Strong Local Polarization Fluctuations Enabled High Electrostatic Energy Storage in Pb-Free Relaxors.

Electrostatic energy-storage ceramic capacitors are essential components of modern electrified power systems. However, improving their energy-storage density while maintaining high efficiency to facilitate cutting-edge miniaturized and integrated applications remains an ongoing challenge. Herein, we report a record-high energy-storage density of 20.3 J cm-3 together with a high efficiency of 89.3% achieved by constructing a relaxor ferroelectric state with strongly enhanced local polarization fluctuations. This is realized by incorporating highly polarizable, heterovalent, and large-sized Zn and Nb ions into a Bi0.5Na0.5TiO3-BaTiO3 ferroelectric matrix with very strong tetragonal distortion. Element-specific local structure analysis revealed that the foreign ions strengthen the magnitude of the unit-cell polarization vectors while simultaneously reducing their orientation anisotropy and forming strong fluctuations in both magnitude and orientation within 1-3 nm polar clusters. This leads to a particularly high polarization variation (ΔP) of 72 µC cm-2, low hysteresis, and a high effective polarization coefficient at a high breakdown strength of 80 kV mm-1. This work has surpassed the current energy density limit of 20 J cm-3 in bulk Pb-free ceramics and has demonstrated that controlling the local structure via the chemical composition design can open up new possibilities for exploring relaxors with high energy-storage performance.

Chemical Framework to Design Linear-like Relaxors toward Capacitive Energy Storage.

ABO3-type perovskite relaxor ferroelectrics (RFEs) have emerged as the preferred option for dielectric capacitive energy storage. However, the compositional design of RFEs with high energy density and efficiency poses significant challenges owing to the vast compositional space and the absence of general rules. Here, we present an atomic-level chemical framework that captures inherent characteristics in terms of radius and ferroelectric activity of ions. By categorizing A/B-site ions as host framework, rattling, ferroelectrically active, and blocking ions and assembling these four types of ions with specific criteria, linear-like relaxors with weak locally correlated and highly extendable unit-cell polarization vectors can be constructed. As example, we demonstrate two new compositions of Bi0.5K0.5TiO3-based and BaTiO3-based relaxors, showing extremely high recoverable energy densities of 17.3 and 12.1 J cm-3, respectively, both with a high efficiency of about 90%. Further, the role of different types of ions in forming heterogeneous polar structures is identified through element-specific local structure analysis using neutron total scattering combined with reverse Monte Carlo modeling. Our work not only opens up new avenues toward rational compositional design of high energy storage performance lead-free RFEs but also sheds light on atomic-level manipulation of functional properties in compositionally complex ferroelectrics.

Thermally Induced Oxygen Vacancies and High Oxide Ion Conduction in K2ZnV2O7 with a Melilite-Related Structure.

Donor-doped melilite materials with interstitial oxygen defects in the structure are good oxide ion conductors with negligible electronic conduction and show great potential in the ceramic electrolyte of intermediate-temperature solid oxide fuel cells (IT-SOFC). However, the parent melilite-structured materials with stoichiometric oxygen are usually insulators. Herein, we reported high and pure oxide ion conduction in the parent K2ZnV2O7 material with a melilite-related structure, e.g., ∼1.14 × 10-3 S/cm at 600 °C, which is comparable to that of the state-of-the-art yttrial-stabilized ZrO2 applied in practical fuel cells. Neutron diffraction data revealed the interesting thermally induced formation of oxygen vacancies at elevated temperatures, which triggered the transformation of the material from electronically conducting to purely and highly oxide ion-conducting. The VO4 tetrahedron with non-bridging terminal oxygen in K2ZnV2O7 was proved to be the key structural factor for transporting oxygen vacancies. The molecular dynamic simulation based on the interatomic potential approach revealed that long-range oxide ion diffusion was achieved by breaking and re-forming the 5-fold MO4 (M = Zn and V) tetrahedral rings. These findings enriched our knowledge of melilite and melilite-related materials, and creating oxygen vacancies in a melilite-related material may be a new strategy for developing novel oxide ion conductors.

Tunable Microwave Dielectric Properties in Rare-Earth Niobates via a High-Entropy Configuration Strategy To Induce Ferroelastic Phase Transition.

