 N. Compared to the nominally pure TiB₂ ceramic obtained under the same processing conditions, the (Ti_0.9Cr_0.1)B₂ ceramic had higher values under the same load due to the finer average grain size (2.4 ± 1.0 μm), higher relative density, and solid solution hardening. The results indicated that the Cr addition promoted densification, suppressed grain growth, and improved the hardness of TiB₂ ceramics. This is the first report for dense and single-phase (Ti,Cr)B₂ ceramics as superhard materials.     

High-entropy carbide-based ceramic cutting tools

In this study, a novel high-entropy carbide-based ceramic cutting tool was developed. The cutting performance of three kinds of high-entropy carbide-based ceramic tools with different mechanical properties for the ISO C45E4 steel were evaluated. Although the pure (Ti_0.2Zr_0.2Nb_0.2Ta_0.2Mo_0.2)C_0.8 ceramic cutting tool exhibited the highest hardness of 25.06 ± 0.32 GPa, the cutting performance was poor due to the chipping and catastrophic failure caused by the low toughness (2.25 ± 0.27 MPa m^1/2). The (Ti_0.2Zr_0.2Nb_0.2Ta_0.2Mo_0.2)C_0.8–15 vol% cobalt cutting tool with highest fracture toughness (6.37 ± 0.24 MPa m^1/2) and lowest hardness (17.29 ± 0.79 GPa) showed the medium cutting performance due to the low wear resistance caused by the low hardness. The (Ti_0.2Zr_0.2Nb_0.2Ta_0.2Mo_0.2)C_0.8–7.7 vol% cobalt cutting tool showed the longest effective cutting life of ∼67 min due to the high wear resistance and chipping resistance caused by the high hardness (21.05 ± 0.72 GPa), high toughness (5.35 ± 0.51 MPa m^1/2), and fine grain size (0.60 ± 0.15 μm). The wear mechanisms of the cobalt-containing (Ti_0.2Zr_0.2Nb_0.2Ta_0.2Mo_0.2)C_0.8 ceramic cutting tools included adhesive wear and abrasive wear and oxidative wear. This research indicated that the high-entropy carbide-based ceramics with high hardness and high toughness have potential use in the field of cutting tool application.     

High Electric‐Induced Strain and Temperature‐Dependent Piezoelectric Properties of 0.75BF–0.25BZT Lead‐Free Ceramics

0.75BiFeO₃–0.25Ba(Zr_xTi_1?x) + 0.6 wt% MnO₂ (0.75BF–0.25BZT) ceramics with Mn addition were prepared by the solid‐state reaction method. The high‐field strain and high‐temperature piezoelectric properties of 0.75BF–0.25BZT ceramics were studied. Introduction of Zr in the solid solutions decreased the Curie temperature slightly, and improved the dielectric and piezoelectric properties obviously. The piezoelectric properties of 0.75BZT–0.25BT ceramics reached the maximum at Zr content of 10 mol%. The Curie temperature T_c, dielectric constant ε and loss tanδ (1 kHz), piezoelectric constant d₃₃, and planner electromechanical coupling factor k_p of 0.75BF–0.25BZT ceramics with 10 mol% Zr were 456°C, 650, 5%, 138 pC/N, and 0.30, respectively. The high‐field bipolar and unipolar strain under an electric field of 100 kV/cm reached up to 0.55% and 0.265%, respectively, which were comparable to those of BiScO₃–PbTiO₃ and “soft” PZT‐based ceramics. The typical “butterfly”‐shaped bipolar strain and frequency‐dependent peak‐to‐peak strain indicated that the large high‐field‐induced strain may be due to non‐180° domain switching. Rayleigh analysis reflected that the improved piezoelectric properties resulted from the enhanced extrinsic contribution by Zr doping. The unipolar strain of 0.75BF‐0.25BZT ceramics with 10 mol% Zr was almost linear from RT to 200°C. These results indicated that 0.75BF–0.25BZT ceramics were promising candidates for high‐temperature and lead‐free piezoelectric actuators.     

High-entropy (HfTaTiNbZr)C and (HfTaTiNbMo)C carbides fabricated through reactive high-energy ball milling and spark plasma sintering

Powders of high-entropy Hf_0.2Ta_0.2Ti_0.2Nb_0.2Zr_0.2C (HEC_Zr) and Hf_0.2Ta_0.2Ti_0.2Nb_0.2Mo_0.2C (HEC_Mo) carbides were fabricated through the reactive high-energy ball milling (R-HEBM) of metal and graphite particles. It was found that 60 min of R-HEBM is adequate to achieve a full conversion of the initial precursors into a FCC solid solution for both compositions. The HEC_Zr powder possesses a unimodal particle size distribution (40% d ≤ 1 μm, 95% d ≤ 10 μm), and the HEC_Mo powder features a bimodal distribution with a slightly larger particle size overall (30% d ≤ 1 μm, 80% d ≤ 10 μm). Bulk high-entropy ceramics with a minor presence of an oxide phase were fabricated through the spark plasma sintering of these high-entropy powders at 2000 °C with a 10 min dwelling time. The HEC_Zr ceramics possess a relative density of up to 94.8%, hardness of 25.7 ± 3.5 GPa, Young's modulus of 473 ± 37 GPa, and thermal conductivity of 5.6 ± 0.1 W/m·K. HEC_Mo ceramics with a relative density of up to 93.8%, hardness of 23.8 ± 2.7 GPa, Young's modulus of 544 ± 48 GPa, and thermal conductivity of 5.9 ± 0.2 W/m·K were also fabricated. A comparison of the properties of the HECs produced in this study and those previously reported is also provided.     

Pyroelectric energy harvesting using low–TC (1–x)(Ba0.7Ca0.3)TiO3–xBa(Zr0.2Ti0.8)O3 bulk ceramics

Lead‐free ferroelectric ceramics (1–x)(Ba_0.7Ca_0.3)TiO₃–xBa(Zr_0.2Ti_0.8)O₃ (BCTZ100x) with x = 0.20, 0.30, 0.40, 0.50, 0.60, 0.70, and 0.80 were evaluated for their pyroelectric energy harvesting performance, using the Olsen cycle. As the composition ratio x increased, the crystal phase changed to tetragonal, orthorhombic, rhombohedral, and cubic; the phase boundaries crossed each other in the vicinity of BCTZ70. The crossover phase transition behavior between first‐order and diffuse phase transition changed to only the diffusion phase transition with increasing x. A pinching effect occurred because an increase in dielectric constant was also observed. Energy densities N_D of 229 mJ/cm³ and 256 mJ/cm³ for BCTZ50 and BCTZ80 were obtained, respectively, in temperature of 30°C‐100°C and an electric field of 0‐30 kV/cm. These N_D values are over two times higher than that of soft–Pb(Ti,Zr)O₃ (PZT), which exhibits piezoelectric performance equivalent to BCTZ50 at room temperature. Compared with soft–PZT, BCTZ50 and BCTZ80 exhibited larger N_D values owing to their lower Curie temperatures (T_C ~ 50°C‐110°C). We conclude that low–T_C ferroelectrics are useful for pyroelectric energy conversion based on the Olsen cycle even if they are unsuitable for piezoelectric applications at high temperatures.