Free energy of conformational change in a single chain of polyvinylidene fluoride using molecular simulations

Polyvinylidene fluoride (PVDF) has several crystal forms of which the α-form is nonpolar, while the β-form is polar and has the highest piezoelectric constant. α PVDF, when stretched, transforms into the β form, which has wide applications in sensors and actuators. Steered molecular dynamics simulations are used to study the transformation of a single chain of PVDF from a trans–gauche conformation to an all trans one. The Helmholtz free energy change (∆F) is estimated using Jarzynski's equality. The transformation starts at the chain ends followed by the transformation of the remaining chain. The free energy change for the transformation is found to be always positive, indicating that the TGTG' form has higher thermodynamic stability than the all trans form throughout the studied temperature range. With increasing temperature, free energy change for the transformation increases monotonically.     

冷低压分离器油相系统铵盐垢下腐蚀风险的模拟预测

为探究某加氢装置高压换热器管束腐蚀泄漏原因，利用Aspen Plus工艺模拟软件计算了冷低压分离器油相（简称冷低分油）中水质量分数分别为1%,2%,3%时，冷低分油系统的露点温度、氯化铵结晶温度、氯化铵潮解点温度和相对湿度。结果表明：相较于经验的露点温度预测方法，通过引入潮解点、划分系统“湿环境”温度范围判断氯化铵垢下腐蚀风险区域的方法与实际腐蚀案例更为切合；在3种油相含水条件下，换热器管束存在氯化铵垢下腐蚀的“湿环境”温度范围分别为：50~103 ℃,50~161 ℃,50~176 ℃；随着油相中含水量的提高，“湿环境”腐蚀区域逐渐向高温部位迁移，预计铵盐导致的垢下腐蚀将会愈加严重。     

Nitrate Additives Coordinated with Crown Ether Stabilize Lithium Metal Anodes in Carbonate Electrolyte

Lithium metal anodes (LMAs) are promising for next-generation batteries but have poor compatibility with the widely used carbonate-based electrolytes, which is a major reason for their severe dendrite growth and low Coulombic efficiency (CE). A nitrate additive to the electrolyte is an effective solution, but its low solubility in carbonates is a problem that can be solved using a crown ether, as reported. A rubidium nitrate additive coordinated with 18-crown-6 crown ether stabilizes the LMA in a carbonate electrolyte. The coordination promotes the dissolution of NO₃⁻ ions and helps form a dense solid electrolyte interface that is Li₃N-rich which guides uniform Li deposition. In addition, the Rb (18-crown-6)⁺ complexes are adsorbed on the dendrite tips, shielding them from Li deposition on the dendrite tips. A high CE of 97.1% is achieved with a capacity of 1 mAh cm⁻² in a half cell, much higher than when using the additive-free electrolyte (92.2%). Such an additive is very compatible with a nickel-rich ternary cathode at a high voltage, and the assembled full battery with a cathode material loading up to 10 mg cm⁻² shows an average CE of 99.8% over 200 cycles, indicating a potential for practical use.     

“高电压技术”课程线上线下混合式教学

本文采用超星学习通线上教学平台，以 “高电压技术”课程为对象，实施了规模为120余人的线上线下混合式教学。基于线上教学和传统教学的优势互补，设计了“高电压技术”多个教学环节。归纳分析了混合式教学在各个教学环节取得的效果和问题，并根据学生反馈提出了持续性的改进措施。     

Influence of the stoichiometry,microstructure, and metallization method on the dielectric properties of 0.94 Na0.5Bi0.5TiO3-0.06 BaTiO3