In this study, (La0.2Nd0.2Sm0.2Ho0.2Y0.2)(Nb1-xVx)O4 (0.1 ≤ x ≤ 0.4) ceramics were prepared using a high-entropy strategy via the solid-phase method. The crystal structure, microstructure, vibration modes, and phase transition were studied by X-ray diffraction, scanning electron microscopy/transmission electron microscopy (SEM/TEM), and Raman spectroscopy techniques. The phase of ceramics was confirmed to be a monoclinic fergusonite in the range of x ≤ 0.28, a tetragonal scheelite was in the range of 0.3 ≤ x ≤ 0.32, a complex phase of tetragonal scheelite, and zircon was observed in the ceramics when x ≥ 0.35. A zircon phase was also detected by TEM at x = 0.4. The ceramic at x = 0.25 exhibited outstanding temperature stabilization with εr = 18.06, Q × f = 56,300 GHz, and τf = -1.52 ppm/°C, while the x = 0.2 ceramic exhibited a low dielectric loss with εr = 18.14, Q × f = 65,200 GHz, and τf = -7.96 ppm/°C. Moreover, the permittivity, quality factor, and the temperature coefficient of resonance frequency were related to the polarizability, packing fraction, density, and the temperature coefficient of permittivity caused by phase transition. This is an effective method to regulate near-zero τf by the synergism of the high-entropy strategy and substituting Nb with V in LnNbO4 ceramics.

Suppression of Secondary Electron Emission from Nickel Surface by Graphene Composites Based on First-Principles Method.

Secondary electron emission (SEE) is a fundamental phenomenon of particle/surface interaction, and the multipactor effect induced by SEE can result in disastrous impacts on the performance of microwave devices. To suppress the SEE-induced multipactor, an Ni (111) surface covered with a monolayer of graphene was proposed and studied theoretically via the density functional theory (DFT) method. The calculation results indicated that redistribution of the electron density at the graphene/Ni (111) interface led to variations in the work function and the probability of SEE. To validate the theoretical results, experiments were performed to analyze secondary electron yield (SEY). The measurements showed a significant decrease in the SEY on an Ni (111) surface covered with a monolayer of graphene, accompanied by a decrease in the work function, which is consistent with the statistical evidence of a strong correlation between the work function and SEY of metals. A discussion was given on explaining the experimental phenomenon using theoretical calculation results, where the empty orbitals lead to an electron trapping effect, thereby reducing SEY.

Defect Dipole Behaviors on the Strain Performances of Bismuth Sodium Titanate-Based Lead-Free Piezoceramics.

Bismuth sodium titanate (BNT)-based, lead-free piezoelectric materials have been extensively studied due to their excellent strain characteristics and environmental friendliness. In BNTs, the large strain (S) usually requires a relatively large electric field (E) excitation, resulting in a low inverse piezoelectric coefficient d33* (S/E). Moreover, the hysteresis and fatigue of strain in these materials have also been bottlenecks impeding the applications. The current common regulation method is chemical modification, which mainly focuses on forming a solid solution near the morphotropic phase boundary (MPB) by adjusting the phase transition temperature of the materials, such as BNT-BaTiO3, BNT-Bi0.5K0.5TiO3, etc., to obtain a large strain. Additionally, the strain regulation based on the defects introduced by the acceptor, donor, or equivalent dopant or the nonstoichiometry has proven effective, but its underlying mechanism is still ambiguous. In this paper, we review the generation of strain and then discuss it from the domain, volume, and boundary effect perspectives to understand the defect dipole behavior. The asymmetric effect caused by the coupling between defect dipole polarization and ferroelectric spontaneous polarization is expounded. Moreover, the defect effect on the conductive and fatigue properties of BNT-based solid solutions is described, which will affect the strain characteristics. The optimization approach is appropriately evaluated while there are still challenges in the full understanding of the defect dipoles and their strain output, in which further efforts are needed to achieve new breakthroughs in atomic-level insight.

Full-Scale Fatigue Test and Finite Element Analysis on External Inclined Strut Welded Joints of a Wide-Flanged Composite Box Girder Bridge.

