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Rare-earth titanate oxides are believed to be prospective functional materials for photocatalytic and photoluminescent applications because of their excellent optical properties and thermal stability of their physical properties. However, the relationships between optical properties and photoelectron trapping mechanisms are unclear. Herein, the structure, electronic, and optical properties of pyrochlore-structure Re2Ti2O7 (Re = Sm and Eu) were investigated using the first-principles approach with the Hubbard parameter U (GGA + U). The calculated bandgap is 2.5 eV for Sm2Ti2O7 and 2.4 eV for Eu2Ti2O7, which is in good agreement with the experimental observation. The results indicate that the strongly localized f states at the top of valence band are charge-trapping sites for photoexcitation of Re2Ti2O7, where electrons can absorb photon energy and transfer from the valence band to the conduction band, resulting in the photocatalytic and/or fluorescent effects in the visible and early UV regions. The important optical parameters, dielectric function ε (ω) , refractive index n (ω) , extinction coefficient k (ω) , reflectivity R (ω) , absorption coefficient I (ω) , optical conductivity σ (ω) , and electron energy-loss L (ω) were studied in detail, indicating that these optical parameters of Sm2Ti2O7 and Eu2Ti2O7 are insensitive to the ultra-violet (UV) radiation, but both Sm2Ti2O7 and Eu2Ti2O7 exhibit excellent optical properties in the visible and early UV regions. This work provides a clear understanding on the photoelectron trapping mechanism of pyrochlore-structure Re2Ti2O7, which will help to improve the photocatalytic and photoluminescent performance of Re2Ti2O7 and broaden their applications. [ABSTRACT FROM AUTHOR]

In this study, K2Ti6O 1 3 (KTO) nanowires were doped with carbon (CKTO) via a novel solid-phase approach at 800∘C for the first time using ethanol, KF, and TiO2. In addition to the lower sintering temperature, a shorter insulation period was achieved compared to the conventional solid-phase method. Furthermore, by combining and calcining CKTO and g-C3N4, a CKTO/g-C3N4 heterojunction composite was produced. The rate at which CKTO/g-C3N4 photocatalytically degraded methylene blue was higher than those of pure CKTO and g-C3N4. Our study indicates that adding g-C3N4 enhances photocatalytic performance by reducing the recombination rate of photogenerated electron–hole pairs and narrowing the bandgap of the CKTO/g-C3N4 heterostructure. This paper presents a novel method for creating KTO composites in an eco-friendly and productive manner for the photocatalytic degradation of organic colors. [ABSTRACT FROM AUTHOR]

A new method is described to characterize the transformation kinetics of reconstructive systems at high temperatures using synchrotron X‐ray radiation, a quadrupole lamp furnace, and a detector capable of collecting a diffraction pattern of sufficient range in a minimal amount of time. Using this method, the activation energy for a reconstructive phase transformation in Dy2TiO5 was determined to be 149 kJ/mol. This value is more reasonable when compared with the uncertain values determined using conventional methods such as differential scanning calorimetry. In addition, the new method also provides higher quality data with improved time resolution, leading to better determination of fitted kinetic parameters. [ABSTRACT FROM AUTHOR]

The work is devoted to the study of the magnetic DC and AC susceptibilities, as well as to the analysis of spin dynamics (relaxation processes) of yttrium- and bismuth-doped rare earth holmium titanates. An influence of doping degree and the type of dopant on the magnetic properties of holmium titanates have been evaluated. The magnetization curves were measured. The measurement of frequency dependence of the AC susceptibility allowed us to analyze spin dynamics and estimate characteristic magnetic relaxation times in the studied systems. [ABSTRACT FROM AUTHOR]

The choice of efficient methods for the immobilization of high-level waste (HLW) resulting from the reprocessing of spent nuclear fuel (SNF) is an important scientific and practical task. The current policy of managing HLW within a closed nuclear fuel cycle envisages its vitrification into borosilicate (B-Si) or alumina–phosphate (Al-P) glasses. These wasteforms have rather limited waste loading and can potentially impair their retaining properties on devitrification. The optimal solution for HLW immobilization could be separating radionuclides into groups using dedicated capacious durable matrices. The phases of the Nd2O3–ZrO2–TiO2 system in this respect are promising hosts for the REE (rare earth elements: Nd, Ce, La, Pr, Sm, Gd, Y) –MA (MA: Am, Cm) fraction of HLW. In this manuscript, we present data on the composition of the samples analyzed, their durability in hot water, their behavior under irradiation, and their industrial manufacturing methods. [ABSTRACT FROM AUTHOR]

Polycrystalline samples (1-x)CaTiO3-xNaNbO3 (x = 0, 0.10, 0.20, 0.30 and 0.40) were synthesized using solid state reaction method. Powder X-ray diffraction at room temperature showed that all of the samples' crystal structures were orthorhombic with Pbnm space group. Low Χ² values were obtained and there was good agreement between the computed and observed XRD patterns according to the Rietveld refinement. Impedance spectroscopy of the samples was investigated over a broad frequency and temperature range. Nyquist plots of the samples depicted a thermally activated non-Debye type relaxation mechanism. A decrease in dispersive nature of dielectric constant (ε') and tangent loss (tan δ) at low frequencies is noticed in the NaNbO3 substituted samples rendering them a better stability. The samples became more resistive with NaNbO3 substitution in CaTiO3 lattice. Correlation between charge carriers and lattice has been established using modulus formalism. Imaginary impedance (Z'') and imaginary modulus (M'') have been employed to comprehend the conduction process in all the samples. [ABSTRACT FROM AUTHOR]