The morphotropic composition of the lead-free solid solution between Na_0.5Bi_0.5TiO₃ and BaTiO₃ (0.94 Na_0.5Bi_0.5TiO₃-0.06 BaTiO₃ or NBT-6BT) is of particular interest for the next generation of high-temperature capacitors but remains plagued by the diversity of dielectric properties reported in the literature. In order to explain the apparent inconsistencies among the reported dielectric properties of NBT-6BT, we examine the influence of stoichiometry, phase separation, and metallization method. We show that the nominal stoichiometry has a crucial effect, since increasing the nominal Na/Bi ratio increases conductivity and dielectric losses (tan δ). It also increases the real part of the permittivity (ε’) and the frequency dispersion of both ε’ and tan δ, thereby altering the shape of the evolution with temperature of the dielectric properties. Moreover it increases the depolarization temperature (T_d) and decreases the temperature of maximum permittivity (T_m). Phase separation also occurs during the synthesis of NBT-6BT as Na evaporation leads to the formation of secondary Ba-containing phases. We report that these phases can have a positive impact on the dielectric properties: a moderate volume fraction (2.5 to 3.0%) and average grain surface (0.9 to 3.0 µm²) of these secondary Ba-containing phases increase the relative permittivity, decrease the dielectric losses, and increase the insulation resistance. We also show that the metallization method impacts the dielectric properties and therefore may contribute to the differences between various reports. The dielectric properties of NBT-6BT samples are measured during successive heating/cooling cycles and reveal that the permittivity value is lower during the first heating when silver paste, even cured, is used. These three components contribute to explaining the diversity of the reported dielectric properties of NBT-6BT.     

Investigation the effect of FeNiCoCrMo HEA addition on properties of B4C ceramic prepared by spark plasma sintering

In this study, monolithic B₄C and B₄C-based ceramics incorporating FeNiCoCrMo dual-phase (FCC and BCC) high entropy alloys (HEAs) were produced by spark plasma sintering (SPS). The effect of additives on the densification behavior, mechanical properties, microstructures, and phase evaluation of the samples were investigated. X-ray analysis confirmed the existence of FCC structured HEA and depletion of BCC structured HEA, after high-temperature reaction between B₄C-HEAs. The addition of HEAs enhanced the densification behavior by liquid phase sintering. Furthermore, hardness and fracture toughness values of the samples increased with increasing HEAs content. Fracture toughness and hardness values for all composites were higher than the monolithic B₄C. A combination of the highest density (∼99.22 %) and the best mechanical properties (32.3 GPa hardness and 4.53 MPa m^1/2 fracture toughness) was achieved with 2.00 vol.% HEA addition.     

Corrosion behaviour of Mg-Gd-Y-Zn-Ag alloy components with different sizes after cooling

The corrosion behaviour of Mg-6Gd-3Y-1Zn-0.3Ag (wt.%) alloy components with different sizes after cooling was investigated. The alloys in the small components (SC) cooled fast, which were composed of α-Mg matrix and coarse long-period stacking ordered (LPSO) phases. The alloys in the large components (LC) cooled slowly, and there were thin lamellar LPSO phases precipitating inside the grains, except for α-Mg matrix and coarse LPSO phases. The hydrogen evolution test revealed that the corrosion rate of LC sample was higher than that of SC sample. Electrochemical impedance spectroscopy (EIS) test showed that the surface film on LC alloys provided worse protection. The corrosion morphologies indicated that the precipitation of the thin lamellar LPSO phases in LC sample caused severe micro-galvanic corrosion, which accelerated the rupture of the surface film.     

Polishing of zirconia ceramics by chemically-induced micro-nano bubbles

This study introduces micro-nano bubbles (MNBs) in the process of polishing zirconia ceramics through sodium borohydride hydrolysis to assist in polishing yttria-stabilized zirconia (YSZ). Compared with conventional silica sol, the material removal rate using this MNB-assisted technology is increased by 261.4%, and a lower surface roughness of 1.28 nm can be obtained. Raman, X-ray diffraction, and X-ray photoelectron spectroscopy are used to study the structural changes and phase stability of the YSZ during different polishing periods. The results show that MNBs are the key factor promoting the transformation from the tetragonal phase to the monoclinic phase on the surface of the YSZ during polishing. The H₂O molecules (or OH^? ions) on the surface of the YSZ are driven by the thermal kinetic energy of the micro-jets formed by the collapse of micro-bubbles, and they permeate to occupy more oxygen vacancies in the crystal lattice. Atomic force microscopy and nano-indentation tests show that the micro-protrusions on the surface of the YSZ preferentially undergo phase transformation, and their hardness decreases. This promotes abrasives to preferentially remove rough spots on the surface and achieve more efficient polishing. We believe this work adds valuable insights regarding low-temperature degradation and ultra-precise machining of YSZ ceramic materials.