三乙四胺钴配合物氧合结构和老化机理

以固相法合成的三乙四胺钴配合物为研究体系,采用正离子电喷雾串联质谱、紫外-可见吸收光谱、拉曼共振光谱和红外光谱等表征手段,研究了配合物与氧分子的相互作用过程及配合物在吸氧过程中的结构变化。结果表明,三乙四胺钴配合物的吸氧过程是一个动态的变化过程,氧合产物由双氧双桥联的氧合配合物CoⅢL-(O2)2-CoⅢL形式向双羟基桥联的老化配合物CoⅢL-(OH)2-CoⅢL形式转变;18O2同位素标记实验验证了Co-O-O-Co的存在。酸解实验说明OH桥联配合物的形成是造成可逆性差的根本原因。这些结果为探知多胺钴配合物的氧合结构和老化机理提供了新的研究方法和实验依据。     

Research on mechanical and dielectric properties of XLPE cable under accelerated electrical‐thermal aging

Research into the electrical‐thermal aging properties of cross‐linked polyethylene (XLPE) cable has great significance, because of its wide application. This study conducted accelerated electrical‐thermal aging tests on 10‐kV XLPE cable in order to assess the cable's mechanical and dielectric properties. After being aged by applying 34.8‐kV AC voltage at the four temperatures of 90, 103, 114, and 135°C, the cable samples were taken out in five stages according to the aging time and cut into slices. The slices were conducted experiments to test the breaking elongation, tensile strength, gel content, breakdown voltage, and frequency spectrums of the dielectric constant and dielectric loss. The results demonstrate that the mechanical strength and gel content of XLPE vary greatly under different aging temperatures, a finding that is associated with the crystallization characteristics of the material. The breakdown voltage shows a slight decreasing trend with aging time. The dielectric constant decreases with aging time in high‐frequency areas (10³–10⁶ Hz), while the dielectric loss factor increases with aging time at low frequencies (10^?2–0 Hz). These two parameters can be used to characterize the degree of aging in cable. Copyright © 2016 John Wiley & Sons, Ltd.     

Cu-Cr-Zr-Ce合金时效行为和电滑动磨损性能研究

在Cu-Cr-Zr合金中加入Ce,采用扫描电子显微镜和透射电子显微镜等观察和分析了Cu-Cr-Zr-Ce合金时效析出行为,将经过拉拔和时效处理(480℃×2h)的合金线材在自制电磨损试验机上进行电滑动磨损试验,并观察其电滑动磨损表面形貌.结果表明:Cu-0.40Cr-0.11Zr-0.059Ce合金在950℃固溶1h再经480℃时效处理后,其显微硬度和导电率较高;时效前冷变形能够加快时效初期第二相的析出并显著提高合金的性能,固溶合金经60%冷变形再经480℃时效2h后,其显微硬度和导电率分别可达153HV和85.26%IACS(相对导电率);而固溶后直接时效处理的合金的显微硬度和导电率仅为121HV和71.62%IACS;合金的磨损量随加载电流的提高而增大,其主要磨损机制为粘着磨损、磨粒磨损及电蚀磨损.     

西安地铁二号线沿线地裂缝未来位错量估算及工程分级

地裂缝在地铁设计使用期内的最大垂直位错量是西安地铁二号线穿越地裂缝结构设计的一个十分重要的参数。本文以历史水准监测资料为基础,分析了西安地铁二号线沿线各地裂缝在不同历史阶段的活动特征与活动原因,对各地裂缝的未来活动趋势进行了预测。然后通过基于不同时间段地裂缝活动速率的最大垂直位错量估算结果的对比分析,得出了地铁设计使用期内各条地裂缝与地铁交汇点处地裂缝的最大垂直位错量,并以此为依据,将西安地铁二号线沿线地裂缝分为Ⅰ、Ⅱ、Ⅲ和Ⅳ级等4个工程级别。     

The hydrolytic effect of moisture and hygrothermal aging on poly(butylene succinate)/organo-montmorillonite nanocomposites

The study of hydrolysis on biodegradable poly(butylene succinate) (PBS) is essential to predict the materials properties in a humid environment. In this study, PBS nanocomposites were exposed to different conditions of relative humidity (RH) and temperature. The moisture uptake increased with organo-montmorillonite (OMMT) loading and the RH of the testing environment. The exposure of PBS and the nanocomposites to a humid environment caused changes in the mechanical properties. The hydrolytic degradation becomes more pronounced upon hygrothermal aging at high temperature, whereby premature failure occurred. PBS nanocomposites were found to exhibit a better hydrolytic stability than neat PBS. The degradation was evaluated through Fourier transform infrared (FTIR) spectroscopy and gel permeation chromatography (GPC). A drastic reduction in the molecular weight of PBS has revealed the occurrence of degradation after exposure to moisture and heat. This has led to an alteration of the thermal behavior as investigated using differential scanning calorimetry (DSC).     