Y2TiO5 belongs to the Ln2TiO5 (Ln = lanthanide or Y) family of ceramic materials and exhibits a range of desirable material properties such as radiation tolerance, frustrated magnetism, and large dielectric constant. However, understanding the complex crystal structure of Y2TiO5 remains elusive, given that Y2TiO5 can adopt multiple polymorphs such as cubic, orthorhombic, and hexagonal phases within the lattice. In this work, we report a detailed structural analysis of Y2TiO5 using four‐dimensional scanning transmission electron microscopy coupled with unsupervised machine learning. The pyrochlore nanodomains, characterized by the ordered arrangement of yttrium cations on the A site of their A2BO5 structure, are present within the matrix of a predominantly fluorite‐structured Y2TiO5 along with a third polymorph, the hexagonal phase. The pyrochlore phase is found to form 2 nm boundary regions around hexagonal phase stacking faults, highlighting the potential influence of the hexagonal phase on the occurrence and distribution of the pyrochlore phase. Lastly, we identify a unique pyrochlore phase with asymmetric arrangement of cation ordering along a single planar direction. Our findings provide invaluable insights into the possible mechanisms stabilizing pyrochlore nanodomains within the fluorite lattice of Y2TiO5. [ABSTRACT FROM AUTHOR]

Reversible cross‐linked structures are widely used to turn thermoset plastics into recyclable and self‐healing vitrimer materials, but seldom applied in traditional flexible rubber/ceramic composites. In this paper, dioxaborolanes based flexible poly (isoprene (IP)‐co‐acrylonitrile (AN)) vitrimer is synthesized as the rubber matrix by copolymerizing with functional monomers at 5°C for 7 h, and mixed with 5 wt% modified barium titanates (BT) to prepare flexible high dielectric vitrimer composite. The materials are characterized by FTIR, TGA, SEM, DMA, etc. The results indicate that reversible crosslinking can occur above 76.4°C, and copolymerizing with the dioxaborolanes based monomers can turn poly (IP‐co‐AN) into the flexible vitrimer. The poly (IP‐co‐AN)/BT vitrimer composite not only shows a good thermal stability below 145.6°C, but also exhibits an excellent particle dispersivity and a certain self‐healing function at 80°C. The poly (IP‐co‐AN)/BT vitrimer composite has a storage modulus E' about 3.18 MPa at 25°C and Tg about −5.4°C, and shows a higher relative permittivity about 7.5 and lower dielectric loss about 0.156 at 1 k Hz. The results indicate that this paper provides a new method to achieve multifunction and high dielectricity for composites. Highlight: Reversible cross‐linked structures are applied in rubber / ceramic compositesCross‐linked flexible composites are reprocessable and self‐healingReversible bonds between particles and matrix improve compatibilitySynergism of BaTiO3 and cross‐linked structure enhances dielectric properties [ABSTRACT FROM AUTHOR]

Perovskite rare‐earth titanates RTiO3 display a rich array of magnetic and electronic properties, with a Mott‐insulating ground state and ferro‐ or antiferromagnetic spin orders depending on the rare‐earth R. The nominal Ti valence is 3+ with a corresponding 3d1 configuration. Yet, at the surface of both bulk and thin films of RTiO3, the Ti valence has been found to strongly deviate towards the more stable 4+ state, adversely affecting magnetic properties. While this finding is rather ubiquitous, its exact origin is still poorly understood, which hampers the integration of RTiO3 into complex heterostructures harnessing their rich physics. Here, scanning transmission electron microscope and electron energy loss spectroscopy experiments are used to analyze the top part of an epitaxial DyTiO3 thin film displaying a well‐developed Ti4+‐rich layer over several nanometres. It shows that this valence evolution is related to a combination of short‐range ordered interstitial oxygen planes and Ti‐Dy cationic imbalance. Both defects synergistically contribute to enough hole doping for a complete transition toward Ti4+ over a few unit‐cells from the surface while a structure primarily of the perovskite‐type is maintained. [ABSTRACT FROM AUTHOR]

The simple oxides like titania, zirconia, and ZnO are famous with their antibacterial (or even antimicrobial) properties as well as their biocompatibility. They are broadly used for air and water filtering, in food packaging, in medicine (for implants, prostheses, and scaffolds), etc. However, these application fields can be broadened by switching to the composite multicomponent compounds (for example, titanates) containing in their unit cell, together with oxygen, several different metallic ions. This review begins with a description of the synthesis methods, starting from wet chemical conversion through the manufacturing of oxide (nano)powders toward mechanosynthesis methods. The morphology of these multicomponent oxides can also be very different (like thin films, complicated multilayers, or porous scaffolds). Further, we discuss in vitro tests. The antimicrobial properties are investigated with Gram-positive or Gram-negative bacteria (like Escherichia coli or Staphylococcus aureus) or fungi. The cytotoxicity can be studied, for example, using mouse mesenchymal stem cells, MSCs (C3H10T1/2), or human osteoblast-like cells (MG63). Other human osteoblast-like cells (SaOS-2) can be used to characterize the cell adhesion, proliferation, and differentiation in vitro. The in vitro tests with individual microbial or cell cultures are rather far away from the real conditions in the human or animal body. Therefore, they have to be followed by in vivo tests, which permit the estimation of the real applicability of novel materials. Further, we discuss the physical, chemical, and biological mechanisms determining the antimicrobial properties and biocompatibility. The possible directions of future developments and novel application areas are described in the concluding section of the review. [ABSTRACT FROM AUTHOR]

