Frequency dependence of antiferroelectricferroelectric phase transition of PLZST ceramic

Antiferroelectric (AFE) ceramics are promising for applications in high-power density capacitors, transducers, etc. The forward switching field and backward switching field are critical performance indicators for AFE ceramics, and the coupling between the structure transition and domain orientation makes them different from the coercive field of ferroelectric (FE). Moreover, in practical applications, AFE ceramics are often required to operate at varying frequencies. However, systematic studies regarding the frequency dependence of and are insufficient. In this work, (PLZST) AFE ceramic was fabricated, and two empirical formulas (, ) were proposed to predict the frequency dependence of and . The formulas are based on the electric field–induced phase transition characteristics of AFE and the Kolmogorov–Avrami–Ishibashi domain nucleation-switching model. Furthermore, the dynamic hysteresis loops of PLZST at various frequencies (1–1000 Hz) and temperatures (–) were investigated. The results show that the electric field–induced phase transition of AFE ceramic is dominated by the coupling between the structural transition and domain orientation. The domain orientation hinders the structure transition, leading to an increase in and a decrease in as the frequency of applied electric field increases. Meanwhile, the domain growth process is affected by the structure of AFE, and the value of (domain growth dimensionality) increases with the stability of the AFE structure. For comparison, (PLBZST) relaxor FE ceramic was fabricated. Due to the high mobility of the microdomain, the dynamic hysteresis loop of PLBZST ceramic exhibits excellent frequency stability. The charge–discharge experiment with an ultrahigh equivalent frequency (100 kHz) was performed to investigate the frequency stability of energy release of PLZST and PLBZST. The results may provide guidance for research pertaining to ceramic capacitors with high-power density and high-frequency stability.     

Thermoelectric properties and phase transition of doped single crystals and polycrystals of Bi2Te3

The temperature dependences of the electrical conductivity , Seebeck coefficient , and heat capacity C_p(T) of polycrystalline samples of Bi₂Te₃, Bi₂Te₃+1%CuI, and Bi₂Te₃+1%(CuI+1/2Pb) are investigated in the temperature range below room temperature. Based on the temperature dependences of all investigated physical properties, it is discovered that phase transition occurs at 120–200 K. Investigation of single crystals shows that anomalies in the electrical resistivity occur only across the crystal growth axis (across the well-conducting Bi–Te plane). Investigation of the low-temperature dependence of electrical conductivity shows that all polycrystalline samples exhibit quasi-two-dimensional electron transport. Additionally, quasi-two-dimensional transport is detected in single crystals based on anisotropy analysis (where is the resistivity along the crystal growth axis, and is resistivity across the crystal growth axis) and temperature dependence below 50 K. The Fermi energy is estimated using the temperature dependence of . It is discovered that an increase in at T > 200 K is associated with the phase transition. For single-crystal samples, the maximum thermoelectric figure of merit ZT, as observed along the crystal growth axis, increases with doping. A maximum ZT value of ∼1.1 is observed for the Bi₂Te₃+1%(CuI+1/2Pb) sample at room temperature ().     

Synchrotron x-ray spectroscopy investigation of the Ca1−xLnxZrTi2−x(Al,Fe)xO7 zirconolite ceramics (Ln = La,Nd, Gd,Ho, Yb)

When incorporating actinides into zirconolite for high-level radioactive waste immobilization, Al³⁺ and Fe³⁺ ions generally act as charge compensators. In this study, we rationally designed a series of (Ln = La, Nd, Gd, Ho, Yb) to unravel the dopant solubility and evolutions of the crystalline phase and local environment of cations through synchrotron X-ray methods. It was found that single zirconolite phase is difficult to obtain and the fraction of perovskite have an increase with x from 0.1 to 0.9 in . Formation of both zirconolite-2M and zirconolite-3O phases was observed in and . Phase transformation from zirconolite-2M to 3O occurs at x = 0.7 for while x = 0.9 for . The solubility of and to form single zirconolite-2M can reach to 0.9 f.u. and 0.7 f.u., respectively. The evolution of lattice parameters of zirconolite in is greatly related to the ionic radii of cations and substitution mechanism among the cations. X-ray absorption near edge spectroscopy revealed that Fe³⁺ ions replace both five- and six-coordinated Ti sites and the ratio of TiO₅ to TiO₆ decreases when increasing dopant concentration in the . For the local environment of Zr⁴⁺, the major form is ZrO₇ with a trace of ZrO₈.     