Storage Stability of LiFePO4/C in Humid‐hot Air

Storage stabilities of LiFePO₄/C composite at different conditions are investigated in terms of structural and electrochemical evolutions. The results from different aging tests indicate that moisture and temperature are the key factors that have the most profound effects on the structure homogeneity which in turn influences the electrochemical performance of LiFePO₄/C. Although the storage in a humid‐hot environment, such as saturated humidity air at 50°C, does not greatly influence the discharging capacity of LiFePO₄/C, it does reduce the initial charging capacity, thus the amount of reversible Li⁺ ions in a practical LiFePO₄/graphite cell decreases. This impact is explained by the lithium extraction during the storage, forming olivine FePO₄ and associated Li₃PO₄. Elevated storage temperature also favors the delithiation process. The degree of delithiation increases from about 6% at 50°C to 18% at 80°C. It is also found that re‐calcination at 650°C effectively resolves the problem of the structural heterogeneity of the stored LiFePO₄/C. Therefore both the initial charging capacity and coulombic efficiency of the stored sample in the first cycle revert to the original value of the fresh one.     

Biliverdin reductase A in the prevention of cellular senescence against oxidative stress

Biliverdin reductase A (BLVRA), an enzyme that converts biliverdin to bilirubin, has recently emerged as a key regulator of the cellular redox cycle. However, the role of BLVRA in the aging process remains unclear. To study the role of BLVRA in the aging process, we compared the stress responses of young and senescent human diploid fibroblasts (HDFs) to the reactive oxygen species (ROS) inducer, hydrogen peroxide (H2O2). H2O2 markedly induced BLVRA activity in young HDFs, but not in senescent HDFs. Additionally, depletion of BLVRA reduced the H2O2-dependent induction of heme oxygenase-1 (HO-1) in young HDFs, but not in senescent cells, suggesting an aging-dependent differential modulation of responses to oxidative stress. The role of BLVRA in the regulation of cellular senescence was confirmed when lentiviral RNAi- transfected stable primary HDFs with reduced BLVRA expression showed upregulation of the CDK inhibitor family members p16, p53, and p21, followed by cell cycle arrest in G0-G1 phase with high expression of senescence-associated β-galactosidase. Taken together, these data support the notion that BLVRA contributes significantly to modulation of the aging process by adjusting the cellular oxidative status.     

Influence of thermal aging on tensile and creep behavior of thermoplastic polyurethane

Changes in mechanical and physical properties of polyurethane thermoplastic during aging at 70 °C and 90 °C were investigated. The loss weight response was analyzed by gravimetric measurements under these temperatures. Changes in appearance and morphology of TPU after thermal aging were revealed by optical microscopy. The prolongation of the thermal exposure time, up to 270 days, leads to a progressive increase in tensile strength. In fact, elastic modulus and stress at 200% of strain were increased with thermal exposure time. These results can be explained by the increase of thermal stability due to the increase of material rigidity and the decrease in chain mobility. The evolution of the mechanical properties from tensile tests seems to be well correlated to the creep behavior. Finally, Scanning Electron Microscopy (SEM) revealed the modification of TPU morphology fracture surface after thermal aging.     

Influence of precipitation on the Portevin-Le Chatelier effect in Al-Mg alloys

In the alloy with solute content higher than the limiting solubility, the solute atoms that have failed to dissolve will precipitate from the solid solution and form precipitations. In this study, the Portevin-Le Chatelier (PLC) effects in annealed 5456 and 5052 aluminum alloys with different precipitation contents have been investigated under different applied strain rates. The results suggest that precipitations have significant effect on the PLC effect and the more the precipitations are, the greater the influence is. Furthermore, the solute diffusion is pipe diffusion in 5052 alloy with lower precipitation content. However, for 5456 alloy with higher precipitation content, the diffusion is no longer the case but more complex.     

深井超深井裂缝性地层致密承压封堵实验研究

深井超深井裂缝性地层钻井过程中极易发生钻井液漏失,桥接堵漏材料形成的裂缝封堵层在高温、高压、高地应力等复杂环境下失稳破坏加剧,导致堵漏成功率和裂缝封堵效果难达预期。基于多级多粒桥接堵漏的思路,以川西地区双鱼石区块超深井钻井常用的WNDK-1型架桥材料和耐高温橡胶颗粒为研究对象,系统开展了高温老化环境下堵漏材料性能评价与裂缝封堵模拟实验。实验结果表明,在150℃钻井液中老化24 h后,WNDK-1型刚性材料的粒度分布未产生明显变化,摩擦系数最高降低1.89%,抗压强度降低1.15%;橡胶颗粒的粒度分布D₉₀值增加3.55%,摩擦系数增加1.59%,抗压强度保持不变;将刚性材料、弹性材料和纤维材料以适当浓度与钻井液复配并进行裂缝封堵,形成的封堵层承压能力普遍高于13 MPa,且封堵层具有低孔低渗特征;观察封堵失稳后裂缝内封堵层结构形态可知,高温老化环境下多级多粒桥接堵漏形成的封堵层主要发生摩擦/复合失稳和剪切错位失稳。