Adsorbed water promotes proton conduction in ceramics at ambient conditions prior to its evaporation, apparently leading to the positive temperature coefficient of resistivity (PTCR) effect. Using surface water-containing Cs 2 Ti 6 O 13 (1.8 mol water/mol titanate) as an example, the static conductivity (at 50 °C) of ∼10−5 S cm−1 is one thousand times that at 200 °C due to the enhanced proton conduction. At 50–150 °C, the conductivity decreases by 4 orders of magnitude because water evaporation decreases the number of charge carriers. At 150–400 °C, the conduction in water-free Cs 2 Ti 6 O 13 is thermal-activated with the apparent activation energy E a ∼58–72 kJ mol−1, depending on the formalisms. We show clearly that an endothermic DSC peak (water evaporation) in Cs 2 Ti 6 O 13 coincides with all eight presentations of AC properties examined. Similar correlations are obtained from the TG/DTG curves in Cs 2 Ti 5 O 11 ·H 2 O containing mostly intercalated water. The correlation between thermal analyses and AC properties points out that water molecules essentially contribute to the charge transport at ambient conditions of layered alkali titanates. This scenario might be potentially extended to other humidity-sensitive ceramics. [Display omitted] • Water-induced PTCR effect and Arrhenius-like process are respectively observed in the presence/absence of surface water. • The endothermic water loss peak (DSC) coincides with all representations of AC properties. • Activation energies of conduction from different formalisims were quickly obtained in a single measurement. [ABSTRACT FROM AUTHOR]

Demand on high‐performance ion exchangers is ever‐increasing in energy and environment applications. Among many cation exchangers, layered alkali titanates generally show larger cation exchange capacity, but slower cation exchange rate due to their 2D micrometer‐size particle morphologies, which limits their practical applications. Here, a rational conversion of a layered sodium titanate, Na2Ti3O7, is reported to the corresponding 1D ultra‐narrow nanowires via hydrothermal treatment under basic conditions. The formation of nanowires is thought to involve the partial exfoliation of Na2Ti3O7 to form thin plate‐like particles that subsequently split into nanowires along a crystallographically defined, chemically selective weakness in the Na2Ti3O7 crystals. This process is similar to a recently burgeoning materials design using atomic‐level weakness in solids, such as zeolites and metal‐organic frameworks. The proposed formation scheme is further supported by comparative experiments performed on another layered alkali titanate, K0.8Ti1.73Li0.27O4, which possesses randomly distributed defects at the Ti sites. Thanks to the shortening of diffusion path lengths of the interlayer cations, the resulting Na2Ti3O7 nanowires show an excellent cation exchange performance toward Cd2+ in aqueous solution, exceeding several existing cation exchangers such as zeolites and organic resins. [ABSTRACT FROM AUTHOR]

The world's steadily growing population and global heating due to climate change are a threat to food security. To meet this challenge, novel technologies are needed to increase crop production in a sustainable way. In this work, the use of luminescent down‐shifting (LDS) materials based on molecular Eu3+‐containing polyoxotitanates for plant growth enhancement is investigated. Using a systematic design strategy to optimize down‐shifting properties, conversion of the ultraviolet spectral range to the photosynthetically active radiation (PAR) is achieved with quantum yields as high as 68%. The prototype Eu3+‐compound can be incorporated into water‐based acrylic varnish that can be spray‐coated onto existing greenhouses. Comparing coated with uncoated greenhouses, basil plants produce 9% more leaf dry weight per plant, and a highly significant 10% increase in individual leaf dry weight. The coating reduces the amount of transmitted PAR by 8% but has advantageous effects on diffuse radiation and in reducing the internal mean temperature. Although there is some uncertainty as to the contribution of down‐shifting, with the bulk of the increase probably being due to higher diffused light and the reduction in maximum daily temperatures, this study establishes a model for the design of LDS paints for real‐world agricultural applications. [ABSTRACT FROM AUTHOR]

Single crystals of hexahydrates of divalent fluoridotitanates MTiF6·6H2O (M = Mn, Co, Ni, Zn) are synthesized. Their crystal structures are determined by X-ray diffraction at room temperature (RT-structure) and below the phase transition (LT structure). The phase transition is accompanied by a transformation of the disordered trigonal lattice into the ordered monoclinic one. The initial RT-structures differ in the set and strength of O–H⋯F hydrogen bonds linking isolated [M(H2O)6]2+ and [TiF6]2– octahedra into a 3D framework. There is a correlation between the strength of hydrogen bonds and the thermal behavior of the complexes. [ABSTRACT FROM AUTHOR]

The isobaric heat capacity of pyrochlore gadolinium titanate Gd2Ti2O7 is measured in the 2–1825 K range of temperatures. Thermodynamic functions (entropy, enthalpy change, reduced Gibbs energy) are calculated using consistent smoothed values of heat capacity. The Gibbs energy of the formation of Gd2Ti2O7 from oxides in the high temperature range is estimated. [ABSTRACT FROM AUTHOR]