Ultralow dielectric loss in Y-doped SrTiO3 colossal permittivity ceramics via designing defect chemistry

Effects of doping of Y and sintering atmosphere on the dielectric properties of Sr_1-1.5xY_xTiO₃ ceramics (SYT, x = 0-0.014) were systematically investigated. The SYT14 (x = 0.014) ceramic sintered in N₂ attains a colossal permittivity (CP, Ɛ_r = 28 084@ 1kHz, 27 685@ 2MHz) and an ultralow dielectric loss (tanδ = 0.007@ 1kHz, 0.003@ 2MHz) at room temperature. Because of using of the A-site deficient, there are in SYT ceramics. Through the comprehensive analysis of dielectric responses, X-ray photoelectron spectroscopy (XPS), electron paramagnetic resonance (EPR), and complex impedance data, it is proved that doping of Y promotes the formation of (Y³⁺ are located at Sr²⁺ site), (Y³⁺ are located at Ti⁴⁺ site), and Ti³⁺, and sintering in reducing atmosphere of N₂ results in more (oxygen vacancy) and (strontium vacancy) generating in SYT ceramics. The defect dipoles, , , , , , and formed by introduced defects make charge carriers localized in SYT ceramics. The combined action of the massive defect dipoles is responsible for the ultralow tanδ and CP in SYT14 ceramics sintered in N₂.     

Design of a defect-induced orange persistent luminescence phosphor BaZnGeO4:Bi3+

We report a novel bright orange persistent luminescence (PersL) phosphor BaZnGeO₄:Bi³⁺ with broad emission and PersL spectra. Its crystal structure, photoluminescence (PL) spectra, thermoluminescence (TL) spectra and PersL spectra were investigated in detail. The two emission bands at 440 nm and 595 nm originate from Bi³⁺ ions in normal Ba²⁺ sites (Bi1) and Ba²⁺ sites close to vacancy defects (Bi2), respectively. The introduction of and defects improves the emission intensity of Bi2 more than that of Bi1, demonstrating that Bi2 is related to the vacancy defects. The orange emission and PersL properties of BZGO:Bi³⁺ can be improved when a little and defects are introduced, because the introduction of and defects makes it easier for Bi³⁺ to enter in Ba²⁺ sites; and for PersL, and defects can perform as the effective trap centers to capture more charges, which is beneficial for PersL. BZGO:Bi³⁺ has quite good thermal stability, and the bright orange PersL can be observed by the naked eye for 1 h. Finally, a feasible PersL mechanism of BZGO:Bi³⁺ was proposed to clarify the PersL-generation process.     

Fabrication and characterization of tetragonal yttria-stabilized zirconia single-crystalline thin film

Tetragonal yttria-stabilized zirconia thin film was successfully fabricated by a pulsed laser deposition method. The thin film grew heteroepitaxially with the orientation relationship of ZrO₂‖Al₂O₃. Energy dispersive X-ray spectroscopy mapping revealed that Y³⁺ ions were distributed homogeneously without local segregations. X-ray and electron-diffraction analysis confirmed a single crystalline structural feature of the film. On the other hand, high-resolution scanning transmission electron microscopy observations show that this film contains small-angle tilt grain boundaries, which is composed of the periodic array of dislocations with the Burgers vector .     

