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.     

Comb-shaped sulfonated poly(aryl ether sulfone) proton exchange membrane for fuel cell applications

Structure design is the primary strategy to acquire suitable ionomers for preparing proton exchange membranes (PEMs) with excellent performance. A series of comb-shaped sulfonated fluorinated poly(aryl ether sulfone) (SPFAES) membranes are prepared from sulfonated fluorinated poly(aryl ether sulfone) polymer (SPFAE) and sulfonated poly(aryl ether sulfone) oligomer (SPAES-Oligomer). Chemical structures of the comb-shaped membranes are verified by ¹H nuclear magnetic resonance (NMR) and Fourier transform infrared (FT-IR) spectra. The comb-shaped SPFAES membranes display more continuous hydrophilic domains for ion transfer, because the abundant cations and flexible side-chains structure possess higher mobility and hydrophilicity, which show significantly improved proton conductivity, physicochemical stability, mechanical property compared to the linear SPFAE membranes. In a H₂/O₂ single-cell test, the SPFAES-1.77 membrane achieves a higher power density of 699.3 mW/cm² in comparison with Nafion® 112 (618.0 mW/cm²) at 80 °C and 100% relative humidity. This work offers a promising example for the synthesis of highly branched polymers with flexible comb-shaped side chains for high-performance PEMs.     

Synthesis and characterization of a long side-chain double-cation crosslinked anion-exchange membrane based on poly(styrene-b-(ethylene-co-butylene)-b-styrene)

By choosing a triple block polymer, poly(styrene-b-(ethylene-co-butylene)-b-styrene) (SEBS), as the backbone and adopting a long side-chain double-cation crosslinking strategy, a series of SEBS-based anion-exchange membranes (AEMs) was successively synthesized by chloromethylation, quaternization, crosslinking, solution casting, and alkalization. The 70C16-SEBS-TMHDA membrane showed high OH⁻ conductivity (72.13 mS/cm at 80 °C) and excellent alkali stability (only 10.86% degradation in OH⁻ conductivity after soaking in 4-M NaOH for 1700 h at 80 °C). Furthermore, the SR was only 9.3% at 80 °C and the peak power density of the H₂/O₂ single cell was up to 189 mW/cm² at a current density of 350 mA/cm² at 80 °C. By introducing long flexible side chains into a polymer SEBS backbone, the structure of the hydrophilic–hydrophobic microphase separation in the membrane was constructed to improve the ionic conductivity. Additionally, network crosslinked structure improved dimensional stability and mechanical properties.     

Surface treatment of titanium dioxide nanopowder using rotary electrode dielectric barrier discharge reactor

Titanium dioxide (TiO2) nanopowder (P-25;Degussa AG) was treated using dielectric barrier discharge (DBD) in a rotary electrode DBD (RE-DBD) reactor.Its electrical and optical characteristics were investigated during RE-DBD generation.The treated TiO2 nanopowder properties and structures were analyzed using x-ray diffraction (XRD) and Fourier-transform infrared spectroscopy (FTIR).After RE-DBD treatment,XRD measurements indicated that the anatase peak theta positions shifted from 25.3° to 25.1°,which can be attributed to the substitution of new functional groups in the TiO2 lattice.The FTIR results show that hydroxyl groups (OH) at 3400 cm-1 increased considerably.The mechanism used to modify the TiO2 nanopowder surface by air DBD treatment was confirmed from optical emission spectrum measurements.Reactive species,such as OH radical,ozone and atomic oxygen can play key roles in hydroxyl formation on the TiO2 nanopowder surface.     

Theoretical estimation of dielectric loss of oxide glasses using nonequilibrium molecular dynamics simulations

To theoretically explore amorphous materials with a sufficiently low dielectric loss, which are essential for next-generation communication devices, the applicability of a nonequilibrium molecular dynamics simulation employing an external alternating electric field was examined using alkaline silicate glass models. In this method, the dielectric loss is directly evaluated as the phase shift of the dipole moment from the applied electric field. This method enabled us to evaluate the dielectric loss in a wide frequency range from 1 GHz to 10 THz. It was observed that the dielectric loss reaches its maximum at a few THz. The simulation method was found to qualitatively reproduce the effects of alkaline content and alkaline type on the dielectric loss. Furthermore, it reasonably reproduced the effect of mixed alkalines on the dielectric loss, which was observed in our experiments on sodium and/or potassium silicate glasses. Alkaline mixing was thus found to reduce the dielectric loss.     

Colossal dielectric response and relaxation behavior in novel system of Zr4+ and Nb5+ co-substituted CaCu3Ti4O12 ceramics

In this work, we developed a novel system of isovalent Zr⁴⁺ and donor Nb⁵⁺ co-doped CaCu₃Ti₄O₁₂ (CCTO) ceramics to enhance dielectric response. The influences of Zr⁴⁺ and Nb⁵⁺ co-substituting on the colossal dielectric response and relaxation behavior of the CCTO ceramics fabricated by a conventional solid-phase synthesis method were investigated methodically. Co-doping of Zr⁴⁺ and Nb⁵⁺ ions leads to a significant reduction in grain size for the CCTO ceramics sintered at 1060 °C for 10 h. XRD and Raman results of the CaCu₃Ti_3.8-xZr_xNb_0.2O₁₂ (CCTZNO) ceramics show a cubic perovskite structure with space group Im-3. The first principle calculation result exhibits a better thermodynamic stability of the CCTO structure co-doped with Zr⁴⁺ and Nb⁵⁺ ions than that of single-doped with Zr⁴⁺ or Nb⁵⁺ ion. Interestingly, the CCTZNO ceramics exhibit greatly improved dielectric constant (~10⁵) at a frequency range of 10²–10⁵ Hz and at a temperature range of 20–210 °C, indicating a giant dielectric response within broader frequency and temperature ranges. The dielectric properties of CCTZNO ceramics were analyzed from the viewpoints of defect-dipole effect and internal barrier layer capacitance (IBLC) model. Accordingly, the immensely enhanced dielectric response is primarily ascribed to the complex defect dipoles associated with oxygen vacancies by co-doping Zr⁴⁺ and Nb⁵⁺ ions into CCTO structure. In addition, the obvious dielectric relaxation behavior has been found in CCTZNO ceramics, and the relaxation process in middle frequency regions is attributed to the grain boundary response confirmed by complex impedance spectroscopy and electric modulus.     