Bulk samples of holmium and ytterbium rare earth titanates doped with yttrium and bismuth were synthesized. To study the magnetic properties and peculiarities of magnetic interaction in doped and undoped titanates, magnetization curves and temperature dependences of the susceptibility were measured in fields up to 3 T at temperatures from 2 to 300 K. Magnetic properties for doped and undoped titanates with different doping level, as well as doped with different elements, have been compared. Based on study of temperature dependences of the susceptibility, magnetic dipole and exchange interactions have been analyzed. In the case of undoped holmium titanate, the dominant magnetic interaction type has been found to be the dipole one. When doping of holmium titanate with yttrium and bismuth, the magnetic interactions between the rare earth ions are sharply weak. Undoped ytterbium titanates have shown a predominance of the superexchange interaction. Presence of a large number of randomly distributed yttrium or bismuth ions, which occupy positions of ytterbium ions in crystal lattice, leads to the decrease in concentration of R3+-O-R3+ ion pairs in this rare earth titanate, between which there is superexchange. Therefore, in doped compounds, the magnetic dipole interaction capable to act at large distances contrary to the superexchange one begins to predominate. The values of the g-factor have been estimated by the fit of the measured magnetization curves. [ABSTRACT FROM AUTHOR]

Exploring semiconductor materials with enhanced photocatalytic activity is essential for practical applications. This review provides a comprehensive overview of the photocatalytic reaction mechanisms. The discussion highlights recent progress in perovskite oxide materials for various environmental and energy applications, including H2/O2 production, organic pollutant degradation, heavy metal removal, radionuclide removal, CO2 reduction, and N2 fixation. The structural characteristics of perovskite oxides including titanates, tantalates, niobates, ferrites, and complex perovskite oxides are discussed, focusing on current strategies to enhance their photocatalytic activity. Furthermore, recent advances in the design and development of perovskite-based photocatalytic reactors are reviewed, emphasizing their potential for increased efficiency and practical implementation. This review aims to provide insights into the abilities, research gaps, future perspectives, and recommendations for further studies of perovskite oxide photocatalysts in addressing significant environmental and energy challenges. [ABSTRACT FROM AUTHOR]

Adding excessive metal oxide doping to a powder batch is a known way to compensate for the loss of volatile cation species during high temperature sintering. An important case in the piezoelectric ceramics is the bismuth oxide in the lead-free ferroelectric ceramic bismuth sodium titanate (BNT). Building from the earlier knowledge about excessive bismuth oxide's influences on the properties of BNT, we further note that varying the sintering temperature can both control the distribution of excessive Bi3+ and impact the relaxor/normal ferroelectric behaviors and corresponding phase transition. In addition to the nature of polarization, the sintering temperature also significantly manipulates the electrical conductivity. A hypothetical mechanism for the resistive grain boundary is proposed, based on inferences from electrical—microstructure—processing relations in 85% Bi0.5Na0.5TiO3-15% BaTiO3 with batched Bi2O3 excess and acceptor Mg2+ in a co-doped strategy. [ABSTRACT FROM AUTHOR]

Whispering gallery mode resonators (WGMRs) have garnered significant interest due to their potential applications in the fields of electro-optic modulation and microwave to optical photon conversion. In this study, we have leveraged an electro-optic crystal, lead indium niobate-lead magnesium niobate-lead titanate (PIN-PMN-PT), to fabricate a high-quality WGMR. Our investigation revealed that the crystal composition used in this work is 0.24PIN-0.45PMN-0.31PT, and each element of the whole sample is homogeneously distributed. The dielectric properties of the sample revealed the necessity of limiting the temperature and external electric field frequency to below 100 °C and 106 Hz, respectively. The obtained optical quality factor value (Q value) of the resonator is ∼0.7 × 105. Impressively, our resonator could be conveniently tuned by exploiting the enormous inverse piezoelectric effect d31 of the crystal, thereby alleviating the need for precise fabrication. Furthermore, a theoretical analysis of our resonator revealed that a calculated resonance wavelength shift is within a broad range of 2.16 nm. Intriguingly, if the surface roughness of the resonator is reduced tenfold, we can increase the calculated Q value dependent on surface scattering by 104. Our finding showcases the tremendous potential of the PIN-PMN-PT crystal-based WGMR as versatile building blocks for a variety of applications in the burgeoning field of photonic technology. [ABSTRACT FROM AUTHOR]