Influence of water activity on belite (β-C2S) hydration

The hydration of the two most reactive phases of ordinary Portland cement (OPC), tricalcium silicate (C₃S), and tricalcium aluminate (C₃A) is successfully halted when the activity of water () falls below critical thresholds of 0.70 and 0.45, respectively. It has been established that the reduction in relative humidity (RH) and  suppresses the hydration of all anhydrous phases in OPC, including less explored phases like dicalcium silicate, that is, belite (β-C₂S). However, the degree of suppression, that is, the critical threshold, for β-C₂S, standalone has yet to be established. This study utilizes isothermal microcalorimetry and X-ray diffraction techniques to elucidate the influence of on the hydration of -C₂S suspensions via incremental replacements of water with isopropanol (IPA). Experimentally, this study shows that with increasing IPA replacements, hydration is increasingly suppressed until eventually brought to a halt at a critical threshold of approximately 27.7% IPA on a weight basis (wt.%_IPA). From thermodynamic estimations, the exact critical threshold and solubility product constant of -C₂S () are established as 0.913 and 10^−12.68, respectively. This study enables enhanced understanding of β-C₂S reactivity and provides thermodynamic parameters during the hydration of β-C₂S-containing cementitious systems such as OPC-based and calcium aluminate-based systems.     

The effect of the third invariant on the strength and failure of boron carbide and silicon carbide

This article presents new test data to assess the effect the third invariant has on the strength and failure of two ceramic materials: boron carbide and silicon carbide. Two experimental techniques are used: the Brazilian test that produces a biaxial state of stress, and a new technique that uses a high-pressure confinement vessel to load a specially designed dumbbell specimen in triaxial extension. The dumbbell geometry provides two important advantages over the typically used cylindrical specimen: no adhesive is required to bond the specimen to the load cell because the dumbbell geometry naturally takes the specimen into tension, and any loading asymmetries are essentially eliminated due to the axisymmetric geometry. The results show that when the stress state is on the tensile meridian the equivalent stress at failure is constant, independent of the hydrostatic pressure. The average equivalent stress at failure is for boron carbide and for silicon carbide. The Brazilian test was only performed on boron carbide and failed at , much higher than when on the tensile meridian () indicating that the effect of the third invariant is significant (because of the difference in the failure strength) and must be accounted for to accurately predict when failure will occur.     

Role of oxygen-vacancy in piezoelectric properties and fatigue behavior of (Bi0.5Na0.5)0.93Ba0.07Ti1+xO3 ceramics

In this reported study, (Bi_0.5Na_0.5)_0.93Ba_0.07Ti_1+xO₃ (abbreviated as BNBT_1+x) ceramics, containing Ti-nonstoichiometry that ranged from a 2% deficiency to a 1% excess, were designed and systematically characterized. The results of the X-ray diffraction Rietveld refinement and X-ray photoelectron spectroscopy analysis of these materials revealed that the amount of Ti in the BNBT_1+x ceramics significantly affected the degree of coexistent rhombohedral/tetragonal phases and also affected the content of singly/doubly charged oxygen-vacancy (/) in the ceramics. After poling and 10⁵ fatigue cycles, the variation in Raman resonance line-width of the Ti–O bond in the BNBT_1+x ceramics was found to be strongly dependent on the amount of Ti in the ceramic. The → transformation and clustering of the defects under electrical loading were considered to be a critical factor in electric field-induced structural transition and fatigue properties of the material.     

Mechanical characterization of boron carbide single crystals

Out-of-plane anisotropy in the mechanical response of boron carbide was studied by performing nanoindentation experiments on four specific crystallographic orientations of single crystals, that is, , , , and . For each orientation of the single crystals, in-plane variations of indentation modulus and hardness were also studied by monitoring the relative rotation between the crystal surface and a Berkovich indenter tip. A significant out-of-plane anisotropy in indentation modulus was observed with ~80 GPa difference between the highest and lowest values. A smaller but measurable out-of-plane anisotropy in indentation hardness was also observed. In-plane anisotropy, on the other hand, was found to be significantly influenced by the scatter in the data and geometrical imperfections of the indenter tip. Investigations of indentation pop-in events suggested that deformation is entirely elastic prior to the first pop-in. Furthermore, quasi-plastic flow along the orientation of the single crystals was found to be more homogeneous than the other tested orientations. For select indents, cross-sectional transmission electron microscopy (TEM) of the indented regions showed formation of a quasi-plastic zone in the form of lattice rotation and various microstructural defects. The quasi-plastic zone grew in size with increasing the indentation depth. The TEM observations also suggested the crystal slip to be a potential mechanism of quasi-plasticity and a precursor for formation of amorphous bands that could eventually lead to cracking and fragmentation. The proposed failure mechanism provides valuable insights for calibrating constitutive computational models of failure in boron carbide.     

