物理气相沉积中等离子体参数表征的研究进展

物理气相沉积作为制备表面防护薄膜的重要方法,一直是表面薄膜领域研究重点,而物理气相沉积中等离子体作为直接影响薄膜性能的关键因素,其参数的表征对优化沉积工艺和提高薄膜性能具有重要指导意义.概述了常用物理气相沉积方法及其发展,包括电弧离子镀、磁控溅射和电弧磁控复合技术的原理及发展历程.归纳了目前生产中常用的等离子体参数表征方法——Langmuir探针法、汤姆逊散射法、微波干涉法和发射光谱法,阐明了这些表征方法诊断等离子体参数的原理,分析了不同表征方法的优缺点和存在的主要问题,并对常用物理气相沉积中等离子体参数表征相关研究的发展和现状作了综合论述和总结,分别整理了电弧离子镀和磁控溅射中等离子体参数诊断的发展历程和近期研究.两种物理气相沉积方法最常用的等离子体参数表征方法都是Langmuir探针法和发射光谱法,早期的研究侧重于探索等离子体瞬态参数和薄膜结构性能的关系.随着现代技术的进步,早期诊断方法不断与新技术融合,研究方向也逐渐偏向于研究等离子体参数的时间变化和优化薄膜工艺、性能评价方法.最后分析了当前物理气相沉积中等离子体参数表征存在的问题和不足,展望了等离子体参数未来的研究趋势.     

MgCl2-NaCl-KCl熔盐体系中金属Mg对316H不锈钢的缓蚀性能研究

通过电化学方法结合浸泡腐蚀测试考察了金属Mg对MgCl₂-NaCl-KCl(MNKC)熔盐的净化和腐蚀抑制作用。结果表明,金属Mg的加入量在500μg·g^-1以上时,316H不锈钢在600℃MNKC熔盐中的腐蚀电位Ecorr<-0.80 V vs NiCl₂/Ni,腐蚀电流密度Icorr<25μA/cm²,线性极化电阻Rp>800Ω·cm²,熔盐对316H不锈钢的腐蚀得到显著抑制。并对金属Mg对MNKC熔盐的净化和腐蚀抑制机理进行了探讨。     

脉冲偏压频率对TiSiN薄膜的微观结构和性能的影响

采用脉冲偏压电弧离子镀技术,通过改变脉冲偏压频率在M2高速钢基体上沉积TiSiN薄膜,利用扫描电镜(SEM)、能谱仪(EDS)、X射线衍射仪(XRD)等仪器,研究脉冲偏压频率对TiSiN薄膜的表面和截面形貌、元素成分、相结构的影响,并通过纳米压痕仪测试了TiSiN薄膜的纳米硬度和弹性模量。在统计的视场内(9×10³ μm²),TiSiN薄膜表面的大颗粒直径在0.30~7.26 μm之间,脉冲偏压频率从40 kHz到60 kHz,数量由495个减少到356个,之后随着脉冲偏压频率增加到80 kHz,大颗粒数量又增加到657个;当脉冲偏压频率为60 kHz时,TiSiN薄膜表面大颗粒和微坑缺陷数量最少,Si原子含量达到最小值0.46%;脉冲偏压频率为50 kHz时,TiSiN薄膜以非柱状晶的结构进行生长,厚度达到最小值1.63 μm;脉冲偏压频率为60 kHz时,柱状晶结构细化,薄膜的致密度增加。不同脉冲偏压频率下TiSiN薄膜都在(111)晶面位置出现择优取向,Si以非晶态Si₃N₄的形式存在于TiSiN薄膜中,没有检测到Si的峰值,形成了TiN晶体和Si₃N₄非晶态的复合结构。脉冲偏压频率60 kHz下TiSiN薄膜的表面大颗粒最少,纳米硬度达到最大值34.56 GPa,比M2高速钢基体的硬度提高了约3倍。当脉冲偏压频率为50 kHz时,TiSiN薄膜的腐蚀电位达到最大值－0.352 V(vs SCE),比基体提高了723 mV,自腐蚀电流密度达到0.73 μA/cm²;当脉冲偏压频率为70 kHz时,TiSiN薄膜的腐蚀电位达到－0.526 V(vs SCE),自腐蚀电流密度达到最小值 0.66 μA/cm²。     

离子迁移率测量装置研制及其在不同温、湿度下的变化规律

离子迁移率是直流输电线路离子流场计算的关键参数。为研究不同温、湿度条件下离子流场中的离子迁移率变化规律,在分析推导Gerdien离子迁移率测量原理的基础上,提出了一种在常规Gerdien管传感器两端设置屏蔽电极来抑制外部合成电场对测量区电场畸变效应的方法,研制出一套直流输电线路合成电场离子迁移率测量传感器及测控装置。在人工气候室中,搭建了直流输电线路离子流场模拟试验平台,对测量装置的适用性进行了验证。试验表明:常温常湿条件下正、负离子迁移率分别为1.25 cm2/(V·s)和1.59 cm2/(V·s);温度变化范围为10~40℃、湿度变化范围为3~25 g/m3时,正、负离子平均迁移率呈现出随温度增大而减小,随绝对湿度增大而减小并趋于饱和的变化规律,满足指数变化的拟合公式。分析指出:轻、重离子浓度比例变化与离子的水合反应程度为其变化原因。该研究工作可为直流输电线路离子流场的准确预测提供参考。     