For a wide-flanged composite box girder bridge, the risk of fatigue cracking in the external inclined strut welded joint under the fatigue vehicle load is a problem. The main purposes of this research are to verify the safety of the main bridge of the Linyi Yellow River Bridge, a continuous composite box girder bridge, and to propose suggestions for optimization. In this research, a finite element model of one segment of the bridge was established to investigate the influence surface of the external inclined strut, and, using the nominal stress method, it was confirmed that the fatigue cracking of the welded details of the external inclined strut was risky. Subsequently, a full-scale fatigue test of the external inclined strut welded joint was carried out, and the crack propagation law and S-N curve of the welded details were obtained. Finally, a parametric analysis was conducted with the three-dimensional refined finite element models. The results showed that the welded joint in the real bridge has a fatigue life larger than that of the design life, and methods such as increasing the flange thickness of the external inclined strut and the diameter of the welding hole are beneficial to improve its fatigue performance.

Accumulated Lattice Strain as an Intrinsic Trigger for the First-Cycle Voltage Decay in Li-Rich 3d Layered Oxides.

Li- and Mn-rich layered oxides (LMLOs) are promising cathode materials for Li-ion batteries (LIBs) owing to their high discharge capacity of above 250 mA h g-1. A high voltage plateau related to the oxidation of lattice oxygen appears upon the first charge, but it cannot be recovered during discharge, resulting in the so-called voltage decay. Disappearance of the honeycomb superstructure of the layered structure at a slow C-rate (e.g., 0.1 C) has been proposed to cause the first-cycle voltage decay. By comparing the structural evolution of Li[Li0.2Ni0.2Mn0.6]O2 (LLNMO) at various current densities, the operando synchrotron-based X-ray diffraction results show that the lattice strain in bulk LLNMO is continuously increased over cycling, resulting in the first-cycle voltage loss upon Li-ion insertion. Unlike the LLNMO, the accumulated average lattice strain of LiNi0.8Co0.1Mn0.1O2 (NCM811) and LiNi0.6Co0.2Mn0.2O2 (NCM622) from the open-circuit voltage to 4.8 V could be released on discharge. These findings help to gain a deep understanding of the voltage decay in LMLOs.

B-Site Nanoscale-Ordered Structure Enables Ultra-High Tunable Performance.

Tunable devices constructed by ferroelectric thin films are often desired to possess a low dielectric loss while maintainging a high dielectric tunability over a broad operating temperature range in applications, for example, resonators, filters, or phase shifters. However, it is difficult to simultaneously achieve these characteristics by traditional strategies, such as doping and strain modifying. Here, we demonstrate that the dielectric tunability of the sol-gel-prepared Pb(Sc1/2Nb1/2)0.9(Mg1/3Nb2/3)0.1O3 (PSNMN) thin film can be almost doubled from ~47% to ~80.0% (at 10 kHz) at a low electric field (~530 kV/cm), and the dielectric loss can be sharply reduced by more than an order of magnitude, from ~0.50 to ~0.037 (at 1 kHz) when the thin film was annealed in air at 650°C for 15 h under the help of an atmosphere-compensating-block (ACB) made from the proto-PSNMN gel. Moreover, the PSNMN thin film annealed with ACB also exhibited an extremely high thermally-stable dielectric tunability in an ultrabroad temperature range (>130 K), which could be attributed to the Maxwell-Wagner (MW) effect generated by the interface between the PSNMN disordered matrix and the B-site nanoscale-ordered structure formed during the long-term annealing process. The reduced dielectric loss is mainly benefited from the reduced concentration of oxygen vacancy and the possible MW effects, and the enhanced dielectric tunability could be ascribed to the weaker domain-pinning effect by oxygen vacancy. The breakthrough provides a new universal strategy to achieve utrahigh tunable performance in A(B'1/2B"1/2)O3 ferroelectric thin films with a B-site nanoscale-ordered structure, meanwhile it paves the way for ultraintergrated tunable thin-film-devices with great phase shifter performance in practical applications.

Experimental Study on Seismic Performance of Precast Columns Repaired with CFRP Fabrics.