Sintering-driven effects on the band gap of (Pb,La)(Ti,Ni)O3 photovoltaic ceramics

In this work, the influence of the sintering temperature on the physical properties of (Pb_0.8La_0.2)(Ti_0.9Ni_0.1)O₃ (PLT-Ni) ceramics is reported. The experimental data revealed that the energy band gap of PLT-Ni ceramics could be tailored from approximately 2.7 to 2.0 eV by changing the sintering temperature from 1100°C to 1250°C. It is demonstrated that the simple substitution of Ti⁴⁺ by Ni²⁺ cations is effective to decrease the intrinsic band gap while increasing the tetragonality factor and the spontaneous polarization. However, the additional red-shift observed in the absorption edge of the PLT-Ni with increasing the sintering temperature was associated with a continuous increase in the oxygen vacancies () amount. It is believed that the impact of the creation of these thermally induced is manifold. The presence of and Ni²⁺ ions generate the Ni²⁺- defect-pairs that promoted both a decrease in the intrinsic band gap and an additional increase of the tetragonality factor, consequently, increasing the spontaneous polarization. The creation of Ni²⁺- defects also changed the local symmetry of Ni²⁺ ions from octahedral to a square pyramid, thus lifting the degeneracy of the Ni²⁺ 3d orbitals. With the increase in the sintering temperature, lower-energy absorbing intraband states were also formed due to an excess of , being responsible for an add-on shoulder in the absorption edge, extending the light absorption curve to longer wavelengths and leading to an additional absorption in “all investigated” spectrum as well.     

Effect of pressurization on the fracture toughness of borosilicate glasses

In this study, hot-compression is applied to two multicomponent borosilicate glasses, Borofloat33 (Boro33) and N-BK7, using molecular dynamics simulations. The effects of pressure on elastic properties, surface energy, and fracture toughness ( are investigated. It is found that the impact on is mainly dominated by the change of Young's modulus under pressure, which is proportional to the relative change in density. Between the two glasses under investigation, can be improved more effectively by the hot-compression process for Boro33, due to its higher concentration of 3-coordinated boron (B³), which facilitates densification via B³ to B⁴ conversion under compression.     

Development of magnetically switchable high permittivity microwave dielectrics using La(Al1-xFex)O3

The introduction of transition metal doping, particularly Fe³⁺, into high-performance microwave dielectrics can make “smart” materials that switch between a high-Q, low loss state and a low-Q, high loss state using a small external magnetic field. In this study, the dielectric and magnetic properties of the high permittivity host material LaAlO₃ (ε_r = 22.5), when doped with Fe³⁺, are reported. Spin losses dominate the loss tangent at cryogenic temperatures and survive up to room temperature. Peaks in the loss tangent versus temperature relation are observed near 40, 75, and 215 K. Additional measurements of samples exposed to annealing in varying environments, combined with Debye analysis and the results of native defect energy predictions from density functional calculations[Phys Rev B. 2009;80:104115], allows us to associate the 40, 75, and 215 K peaks to the following reactions, , , and , respectively.     