Plasticized poly(vinyl chloride) composites: Influence of different nanofillers as antimigration agents

In this study, plasticized poly(vinyl chloride) (PVC) composites with different nanofillers, including single‐walled carbon nanotubes (SWCNTs), organoclay, TiO₂, and ZnO nanoparticles, were prepared, and their effects on plasticizer migration were investigated. Scanning electron micrographs revealed the dispersion quality of the nanofillers in the polymer matrix. It had a significant influence on the performance of the nanofillers in the process of plasticizer migration. Migration and exudation tests showed that the nanofillers could efficiently hinder plasticizer migration. On the basis of these results, we concluded that carbon nanotubes were the best antimigration agent in the plasticized system. This was ascribed to the high aspect ratio of the SWCNTs and the good interactions between them and the plasticizer. Also, TiO₂ nanoparticles showed a better performance compared to the ZnO nanoparticles. This was due to the more homogeneous dispersion of the TiO₂ in the polymer matrix and the higher surface area of the particles. The differential scanning calorimetry thermograms were in good agreement with the migration tests. The lowest change in the glass‐transition temperature was observed for the composite filled with SWCNTs. This indicated that a lower amount of the plasticizer migrated from PVC. The thermogravimetric analysis curves showed that the incorporation of the nanofillers improved the thermal stability of the PVC. The results could be useful for determining the efficiency of plasticized PVC in applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42559.     

Degradation kinetics of PVC plasticized with different plasticizers under isothermal conditions

The aim of the present work is to elucidate the degradation kinetics of polyvinyl chloride (PVC) plasticized with some phthalate and nonphthalate plasticizers. A PVC thermomat instrument was utilized to maintain the isothermal degradation conditions at 140 and 160°C, and to suppress the oxidative degradation by means of nitrogen flow. The conductivity measurements were performed to follow hydrogen chloride (HCl) gas which is released upon PVC degradation and trapped in water. Dehydrochlorination of plasticized PVC films occurred with activation energies of about 23–160 and 26–117 kJ mol^?1 and the isokinetic temperatures, at which the dehydrochlorination rate constants of all p‐PVC films would have the same value, were found to be 171 and 128°C for initial and linear regions of dehydrochlorination curve, respectively. Plasticizer incorporation contributes to the stability of the films particularly after the consumption of stabilizer due to the dehydrochlorination. Influence of temperature rise by 20°C on the degradation rate constant is the lowest for DINCH having p‐PVC films as 0.36 and 0.42% increment at the initial region and linear region, respectively. On the other hand, DOTP reveals greater stability than the others do since the compensation ratio of the PVC film having DOTP is greater than the other films. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41579.     

Li[Li_(0.2)Ni_(0.2)Mn_(0.6)]O_2富锂正极材料的制备及性能研究

通过液相法制得了球形Ni(OH)2,再与Mn(NO3)2、CH3COOLi通过固相法制备了富锂正极材料Li[Li0.2Ni0.2Mn0.6]O2。通过X射线衍射光谱法(XRD)、扫描电子显微镜法(SEM)、粒度分析仪、循环伏安、交流阻抗以及充放电测试对样品的结构、形貌和电化学性能进行了表征。结果表明,合成温度为900℃时,材料结晶度高,阳离子混排程度低,颗粒表面光滑均一;在20 m A/g时,首次放电比容量为174.02 m Ah/g,在60 m A/g的高倍率放电条件下比容量仍可达到80.56m Ah/g。     

锂离子电池在充放电过程中的产热研究

为保证电池在使用过程中性能的正常发挥和安全使用,以不同材料组成的商业化圆柱型锂离子电池为研究对象,采用绝热加速量热仪和充放电仪在线研究了锂离子电池充放电过程中的产热行为。结果表明:LiFePO4体系电池在放电过程的放热量最低,因此在车载电池使用中具有绝对优势;Li(Ni0.5Co0.2Mn0.3)O2体系电池产热量略高于LiFePO4体系,从数值分析,尚可应用于车载电池领域,而LiCoO2体系电池由于产热量巨大,而不适宜于在车载电池中的应用。通过对半电池的放热研究发现,LiCoO2体系电池放电过程的产热决定因素为正极;而LiFePO4和Li(Ni0.5Co0.2Mn0.3)O2体系放电过程主要产热因素为负极。     

锂离子电池磷化物负极材料研究进展

锂离子电池的储能密度主要取决于电极材料的容量。金属磷化物由于具备初始放电容量高以及电极极化小等特点成为锂离子电池负极材料的研究热点,被认为是一种极具潜力的锂离子电池负极材料。综述了锂离子电池磷化物负极材料的研究进展,并对各种金属磷化物的合成方法及其作为锂离子电池负极材料的综合电化学性能进行了系统论述。     

锂离子电池SiO/C负极材料制备及电化学性能

以一氧化硅、葡萄糖以及AGP-8石墨为原料,通过行星球磨和后续的高温热解制备SiO/C复合负极材料。采用X射线衍射仪(XRD)和扫描电子显微镜(SEM)对其进行了表征,经较高温度热处理得到的复合物中含有单质硅材料。复合材料电极电化学测试显示,经1 350℃热处理得到复合材料循环38周后,容量保持率接近100%,这主要源于稳定的材料结构能够在一定程度上承受嵌/脱锂过程中硅体积的变化。