Nonstoichiometric effect of A-site complex ions on structural,dielectric, ferroelectric,and electrostrain properties of bismuth sodium titanate ceramics

To investigate the nonstoichiometric effect of (Bi_0.5Na_0.5)TiO₃ (BNT) ceramics on their properties, we propose a novel chemical expression, (Bi_0.5+xNa_0.5−3x)TiO₃. The nonstoichiometric effect of BNT can be explored in compounds with this composition without being hampered by the charge imbalance problem. With x ranging from −0.02 to 0.02, we find that the morphological, dielectric, ferroelectric, and electrostrain properties differ considerably between Na-rich and Bi-rich ceramic samples. The average grain size (AGS) increased significantly in Na-rich samples compared to that in stoichiometric BNT, while it decreased slightly in Bi-rich samples. The dielectric characteristics measured from 30 °C to 500 °C indicate that conductivity is activated in Na-rich nonstoichiometric samples but is effectively suppressed in Bi-rich nonstoichiometric samples. The ferroelectric properties also show the same trend. In Na-rich samples, elliptical polarization against electric field (P-E) hysteresis loops were detected, indicating a conductive character induced by high electric field loading. However, saturated P-E loops are observed in Bi-rich samples with well-inhibited conductivity. Furthermore, compared to stoichiometric BNT and nonstoichiometric x = 0.02 Bi-rich samples, (Bi_0.5+xNa_0.5−3x)TiO₃ samples with x = 0.01 exhibit higher electrostrain from 30 °C to 150 °C. Based on the assumption of charge balance, our findings indicated that the presence of 1 mol% excess Bi would facilitate significant improvement in the dielectric, ferroelectric, and electrostrain properties of BNT and BNT-based systems.     

Toward High-Performance Dihydrophenazine-Based Conjugated Microporous Polymer Cathodes for Dual-Ion Batteries through Donor–Acceptor Structural Design

Recent studies have demonstrated that dihydrophenazine (Pz) with high redox-reversibility and high theoretical capacity is an attractive building block to construct p-type polymer cathodes for dual-ion batteries. However, most reported Pz-based polymer cathodes to date still suffer from low redox activity, slow kinetics, and short cycling life. Herein, a donor–acceptor (D–A) Pz-based conjugated microporous polymer (TzPz) cathode is constructed by integrating the electron-donating Pz unit and the electron-withdrawing 2,4,6-triphenyl-1,3,5-triazine (Tz) unit into a polymer chain. The D–A type structure enhances the polymer conjugation degree and decreases the band gap of TzPz, facilitating electron transportation along the polymer skeletons. Therefore the TzPz cathode for dual-ion battery shows a high reversible capacity of 192 mAh g⁻¹ at 0.2 A g⁻¹ with excellent rate performance (108 mAh g⁻¹ at 30 A g⁻¹), which is much higher than that of its counterpart polymer BzPz produced from 1,3,5-triphenylbenzene (Bz) and Pz (148 and 44 mAh g⁻¹ at 0.2 and 10 A g⁻¹, respectively). More importantly, the TzPz cathode also shows a long and stable cyclability of more than 10 000 cycles. These results demonstrate that the D–A structural design is an efficient strategy for developing high-performance polymer cathodes for dual-ion batteries.     

On the Catalytic Activity of Sn Monomers and Dimers at Graphene Edges and the Synchronized Edge Dependence of Diffusing Atoms in Sn Dimers

In this study, in situ transmission electron microscopy is performed to study the interaction between single (monomer) and paired (dimer) Sn atoms at graphene edges. The results reveal that a single Sn atom can catalyze both the growth and etching of graphene by the addition and removal of C atoms respectively. Additionally, the frequencies of the energetically favorable configurations of an Sn atom at a graphene edge, calculated using density functional theory calculations, are compared with experimental observations and are found to be in good agreement. The remarkable dynamic processes of binary atoms (dimers) are also investigated and is the first such study to the best of the knowledge. Dimer diffusion along the graphene edges depends on the graphene edge termination. Atom pairs (dimers) involving an armchair configuration tend to diffuse with a synchronized shuffling (step-wise shift) action, while dimer diffusion at zigzag edge terminations show a strong propensity to collapse the dimer with each atom diffusing in opposite directions (monomer formation). Moreover, the data reveals the role of C feedstock availability on the choice a single Sn atom makes in terms of graphene growth or etching. This study advances the understanding single atom catalytic activity at graphene edges.     

Enhanced mechanical properties of porous titanium implants via in-situ synthesized titanium carbide in lamellar pore walls

Directional lamellar porous titanium scaffolds are widely used as bone implant bearing materials because of their anisotropic pore structure. Their mechanical properties can be effectively improved by enhancing the strength of pore walls through the introduction of ceramics. In this work, porous titanium implants were prepared by freeze casting combined with TiH₂ decomposition. The graphene was introduced into the pore walls of porous titanium, which could transform into titanium carbide (TiC) in situ upon sintering. TiC was evenly distributed in the lamellar pore walls, and the interface was well bonded. The compression strength of the fabricated implants was up to 389.94 MPa when the graphene content was 3 wt%, which was 377.8% times as high as the porous titanium. The crack propagation was resisted by TiC because of the “pinning” effect on the pore wall. Some of TiC were pulled out from the matrix, and others were fractured. The strength of the fabricated implants was improved significantly by the large consumption of fracture energy. Also, fabricated porous titanium implants with TiC are suitable for bone implantation.     