Physical,chemical, and biological investigations of composites for biomedical applications

In this article, the interplay between structural, electrical, and surface properties in determining the collective behavior of (hydroxyapatite, HAP) and (strontium titanate, ST) composites was reported. The monoliths HAP and ST were synthesized using sol-gel and solid-state reaction, respectively, and were mixed in different atomic concentrations (20, 40, 60, and 80 at.%) to prepare a series of composites. The prepared composites were then subjected to x-ray diffraction (XRD) and Raman analysis for probing the microstructural aspects. The analysis revealed no evidence of a phase that the reaction between the two monoliths might form. The crystallite sizes were in the range of 27.2–37.3 nm, and it increased with the content of ST in the composites. The Raman analysis revealed the presence of rutile that was later found to be the link in the display of bone-like apatite nucleation ability in the monolith ST and its composites. The FESEM analysis revealed that the grain sizes were 64–144 nm between the monoliths and were found to follow a similar trend to the crystallite size. The dielectric constant varied with temperature ranging from 5 to 35 (1 MHz) at 310 K for all the specimens. The dependence of on the grain size of the composites followed a nearly exponential relation. The bone-like apatite forming ability of the composites was studied by incubating the specimens in simulated body fluid (SBF). Additionally, the cytocompatibility (MG63 cell lines) and protein adsorption (bovine serum albumin [BSA]) of the selected specimens were also studied to comprehensively understand the delicate relationship between the electrical and biological properties. The protein adsorption was primarily related to the surface charge, and its dependence was found to be linear. Additionally, the of the composites was ≤35, which compliments the protein adsorption behavior of the specimens. The amount of adsorbed protein for all the specimens considered in this study was in the range of 3–32 μ g/ml. Furthermore, the specimens exhibited excellent cell viability of more than 90%. Based on the physical and biological investigations, 20H-80S was established as the best specimen that blends the characteristic feature of both the monoliths. Finally, the TEM and STEM mapping of the best specimen, projecting the suitability of 20H-80S in the design of electrically active scaffolds and possibly bioelectrets for biomedical applications, was also studied.     

Ni-YSZ(001) solid-solid interfacial energy and orientation relationships

Equilibrated Ni particles were produced via solid-state dewetting of continuous Ni films deposited on the (001) surface of yttrium stabilized zirconia (YSZ). The solid-solid interface energy of the equilibrated Ni(111)-YSZ(001) interface was determined using Winterbottom analysis. Two low-index orientation relationships (ORs) were found using the selected area electron diffraction patterns in transmission electron microscopy: (OR₁) and (OR₂). However, many particles were found to deviate from these low-index ORs while maintaining the out-of-plane orientation, . The interface energy was measured to be 2.5 ± 0.1 J/m² regardless of the in-plane orientation. The orientation distribution was determined using electron backscattered diffraction for Ni particles on both (111) and (001) YSZ substrates and was found to correlate well with the interface energies measured in a previous study for the Ni-YSZ(111) interface and in the present study for the Ni-YSZ(001) interface.     

Frequency dispersion model of the complex permeability of soft ferrites in the microwave frequency range

The complex permeability of Cu-doped nickel-zinc polycrystalline ferrites is strongly dependent on microstructure, particularly, on relative density () and average grain size (). In this study, a mathematical model, able to fit the measured magnetic permeability spectra from 10⁶ to 10⁹ Hz, is proposed and validated for a width range of average grain sizes (3.40–23.15 μm) and relative densities (0.83–0.96). To the authors’ knowledge, domain-wall motion and spin rotation contributions to magnetic permeability have been integrated jointly with the microstructure for the first time in the proposed model, highlighting the relative influence of each magnetizing mechanism and microstructure on the magnetic permeability at different angular frequencies.     