Earthquakes worldwide highlight the seismic vulnerability of reinforced concrete (RC) bridge columns. RC bridges are likely to collapse or lose service function due to damage to the bridge columns from strong earthquakes. Rapid repair of RC bridge columns is of great significance for maintaining traffic lines for emergency rescue work after earthquakes. In this study, an improved rapid repair method was developed to restore the bearing capacity of a damaged precast column after earthquake damage. A cyclic loading test was performed to simulate the seismic loading. The original column and the repaired column were both tested. The test results showed that the bearing capacity of the repaired columns was increased by 8%, and the energy dissipation capacity was 53% higher than that of the original column. The ductility decreased because the test for the repaired specimen ended in advance. The initial stiffness of the repaired columns was reduced, but the stiffness was significantly developed in the later loading stage. The rapid repair method proposed in this study exhibited an excellent effect on restoring the seismic resistance of the damaged columns.

Experimental and Numerical Evaluation on the Performance of Perfobond Leiste Shear Connectors in Steel-SFRCC Composite Beams.

The difference between the shear performances of Perfobond Leiste (PBL) shear connectors embedded in steel fiber-reinforced cementitious composite (SFRCC) structure and normal strength concrete (NC) structure was investigated by push-out tests and finite element (FE) simulations. Push-out tests were carried out on nine steel-SFRCC specimens and nine steel-NC specimens. The mechanical behavior of the PBL shear connector was examined according to the failure modes, load-slip curves, and strain distribution laws of the push-out specimens. Experimental results revealed that the extension of cracks in SFRCC was hindered by steel fibers, and the number and width of cracks in SFRCC were smaller than those in NC. The failure mode of the steel-SFRCC specimens and the single-hole steel-NC specimens was the shear failure of the penetrating reinforcement, whereas that of the multi-hole NC specimens was concrete slab cracking. The ultimate shear bearing capacity of PBL shear connectors in the steel-SFRCC specimens was 47.8% greater than that in the steel-NC specimens. Furthermore, an FE model verified by the test results was established to conduct parametric analyses. It was found that the hole diameter and thickness of the steel plate and the yield strength of the penetrating rebar greatly affected the shear bearing capacity of PBL shear connectors. Finally, based on the experimental and FE simulation results, an expression for calculating the ultimate shear bearing capacity of PBL shear connectors in the steel-SFRCC composite structure was developed by considering the bearing effects of concrete dowels, penetrating rebars, and end parts.

Experimental and Numerical Analyses of Stud Shear Connectors in Steel-SFRCC Composite Beams.

To investigate the shear performance and failure mechanism of stud shear connectors in steel fiber-reinforced cementitious composite (SFRCC) beams, six steel-SFRCC and six steel-normal strength concrete (NC) push-out specimens with two heights (80 mm, 120 mm) and three diameters (14 mm, 18 mm, 22 mm) of stud connectors were prepared. The experimental results revealed that the stud shearing failure was the main failure mode of all push-out specimens. In comparison to the steel-NC specimens, the development of cracks in the SFRCC beams was efficiently restrained due to the existence of high-strength steel fibers added to the normal concrete. The shear resistance and stiffness of studs in the steel-SFRCC beams were, respectively, 22.3% and 15.1% greater than those in the steel-NC specimens; however, their ductility was reduced, and the stud shear connectors failed in advance. The finite element (FE) model was developed and verified by push-out test results. FE analysis results indicated that the shear resistance of stud shear connectors was significantly improved with the increase in the concrete compressive strength, the stud diameter and tensile strength, whereas the aspect ratio of studs had a small impact on the ultimate resistance of stud shear connectors. Based on the as-obtained push-out experiment and FE analysis results, empirical formulas were presented to predict the load-slip curves and ultimate shear resistance of stud shear connectors in the steel-SFRCC specimens, and higher accuracy and a wider application range were obtained than with previous formulas.

Ferroelectricity and Schottky Heterojunction Engineering in AgNbO3: A Simultaneous Way of Boosting Piezo-photocatalytic Activity.