Characterization of barium titanate reinforced acrylonitrile butadiene rubber composites for flexible electronic applications: influences of barium titanate content

The aim of this study was to develop high dielectric constant flexible polymers with a highly efficient and cost‐effective approach using acrylonitrile butadiene rubber (NBR) as the polymer matrix and barium titanate (BT) as the high dielectric constant filler. The BT powder was synthesized with a solid‐state reaction and was characterized using a particle size analyzer, XRD, SEM and Fourier transform infrared spectroscopy. NBR/BT composites were fabricated using an internal mixer with various BT loadings up to 160 phr. The influence of BT loading on the cure characteristics and mechanical, dynamic mechanical, thermal, dielectric and morphological properties was determined. The incorporation of BT in the NBR matrix shortened scorch time and increased delta torque. The mechanical properties, thermal stability and dielectric constant were greatly improved and increased with BT loading. The results suggest that the reinforcement effect was achieved due to strong hydrogen bonding or polar–polar interactions between NBR matrix and BT filler. This is further corroborated by the good dispersion of BT filler in the NBR matrix observed with SEM imaging. These findings can be applied to produce high‐performance dielectric elastomers. © 2020 Society of Industrial Chemistry     

减水剂类型对赤泥—矿渣基地聚物注浆材料性能的影响及机理研究

针对赤泥等固体废弃物对环境危害性大且利用率低等问题,以碱激发赤泥-矿渣基地聚物注浆材料为 研究对象,研究了不同掺量的聚羧酸(PA)减水剂、醛酮缩合物(AKC)减水剂和萘系(N)减水剂对材料凝结时间、流动 性及强度等的影响,并通过 XRD、傅里叶红外光谱及 SEM 等设备对减水剂的作用机理进行研究。 结果表明:减水剂增 强了材料的流动性但降低了材料的剪切应力;N 和 PA 减水剂能缩短材料的凝结时间,但 AKC 减水剂会延长材料的凝 结时间;N 和 AKC 减水剂能提高材料的强度,但 PA 减水剂会降低材料的强度;N 减水剂对材料的综合性能提升效果 更加明显,其最优掺量为 0. 7%;减水剂对赤泥-矿渣基地聚物性能提升的作用机理主要是促进地聚合物凝胶的形成。 研究成果为拓展赤泥在工程上的使用途径和效率提供了理论指导。     

Spatiotemporal Magnetocaloric Microenvironment for Guiding the Fate of Biodegradable Polymer Implants

The degradation behavior of implants is significantly important for bone repair. However, it is still unprocurable to spatiotemporally regulate the degradation of the implants to match bone ingrowth. In this paper, a magneto-controlled biodegradation model is established to explore the degradation behavior of magnetic scaffolds in a magnetothermal microenvironment generated by an alternating magnetic field (AMF). The results demonstrate that the scaffolds can be heated by magnetic nanoparticles (NPs) under AMF, which dramatically accelerated scaffold degradation. Especially, magnetic NPs modified by oleic acid with a better interface compatibility exhibit a greater heating efficiency to further facilitate the degradation. Furthermore, the molecular dynamics simulations reveal that the enhanced motion correlation between magnetic NPs and polymer matrix can accelerate the energy transfer. As a proof-of-concept, the feasibility of magneto-controlled degradation for implants is demonstrated, and an optimizing strategy for better heating efficiency of nanomaterials is provided, which may have great instructive significance for clinical medicine.     

Mechanical Properties of Single-Layer Diamond Reinforced Poly(vinyl alcohol) Nanocomposites through Atomistic Simulation

Low-dimensional carbon nanostructures are ideal nanofillers to reinforce the mechanical performance of polymer nanocomposites due to their excellent mechanical properties. Through molecular dynamics simulations, the mechanical performance of poly(vinyl alchohol) (PVA) nanocomposites reinforced with a single-layer diamond – diamane is investigated. It is found the PVA/diamane exhibits similar interfacial strengths and pull-out characteristics with the PVA/bilayer-graphene counterpart. Specifically, when the nanofiller is fully embedded in the nanocomposite, it is unable to deform simultaneously with the PVA matrix due to the weak interfacial load transfer efficiency, thus the enhancement effect is not significant. In comparison, diamane can effectively promote the tensile properties of the nanocomposite when it has a laminated structure as it deforms simultaneously with the matrix. With this configuration, the interlayer sp³ bonds endows diamane with a much higher resistance under compression and shear tests, thus the nanocomposite can reach very high compressive and shear stress. Overall, enhancement on the mechanical interlocking at the interface as triggered by surface functionalization is only effective for the fully embedded nanofiller. This work provides a fundamental understanding of the mechanical properties of PVA nanocomposites reinforced by diamane, which can shed lights on the design and preparation of next generation high-performance nanocomposites.