Crystal structure,phonon modes,and bond characteristics of AgPb2B2V3O12 (B = Mg,Zn) microwave ceramics

AgPb₂B₂V₃O₁₂ (B = Mg, Zn) ceramics with low sintering temperature were synthesized via the conventional solid-state reaction route. Rietveld refinements of the X-ray diffraction patterns confirm cubic symmetry with space group . The number of observed vibrational modes and those predicted by group theoretical calculations also confirm the space group. At the optimum sintering temperature of 750°C/4 hours, AgPb₂Mg₂V₃O₁₂ has a relative permittivity of 23.3 ± 0.2, unloaded quality factor () of 26 900 ± 500 GHz (), and temperature coefficient of resonant frequency of 19.3 ± 1 ppm/°C, while AgPb₂Zn₂V₃O₁₂ has the corresponding values of 26.4 ± 0.2, 28 400 ± 500 GHz () and –18.4 ± 1 ppm/°C at 590°C/4 hours. Microwave dielectric properties of a few reported garnets and Pb₂AgB₂V₃O₁₂ (B = Mg, Zn) ceramics were correlated with their intrinsic characteristics such as the Raman shifts as well as width of A_1g Raman bands. Higher quality factor was obtained for lower full width at half-maxima (FWHMs) values of A_1g modes. The increase in B-site bond valence contributes to high and low |τ_f| with the substitution of Zn²⁺ by Mg²⁺. Furthermore, the high ionic polarizability and unit cell volume with Zn²⁺substitution contribute to increased relative permittivity.     

Combined electromechanical dynamic fracture behavior of lead zirconate titanate (PZT)

Coupon specimens of poled and depoled lead zirconate titanate (PZT) are examined under combined stress wave and electric loading conditions. Mode-I crack initiation and fracture behavior is examined using ultrahigh-speed imaging and two-dimensional digital image correlation. The dynamic critical stress intensity factor () is extracted using measured displacement fields ahead of the impulsively loaded crack tip, and compared between poled and depoled plates that were either under no electric field, positive 0.46 kV/mm electric field, or negative 0.46 kV/mm electric field. Poled specimens had a poling direction and applied electric field direction normal to the crack front. The addition of an electric field resulted in a crack-enhancing effect, where the dynamic fracture toughness of poled specimens under 0.46 kV/mm was almost half that of samples with no electric field. Depoled samples experienced almost no change in dynamic fracture toughness with the addition of an electric field.     

Structural drivers controlling sulfur solubility in alkali aluminoborosilicate glasses

If the direct feed approach to vitrify the Hanford's tank waste is implemented, the low activity waste (LAW) will comprise higher concentrations of alkali/alkaline-earth sulfates than expected under the previously proposed vitrification scheme. To ensure a minimal impact of higher sulfate concentrations on the downstream operations and overall cost of vitrification, advanced glass formulations with enhanced sulfate loadings (solubility) are needed. While, the current sulfate solubility predictive models have been successful in designing LAW glasses with sulfate loadings <2 wt.%, it will be difficult for them to design glass compositions with enhanced loadings due to our limited understanding of the fundamental science governing these processes. In this pursuit, this article unearths the underlying compositional and structural drivers controlling the sulfate solubility in model LAW glasses. It has been shown that the preferentially removes non-framework cations from the modifier sites in the silicate network, thus, leading to the polymerization in the glass network via the formation of ring-structured borosilicate units. Furthermore, though the sulfate solubility slightly decreases with increasing Li⁺/Na⁺ in the glasses, the prefers to be charge compensated by Na⁺, as it is easier for to break Na–O bonds instead of Li–O bonds.     

Asymptotic analysis of radial vibration of thin piezoelectric disks

The one-dimensional radial vibration model of piezoelectric disks has been widely used to determine the relevant material coefficients from admittance measurements. However, the one-dimensional model assumes infinitely thin disks, and therefore cannot predict their axial displacements. We extend the one-dimensional model by performing an asymptotic analysis of the axisymmetric radial vibration of thin disks. The asymptotic expansions include the asymptotic axial displacement and the second-order corrections to the admittance and the radial displacement in the one-dimensional model. We verify the asymptotic expansions and the one-dimensional model with the Chebyshev tau method. In the one-dimensional model, the frequencies of the maximum admittance in the first and second radial modes are accurate to 1% for Pz27 disks with thickness-to-diameter ratios of 0.15 and 0.065, respectively. For a general piezoelectric disk in the forced vibration, the error of in the one-dimensional model can be estimated from the second-order correction of the asymptotic resonance frequency in the free vibration.