Sub-micrometer-sized (0.33 μm) polycrystalline powders of calcium copper titanate (CCTO) were synthesized via the solgel method. Compacted calcined powders were sintered at 900 °C/2h to obtain porous (<80% density) pellets. Subsequently, ZnO or SnO2 pastes (∼10 μm grain size) were smeared on either side of the pellets and sintered at 1100 °C/15 h, which yielded dense (>95% density) ceramics. X-ray structural investigations revealed the presence of ZnO or SnO2 traces in the bulk of the CCTO ceramics. Scanning electron microscopy and energy dispersive spectroscopic studies confirmed the diffusion and the segregation of these oxides at the grain boundaries. The dielectric and varistor properties of the ZnO or SnO2 diffused samples were found to be superior to that of pristine CCTO ceramics. For instance, the dielectric constant (ɛ′) of ZnO diffused ceramics exhibited a value as high as 2.4 × 104 (1 kHz, at room temperature) and a dielectric loss (D) of 0.059. Similarly, SnO2 diffused ceramics exhibited a dielectric constant of 2.7 × 104 (1 kHz, at room temperature) associated with a dielectric loss of 0.047. The figure of merit of varistor performance, i.e., nonlinear coefficient (α = 10.6), of the SnO2 diffused sample is significantly higher than that of ZnO diffused (α = 7.4) and pristine CCTO (α = 4.5) ceramics. The dielectric data obtained for both the pristine and ZnO or SnO2 diffused ceramics were rationalized by invoking Cole–Cole analysis. The thermal activation energy was estimated from the temperature-dependent dielectric data besides current (I)–voltage (V) characteristics. Equivalent circuit modeling of the Nyquist plots demonstrated that the inclusion of ZnO and SnO2 layers in CCTO ceramics remarkably improved the grain boundary resistance (Rgb) by 5-fold and 20-fold, respectively, which resulted in making CCTO a better dielectric. This methodology of fabricating ceramics via interfacial engineering could pave the way for obtaining superior CCTO ceramics associated with exotic functional properties. [ABSTRACT FROM AUTHOR]

Solid solutions of rare earth titanates with high contents of rare earth oxides of up to 50-62% have been synthesized by the co-precipitation method and their structure, microstructure and conductivity in dry and wet air have been studied. Proton conductors have been found for the first time in solid solutions of rare earth titanates with a high content of Ln2O3 (>50%) with a nominal formula composition of (LnxTi1-x)4O8-2x (Ln = Yb, Er, Ho, 0.667 = x = 0.765). Among (LnxTi1-x)4O8-2x (Ln = Yb, Er, Ho, x = 0.684), (HoxTi1-x)4O8-2x (x = 0.684) showed the maximum conductivity in wet air. In this context, four additional compositions (HoxTi1-x)4O8-2x (x = 0.718, 0.734, 0.75, and 0.765) were synthesized in the holmium series. An increase in the holmium content leads to an increase in the proton transfer coefficients; at the same time, a more complex nature of the dependence of the conductivity under dry and wet atmospheres is observed. For the fluorite-like solid solution (HoxTi1-x)4O8-2x (0.701 = x = 0.765), the proton transfer coefficients were found to be ~0.9 in the range of 200-450 °C. As the temperature continues to rise, the proton conductivity decreases quite sharply and the transfer coefficient becomes as low as 0.3 at 700 °C. The increase in proton conductivity in the Yb-Er-Ho series is associated with an increase in the hydrophilic properties of rare earth cations. In the (HoxTi1-x)4O8-2x (x = 0.667 = x = 0.765) series, the conductivity in wet air was ~1 × 10-6 S cm-1 at 450 °C for most compositions. The conductivity of ceramics with x = 0.701 and 0.75 is about 2 times higher, which may be due to the optimal size of pyrochlore nanodomains in the fluorite matrix for x = 0.701 and the formation of pure fluorite for x = 0.75, respectively. [ABSTRACT FROM AUTHOR]

The primary goal of this study is to elucidate the structural and electrical characteristics, alongside potential applications, of ceramic-polymeric composites. These composites are achieved by incorporating lithium-lanthanum titanates (Li 3x La 2/3−x TiO 3 - LLTO) into a polyvinyl alcohol polymeric matrix (PVA). The synthesis of lithium-lanthanum titanates occurred through high-energy ball milling method. Then, three types of composites were produced using the solvent casting method: a sample of pure Poly (vinyl alcohol) polymer (PVA), a second PVA composite with the addition of La 0 · 59 Li 0 · 24 TiO 3 (Li-0.24) and a third sample with La0· 56 Li 0 · 33 TiO 3 (Li-0.33). SEM and AFM analyzes revealed notable changes in the morphology and 3D spatial patterns of the films upon incorporating lithium-lanthanum titanates into the PVA matrix. The PVA film presents a topography featuring a more evenly distributed range of topographic heights, indicating a smoother surface structure. With varying LLTO content, the morphology of the PVA composite underwent changes. The lower roughness of the PVA surface is evident from its measured average roughness value (Ra = 1.9 ± 0.5 nm). Upon incorporating LLTO, the surfaces displayed increased roughness, measuring specifically at 40.1 ± 7.3 nm (Li-0.24) and 22.7 ± 5.5 nm (Li-0.33). Notably, there was an approximately 43 % reduction in the average roughness value from Li-0.24 to Li-0.33. The analysis by Raman allowed the identification of functional groups of the PVA polymeric chain, in addition to the presence of some vibrational modes related to the structure of lithium-lanthanum titanates for the sample with the highest content of Li+ ions (Li-0.33). Finally, the sample Li-0.33 showed the lowest value of electrical resistance (67 kΩ) and of phase angle (16°), compared to the PVA (100 MΩ and 90°). These results show that the presence of the LLTO changed the insulating behavior of the PVA matrix changed and improved potential to electronic applications. [ABSTRACT FROM AUTHOR]