Adenine-functionalized conjugated polymer as an efficient photocatalyst for hydrogen evolution from water

Conjugated polymers have emerged as a promising class of organic photocatalysts for photocatalytic hydrogen evolution from water splitting due to their adjustable chemical structures and electronic properties. However, developing highly efficient organic polymer photocatalysts with high photocatalytic activity for hydrogen evolution remains a significant challenge. Herein, we present an efficient approach to enhance the photocatalytic performance of linear conjugated polymers by modifying the surface chemistry via introducing a hydrophilic adenine group into the side chain. The adenine unit with five nitrogen atoms could enhance the interaction between the surface of polymer photocatalyst and water molecules through the formation of hydrogen bonding, which improves the hydrophilicity and dispersity of the resulting polymer photocatalyst in the photocatalytic reaction solution. In addition, the strong electron-donating ability of adenine group with plentiful nitrogen atoms could promote the separation of light-induced electrons and holes. As a result, the adenine-functionalized conjugated polymer PF6A-DBTO2 shows a high photocatalytic activity with a hydrogen evolution rate (HER) of 25.21 mmol g^?1 h^?1 under UV-Vis light irradiation, which is much higher than that of its counterpart polymer PF6-DBTO2 without the adenine group (6.53 mmol g^?1 h^?1). More importantly, PF6A-DBTO2 without addition of a Pt co-catalyst also exhibits an impressive HER of 21.93 mmol g^?1 h^?1 under visible light (λ > 420 nm). This work highlights that it is an efficient strategy to improve the photocatalytic activity of conjugated polymer photocatalysts by the modification of surface chemistry.     

基于纸浆纤维的贵重物品内包装塑造系统研究

为解决贵重物品与其内包装“契合度”不高的问题，提出基于纸浆纤维的贵重物品内包装塑造系统。系统通过三维扫描获取待包装物品的点云信息，经主控计算机进行数据处理，以下位机为执行中枢，辅之其他外部设备，利用纸浆纤维为贵重物品塑造“量身定制”的内包装，提升内包装契合度，增强保护效果，绿色环保，安全稳定。     

Good dielectric performance and broadband dielectric polarization in Ag,Nb co-doped TiO2

Due to the demand of miniaturization and integration for ceramic capacitors in electronic components market, TiO₂-based ceramics with colossal permittivity has become a research hotspot in recent years. In this work, we report that Ag⁺/Nb⁵⁺ co-doped (Ag_1/4Nb_3/4)_xTi_1−xO₂ (ANTOx) ceramics with colossal permittivity over a wide frequency and temperature range were successfully prepared by a traditional solid–state method. Notably, compositions of ANTO0.005 and ANTO0.01 respectively exhibit both low dielectric loss (0.040 and 0.050 at 1 kHz), high dielectric permittivity (9.2 × 10³ and 1.6 × 10⁴ at 1 kHz), and good thermal stability, which satisfy the requirements for the temperature range of application of X9R and X8R ceramic capacitors, respectively. The origin of the dielectric behavior was attributed to five dielectric relaxation phenomena, i.e., localized carriers' hopping, electron–pinned defect–dipoles, interfacial polarization, and oxygen vacancies ionization and diffusion, as suggested by dielectric temperature spectra and valence state analysis via XPS; wherein, electron-pinned defect–dipoles and internal barrier layer capacitance are believed to be the main causes for the giant dielectric permittivity in ANTOx ceramics.     

Fabrication of NixCo3-xS4 hollow nanosphere as wideband electromagnetic absorber at thin matched thickness

Nowadays, transition metal sulfide (TMS), especially for spinel crystal structure (A_xB_3-xS₄), have been proved to be a promising electromagnetic (EM) absorber if been used to deal with the severe electromagnetic pollution. However, EM performance degradation and absorption layer thickness-decreasing at present remains a big challenge, owning to the poor EM attenuation ability. To overcome this barrier, herein we reported a Ni_xCo_3-xS₄ (x = 0, 0.3, 0.6, 1.0) absorber with hollow sphere structure to realize a good EM performance with a thinner matched thickness (<1.5 mm). The average sizes of these Ni_xCo_3-xS₄ distributed in 450–550 nm. The dielectric loss ability (ε'') can be boosted by tuning the molar ratio of Ni/Co, which attributes to EM performance. Additionally, hollow structure would lead to the electromagnetic multi-reflection, also benefited to EM performance. The results demonstrated that the maximum qualified absorption bandwidth (f_E) of 3.8 GHz can be achieved for the Ni_0·3Co_2·7S₄ sample when specimen thickness only equals to 1.3 mm.     

Simulation of thermal barrier coating spallation induced by the initiation/growth/coalescence of internal crack and interfacial crack based on a real image model

In the furnace cycle test, the growth of oxide film leads to the propagation and coalescence of multiple cracks near the interface, which should be responsible for the spallation of thermal barrier coatings (TBCs). A TBC model with real interface morphology is created, and the near-interface large pore is retained. The purpose of this work is to clarify the mechanism of TBC spallation caused by successive initiation, propagation, and linkage of cracks near the interface during thermal cycle. The dynamic growth of thermally grown oxide (TGO) is carried out by applying a stress-free strain. The crack nucleation and arbitrary path propagation in YSZ and TGO are simulated by the extended finite element method (XFEM). The debonding along the YSZ/TGO/BC interface is evaluated using a surface-based cohesive behavior. The large-scale pore in YSZ near the interface can initiate a new crack. The ceramic crack can propagate to the YSZ/TGO interface, which will accelerate the interfacial damage and debonding. For the TGO/BC interface, the normal compressive stress and small shear stress at the valley hinder the further crack propagation. The growth of YSZ crack and the formation of through-TGO crack are the main causes of TBC delamination. The accelerated BC oxidation increases the lateral growth strain of TGO, which will promote crack propagation and coalescence. The optimization design proposed in this work can provide another option for developing TBC with high durability.