As an efficient and economical way of dealing with organic pollutants, piezo-photocatalysis has attracted great interest. In this work, we demonstrated that ferroelectricity and Schottky heterojunction engineering could significantly enhance the piezo-photocatalytic activity of AgNbO3. The poled 20 mol % K+ doped AgNbO3 disclosed its superior piezo-photocatalytic activity of 0.131 min-1 for 10 mg·L-1 RhB, which is 7.8 times of the pristine one under the condition of illumination only. The designed piezo-photocatalyst also exhibited good piezo-photocatalytic stability after four cycles. These merits are attributed to the built-in electric field associated with the large spontaneous polarization and low coercive field originated from the stable ferroelectric state after ferroelectricity engineering, plus with the electron trapper effect of the in situ precipitated metal Ag particles. Our work not only provides a promising piezo-photocatalyst for degrading organic contaminants but also paves a good way for developing high piezo-photocatalytic activity catalysts.

Hierarchical Nanostructured Electrospun Membrane with Periosteum-Mimic Microenvironment for Enhanced Bone Regeneration.

An ideal periosteum substitute should be able to mimic the periosteum microenvironment that continuously provides growth factors, recruits osteoblasts, and subsequent extracellular matrix (ECM) mineralization to accelerate bone regeneration. Here, a calcium-binding peptide-loaded poly(ε-caprolactone) (PCL) electrospun membrane modified by the shish-kebab structure that can mimic the periosteum microenvironment was developed as a bionic periosteum. The calcium-binding peptide formed by the negatively charged heptaglutamate domain (E7) in the E7-BMP-2 with calcium ion in the tricalcium phosphate sol (TCP sol) through electrostatic chelation not only extended the release cycle of E7-BMP-2 but also promoted the biomineralization of the bionic periosteum. Cell experiments showed that the bionic periosteum could significantly improve the osteogenic differentiation of the rat-bone marrow-derived mesenchymal stem cells (rBMSCs) through both chemical composition and physical structure. The in vivo evaluation of the bionic periosteum confirmed the inherent osteogenesis of this periosteum microenvironment, which could promote the regeneration of vascularized bone tissue. Therefore, the hierarchical nanostructured electrospun membrane with periosteum-mimic microenvironment is a promising periosteum substitute for the treatment of bone defects.

Dielectric Relaxation and Magnetic Structure of A-Site-Ordered Perovskite Oxide Semiconductor CaCu3Fe2Ta2O12.

A new perovskite oxide semiconductor, CaCu3Fe2Ta2O12, was synthesized through a high-pressure and high-temperature approach. The compound possesses an Im3̅ space group, where it crystallizes to an A-site-ordered but B-site partial ordered quadruple perovskite structure. Spin ordering occurs around 150 K owing to the antiferromagnetic coupling between Fe3+ spins and ferromagnetic coupling between Cu2+ spins. The room-temperature dielectric permittivity of CaCu3Fe2Ta2O12 was measured to be approximately 2500 at 1 kHz. More importantly, isothermal frequency-dielectric spectroscopy demonstrates the existence of two dielectric relaxations. Debye-like relaxation is attributed to charge carriers trapped among the oxygen vacancies at low temperatures and Maxwell-Wagner polarization relaxation at high temperatures. CaCu3Fe2Ta2O12 is a new magnetic semiconductor, where A-site ordering is intercorrelated with second-order Jahn-Teller distortion. These findings offer opportunities to design novel perovskite oxides with attractive magnetic and dielectric properties.

ß-Tricalcium phosphate contained beaded-fiber scaffolds characterized by high early osteoinductive activity for vascularized bone regeneration.

The calcium phosphate component and surface topology of a scaffold are considered the two main factors that influence osteogenic differentiation. This research reports a one-step but effective scaffold preparation method that can regulate the morphology of nanofibers and control the distribution and release behavior of calcium phosphate nanoparticles (CaPs). Two beaded-on-string CaPs-loaded electrospun scaffolds (PT7.5 and PT4.5) with composite microstructures of microbeads and nanofibers were fabricated by adjusting the concentration of the electrospinning solution. The presence of the composite microstructure was conducive to the surface exposure and sustained release of bioactive components, which in turn could significantly promote the biomineralization and protein adsorption of the scaffold. A study of the human umbilical vein endothelial cells (HUVECs) and rat-bone marrow-derived mesenchymal stem cells (rBMSCs) revealed that cells cultured on scaffolds with composite microstructures (especially PT4.5) could enhance tube formation of the HUVECs and osteogenic differentiation of rBMSCs. The PT4.5 with significantly different microbead and nanofiber sizes presented the high potential to improve the early osteoinductive activity and angiogenesis of the CaPs-loaded electrospun scaffold and expand its advantage in bone regeneration.