This work demonstrates a mechanism of heterogeneous nucleation for the synthesis of BaTiO 3 nanowires utilizing K 2 Ti 4 O 9 as template by manipulating alkalinity, temperature and reaction time. Results suggest that the synthesis of BaTiO 3 does not occur through a hydrothermal ion-exchange, instead, the predominant mechanism observed is the heterogeneous of dissolution-crystallization. The consistency of crystallographic orientation for BaTiO 3 nanowires is affected by the hydrothermal conditions. BaTiO 3 nanowires synthesized at 190 °C/0.2 M exhibit a uniform (100)/(001) crystallographic orientation, albeit not consistently along the length of the nanowires, while BaTiO 3 crystal grains no longer have the same crystallographic orientation at 190 °C/0.8 M. By investigating the reaction mechanism of BaTiO 3 , this work may have great significance for the synthesis of perovskite-type MTiO 3 (M = Ba,Ca, Sr, Pb) utilizing layered titanates. [ABSTRACT FROM AUTHOR]

Rare-earth titanate pyrochlores have attracted significant attention for their unique magnetic frustration; however, research on the origin of low-temperature dielectric dispersion and the relationship between dielectric properties and structure lags far behind. Here, by systematically investigating the dielectric properties of representative rare-earth titanates R2Ti2O7 (R = La, Nd, Sm, Er, Yb, and Lu), we demonstrate that R2Ti2O7 with a cubic pyrochlore structure exhibits low-temperature dielectric dispersion behavior, while the other compounds with a monoclinic perovskite-like layered structure possess no dispersion behavior but excellent temperature-stable dielectric property. The dielectric dispersion in cubic pyrochlores arises from the structural distortion. Furthermore, the existence of structural distortion is affirmed by the anomalous phonon softening of A1g Raman mode around the dielectric dispersion temperature, and the origin of the structural distortion is attributed to anharmonic phonon–phonon interactions induced by intrinsic vacant oxygen at Wyckoff 8a sites. In addition, with increasing ionic radius from R = Lu to Sm, the increased lattice parameter leads to varied bond length and bond angle of Ti-O(1)-Ti, which strengthens the local lattice distortion of TiO(1)6 octahedra and thus enhances diffusion degree of dielectric dispersion. On the other hand, the absence of intrinsic vacant oxygen site hardly gives rise to the local structural distortion and thus no dielectric dispersion in monoclinic R2Ti2O7. Our work not only clarifies the mechanism of dielectric dispersion but also gives a comprehensive perspective on the structure–property relationship of rare-earth titanates R2Ti2O7, and thus lays a solid foundation for further work on related materials. [ABSTRACT FROM AUTHOR]

High-entropy ceramics have garnered significant attention in recent years owing to their exceptional properties and structural diversity. In this work, single-phase medium/high entropy ceramics, namely (Ca 0.2 Sr 0.4 Ba 0.4)(Zr 0.5 Ti 0.5)O 3 and (Ca 0.2 Sr 0.4 Ba 0.4)(Zr 0.1 Ti 0.9)O 3 , were successfully designed and prepared utilizing Spark Plasma Sintering (SPS). A comprehensive investigation was conducted into the phase structure, microscopic morphology, dielectric properties, and thermal behavior of these ceramics. It was observed that all ceramics maintained a cubic perovskite structure (space group: Pm 3 ‾ m), and the introduction of multi-element doping rendered them more stable across a wide frequency and temperature range. Notably, (Ca 0.2 Sr 0.4 Ba 0.4)(Zr 0.5 Ti 0.5)O 3 exhibited remarkably low dielectric loss (0.0001 at 1 kHz) at room temperature, along with excellent dielectric temperature stability (25–400 °C). By reducing the zirconium concentration in (Ca 0.2 Sr 0.4 Ba 0.4)(Zr 0.1 Ti 0.9)O 3 , a slight decrease in dielectric temperature stability was observed (25–350 °C); however, it demonstrated lower thermal conductivity (0.41 W/(m·K), 1200 °C) and maintained good high-temperature stability. The discovery highlights the promising practicality of both ceramics for high-temperature dielectric applications. [ABSTRACT FROM AUTHOR]

The temperature dependence of the heat capacity of Y2Ti2O7 and Eu2Ti2O7 with a pyrochlore structure in the temperature range of 7–1800 K has been studied. The existence of a small shallow anomaly of the heat capacity of europium titanate in the range of 10–60 K was confirmed. The thermodynamic properties (entropy, enthalpy change, and reduced Gibbs energy) were calculated. Based on the results of calculation of the Gibbs energy of formation of the titanates from oxides it was concluded that both titanates are thermodynamically stable in the high temperature region. [ABSTRACT FROM AUTHOR]

A hierarchical sea urchin-like hybrid metal oxide nanostructure of ZnO nanorods deposited on TiO2 porous hollow hemispheres with a thin zinc titanate interface layer is specifically designed and synthesized to form a combined type I straddling and type II staggered junctions. The HHSs, synthesized by electrospinning, facilitate light trapping and scattering. The ZnO nanorods offer a large surface area for improved surface oxidation kinetics. The interface layer of zinc titanate (ZnTiO3) between the TiO2 HHSs and ZnO nanorods regulates the charge separation in a closely coupled hierarchy structure of ZnO/ZnTiO3/TiO2. The synergistic effects of the improved light trapping, charge separation, and fast surface reaction kinetics result in a superior photoconversion efficiency of 1.07% for the photoelectrochemical water splitting with an outstanding photocurrent density of 2.8 mA cm−2 at 1.23 V versus RHE. [ABSTRACT FROM AUTHOR]