Tribocatalytic degradation of dyes by tungsten bronze ferroelectric Ba2.5Sr2.5Nb8Ta2O30 submicron particles.

Searching for a new approach in environmental remediation in terms of dye degradation is important in industrialized society. In this work, ferroelectric Ba2.5Sr2.5Nb8Ta2O30 (BSNT) submicron powders prepared by the high-temperature solid-phase method are used for dye degradation under magnetic stirring. The dye in solution can be quickly degraded by magnetically stirring BSNT submicron particles in the dark in ambient temperature conditions. More importantly, the degradation efficiency can be greatly improved through simple modification of the stirring materials from glass to polypropylene, with a degradation efficiency of rhodamine B as high as 99% in 1.5 h at a gentle stirring speed of 300 rpm. Control experiments reveal that the degradation of the dye is mainly contributed by the friction between BSNT submicron particles and PTFE stirring rods. It is proposed that the friction between ferroelectric polar BSNT particles and PTFE causes charge transfer and induces a non-zero internal electric field to drive the separation of electron-hole pairs in BSNT particles, resulting in a novel tribocatalytic degradation of the dye, which is proven by the detection of ˙OH and ˙O2 - intermediate products during stirring. This work demonstrates that the friction energy of ferroelectric materials with strong polarization is an alternative approach for highly efficient dye degradation.

A hybrid vascular graft harnessing the superior mechanical properties of synthetic fibers and the biological performance of collagen filaments.

Tissue-engineered small caliber vascular grafts have attracted much research attention as a viable alternative to traditional vascular grafts with their biocompatibility and potential to achieve complete healing. However, the major challenge is to fabricate a scaffold with both satisfactory mechanical properties and fast endothelialization. In this study, a hybrid tubular vascular tissue engineered scaffold has been circular-knitted using novel electrochemically aligned collagen (ELAC) filaments plied together with traditional poly(lactic acid) (PLA) yarn. The collagen component was able to promote the recruitment and proliferation of endothelial cells by increasing the initial cell adhesion 10-fold and the eventual cell population 3.2 times higher than the PLA scaffold alone. At the same time, the PLA yarn was able to provide sufficient mechanical strength and structural stability, as well as facilitate scaffold fabrication on high speed textile production equipment. The tubular hybrid scaffold exhibited excellent bursting strength (1.89 ± 0.43 MPa) and suture retention strength (10.86 ± 0.49 N), and had comparable compliance (3.98 ± 1.94%/100 mmHg) to that of the coronary artery (3.8 ± 0.3%/100 mmHg) under normotensive pressure. With its excellent mechanical and biological performance, this prototype hybrid scaffold is a promising candidate for the construction of a clinically successful and easily translatable tissue-engineered small caliber vascular graft.

Structural Distortion and Dielectric Permittivities of KCoO2-Type Layered Nitrides Ca1-xSrxTiN2.

Among the KCoO2-type phases, the orthorhombic layered nitride CaTiN2 is a newly reported high dielectric permittivity material (εr ∼ 1300-2500 within 104-106 Hz from 80 to 450 K) while the tetragonal SrTiN2 is reported to display an unintentional metallic conduction property. In this work, a Ca1-xSrxTiN2 solid solution was synthesized, in which the insulating SrTiN2 end member and some Sr-doped CaTiN2 samples were successfully obtained, and therefore, the dielectric properties of the Ca1-xSrxTiN2 solid solution were investigated. The Sr substitution for Ca drove an orthorhombic-to-tetragonal phase transformation in Ca1-xSrxTiN2, which reduced the dielectric permittivity significantly. The tetragonal SrTiN2 displays a much lower dielectric permittivity (εr ∼ 20-70 in 105-106 Hz and 10-300 K) than that of CaTiN2. The comparison on the dielectric permittivities and structures of CaTiN2 and SrTiN2 indicates that the structural distortion arising from the splitting of N planes between Ti layers within the TiN2 pyramidal layers could be a plausible structural origin of the high bulk dielectric permittivity of CaTiN2.