Sodium bismuth titanate‐based materials are expected to be an alternative candidate to lead‐based ceramic materials due to their excellent electrical properties. However, the low depolarization temperature (Td) limits their practical application. In this work, the phase structure evolution and microstructure of 0.9(0.4Na1/2Bi1/2TiO3–0.6BiFeO3)–0.1BaTiO3: xZnO (x = 0.01, 0.03, 0.05, and 0.07) (abbreviated as 100xZnO) composite ceramics are investigated, and their piezoelectric properties are improved by combination of constructing 0–3 type composites and quenching treatment technology. The addition of ZnO can increase both Td and d33 because ZnO can enhance the lattice distortion of rhombohedral phase and lead to the increase in ferroelectric order. Specifically, the optimum composition x = 0.03 obtains the d33 value of 106 pC/N (25°C), which retains 84% of the value at room temperature up to 240°C. And the quenching technology further enhances the ferroelectric order and increases Td, which is up to 280°C for x = 0.03. [ABSTRACT FROM AUTHOR]

Advancing the development of high‐temperature piezoelectric sensors requires high‐performance piezoelectric materials with high Curie temperatures, wherein the charge signals can be efficiently collected at elevated temperatures. The bismuth layer‐structured ferroelectric (BLSF) bismuth titanate‐ferrite (Bi5Ti3FeO15, BTF) has recently attracted considerable attention because of its high Curie temperature (TC) of ∼761°C. However, the piezoelectric properties of BTF‐based compounds have not been extensively investigated because of their extremely poor piezoelectric performances and low electrical resistivities at elevated temperatures. Herein, tungsten‐substituted BTF (BTF‐100xW) ceramics were synthesized using a solid‐state reaction method. X‐ray diffraction refinement results confirmed the lattice distortion of the BO6 octahedron, while piezoelectric force microscopy images verified an increase in the domain wall density with tungsten modification, both of which contribute to significant enhancement of the piezoelectric properties of BTF‐100xW as intrinsic and extrinsic contributions, respectively. Remarkably, BTF‐3W exhibits a high TC of 793°C and a large piezoelectric constant (d33) of 24.3 pC/N, which is over three times that of BTF (7.1 pC/N). Importantly, the substitution of tungsten decreases the concentration of oxygen vacancies, increases the direct current electrical resistivity, and improves the electrical homogeneity at high temperatures, resulting in extremely stable piezoelectric and electromechanical properties at high temperatures, with a high in‐situ relative d33 of >90% at 400°C and a small variation in the electromechanical coupling factor (kp) of <8% at temperatures up to 450°C. These results suggest that the tungsten‐substituted BTF is a potential candidate for high‐temperature piezoelectric ceramics, and is a promising material for applications in high‐temperature piezoelectric sensors. [ABSTRACT FROM AUTHOR]

Structurally correlated ferroelectric phase transitions induced by temperature are reported for the solid solution Pb0.6Ca0.4TiO3 compound. Such phase transitions were analyzed by considering different parameters, such as lattice parameters, microstrain, dielectric properties, and thermal analysis. Synchrotron x-ray diffraction and Rietveld refinement studies revealed a tetragonal symmetry from room temperature up to ∼550 K and uniaxial microstrain from room temperature to ∼400 K. The first thermally driven phase transition observed was from displacive ferroelectric tetragonal symmetry to another non-displacive tetragonal symmetry. The next phase transition was from the tetragonal to cubic. The electric permittivity as a function of temperature for frequency from 1 kHz to 1 MHz and the differential scanning calorimetry report features typical of ferroelectric–paraelectric phase transition only around 400 K, and no other abrupt change in properties is observed at 550 K, indicating the sequence of first- and then second-order phase transition. [ABSTRACT FROM AUTHOR]

Single crystals of undoped and Nb doped sodium and potassium-bismuth titanate at the morphotropic phase boundary (MPB) composition [(Na0.41K0.09Bi0.50)TiO3: NKBT] were grown from high temperature solutions. The effect of Nb doping on the electronic property of NKBT was investigated by optical transmission and photoelectron spectroscopy (PES). The optical absorption shows that the bandgap having the lowest energy is indirect in nature and increases with the increase in the Nb concentration in the lattice. The estimated Urbach energy increases with the increase of Nb concentration signifying an increase in the disorder in the lattice on Nb doping. The PES revealed that the valence band maxima (VBM) exhibit red shift on Nb doping. It also revealed the presence of in-gap states probably due to Ti3+ defect and oxygen vacancy. Moreover, inline with the optical measurement, the PES showed that there is a decrease in the energy gap between the VBM and defect state with the Nb doping. Furthermore, the angle resolved PES measurement confirmed the presence of both the direct and indirect bandgaps in the crystal. [ABSTRACT FROM AUTHOR]

Uniformly acceptor doped Pb(Zr0.48Ti0.52)O3 (PZT) films with 2 mol. % Mg or Fe prepared by chemical solution deposition exhibited decreased dielectric constants and remanent polarizations relative to undoped PZT. For highly accelerated lifetime testing (HALT) at 200 °C and an electric field of 300 kV/cm in the field up direction, the HALT lifetimes (t50) for undoped, Mg-doped, and Fe-doped PZT films were shortened from 2.81 ± 0.1 to 0.21 ± 0.1 and 0.54 ± 0.04 h, respectively. Through thermally stimulated depolarization current measurement, significant V O ∙ ∙ electromigration was found in homogeneously Mg-doped PZT thin films, a major factor in their short HALT lifetime. Because the concentration of oxygen vacancies increases with uniform acceptor doping, the lifetime decreases. In contrast, when a thin layer of Mg-doped or Fe-doped PZT was deposited on undoped PZT or Nb-doped PZT (PNZT), the HALT lifetimes were longer than those of pure PZT or PNZT films. This confirms prior work on PNZT films with a Mn-doped top layer, demonstrating that the HALT lifetime increases for composite films when a layer with multivalent acceptors is present near the negative electrode during HALT. In that case, the compensating electrons are trapped, presumably on the multivalent acceptors, thus increasing the lifetime. [ABSTRACT FROM AUTHOR]

Although a large electric-induced strain has been obtained in sodium bismuth titanate (Bi0.5Na0.5TiO3, BNT)-based ceramics using chemical modifications, the effect of initial BNT-based ceramic's polarity on modulating strain properties was rarely reported. Herein, we comparatively studied the effect of tantalum (Ta) doping on two BNT-based ceramics with different ferroelectric polarities, namely, (Bi0.5Na0.5)0.935Ba0.065TiO3–0.7%Bi2FeCrO6 and (Bi0.98Gd0.02)0.5Na0.5TiO3. The former locates at the morphotropic phase boundary (MPB), whereas the latter is close to pristine BNT ceramics. An effective critical point, located at the crossover between ferroelectric and relaxor, is constructed in the former ceramic and significantly enhances strain properties, whereas a useless one is found in the latter ceramic due to the retention of a non-ergodic relaxor and has merely limited ability to promote strain properties. Our results demonstrate that the ferroelectric polarity of the initial BNT-based ceramic matrix also plays an important role in pursuing high strain properties. [ABSTRACT FROM AUTHOR]

The micrometer-sized nickelate–titanate heterojunctions with LaNiO3 (LNO) electrode have been fabricated to investigate the dominant current transport mechanisms under positive and negative bias. The LNO/SmNiO3 (SNO)/Nb:SrTiO3 (NSTO) heterojunction exhibits a highly rectifying feature with a very low leakage in a broad temperature region (from 200 to 425 K), which is attributed to the formation of a Schottky-like barrier at the SNO/NSTO interface. In addition, it is found that the trap defects (i.e., oxygen vacancies) play an essential role in determining the current density (J)–voltage (V) characteristics irrespective of the voltage polarity. The leakage current at low electric fields (<0.25 MV/cm) is dominated by temperature-enhanced trap assisted tunneling process, which is caused by the interface oxygen vacancy induced states. Further analysis suggests that, at high fields (>1.2 MV/cm), the leakage is ascribed to the bulk-limited field enhanced thermal ionization of trapped carriers in the SNO film (i.e., Poole–Frenkel emission). Specially, the oxygen vacancy redistribution near the SNO/NSTO heterointerface driven by a high temperature (425 K) or high electrical field (>3.8 MV/cm) stress is emphasized to account for the transition from the Schottky contact limited to bulk-limited conduction mechanism (i.e., space charge limited conduction). This work will benefit the further analysis of the resistive switching phenomena in nickelate-based devices, showing a potential for nonvolatile memory applications. [ABSTRACT FROM AUTHOR]

An electrothermal analysis for barium-titanate-based ceramics is presented, combining the Heywang–Jonker model for the electric resistivity with a heat dissipation mechanism based on natural convection and radiation in a one-dimensional model on the device level with voltage as the control parameter. Both positive-temperature-coefficient (PTC) and negative temperature coefficient (NTC) effects are accounted for through the double Schottky barriers at the grain boundaries of the material. The problem formulated in this way admits uniform and non-uniform multiple-steady-state solutions that do not depend on the external circuit. The numerical bifurcation analysis reveals that the PTC effect gives rise to several multiplicites above the Curie point, whereas the NTC effect is responsible for the thermal runaway (temperature blowup). The thermal runaway phenomenon as a potential thermal shock could be among the possible reasons for the observed thermomechanical failures (delamination fracture). The theoretical results for the NTC regime and the thermal runaway are in agreement with the experimental flash sintering results obtained for barium titanate, and 3% and 8% yttria-stabilized zirconia.

The bulk photovoltaic effect observed in ferroelectric materials can enable photovoltaic performance beyond the Shockley–Queisser limit of efficiency. This requires the use of ferroelectrics with strong polarization and low bandgap (Eg) that are typically contradictory in the common perovskite oxides ferroelectrics. Here, we use first-principles calculations to study the KNbO3–K(Ti0.5Mo0.5)O3 (KNTM) solid solutions as possible narrow-gap ferroelectric materials. KTM, the end-member of the recently discovered KNTM solid solution system, maintains a ferroelectric polarization similar to that of other K-based systems due to its d0 configuration at the B-site. The substitution of Nb in KTM reduces Eg from 2.9 of KTM to 1.83 eV for an unstrained system and 1.7 eV for a compressively strained system, while maintaining ferroelectricity. The combination of narrow Eg, strong ferroelectricity, low toxicity, and abundance of the constituent elements make Nb-substituted KTM a promising candidate material for photoferroelectric applications. [ABSTRACT FROM AUTHOR]