高频电压下交联聚乙烯电缆绝缘中电树枝生长的动力学模型

针对高压交联聚乙烯电缆绝缘试样,在1000—2000Hz 10kV峰值正弦电压下,采用计算机实时显微数字摄像技术进行了电树枝培养实验.基于半结晶绝缘材料中电树枝生长机理和电树枝结构的分形特征,提出了一个在高频范围定量预测电应力驱动下交联聚乙烯电缆绝缘中电树枝生长特性的动力学模型,获得了电树枝生长率方程和从电树枝生长到击穿过程的寿命公式.将该模型预测值与实验中获得的电树枝生长规律实验数据进行比较,其结果有较好的一致性,表明提出的模型化方法可以应用到交联聚乙烯电缆绝缘中电树枝老化规律的定量分析研究中. 关键词： 交联聚乙烯电缆绝缘 电树枝 施压频率 动力学模型     

等规聚丙烯成核剂的结构和构型分析

成核剂在聚丙烯的结晶过程中作为晶核，参与调节晶体的晶型、大小及其分布，促使形成不同性能的聚丙烯材料．成核剂促进聚合物结晶的机制是聚合物结晶领域的研究热点，但其结构对聚合物结晶的影响尚不清晰；而成核剂通常具有同分异构体，使其结构解析更加困难，但成核剂的结构解析是进一步研究其成核机理的基础．本文综合运用核磁共振（NMR）波谱、傅里叶变换-红外（FT-IR）光谱和扫描电镜能谱分析（SEM-EDS）表征了一种二元羧酸复合物类β晶型聚丙烯成核剂的结构和构型，结果表明该成核剂cis-△4-四氢邻苯二甲酸钙为消旋体，羧酸与钙以桥式螯合方式形成有机羧酸金属盐．     

红外光谱法研究成核剂对聚丙烯光氧化降解的影响

采用红外光谱和显微红外光谱,对添加两种α成核剂(TM-1、TM-3)和一种β成核剂(TMB-5)的聚丙烯(PP)的自然光氧化降解行为及机理进行了研究。结果表明,添加成核剂前后,PP的光氧化降解产物均含有酮、羧酸、酯、醇和不饱和烃等。三种成核剂的加入并没有改变PP的光氧化降解机理和降解产物,但都对PP的光氧化反应起了一定的加速作用。各体系的光氧化速率依次为：PP/TMB-5>PP/TM-3>PP/TM-1>PP。PP与添加成核剂的PP中的光氧化程度沿深度的分布表现出相似的规律：表面处的羰基指数最高,自曝晒表面向内部,羰基指数逐渐降低,到约250 μm处减小到约为0,这个范围称之为表面氧化层。表面氧化层的厚度不随曝晒时间的不同而不同,而是由紫外光的穿透能力、氧气的扩散、尤其是加工时样品中的温度梯度所决定的。     

发展在XLPE电缆绝缘内外侧的电树枝

以XLPE高压电力电缆内外侧绝缘中的电树枝特性为研究对象，通过分析电树枝引发与生长的统计实验规律和采用扫描电子显微镜分析发现，由于不同结晶状态的影响，电缆绝缘内外侧的电树枝特性存在很大的差异.引发于绝缘内侧电树枝引发时间短、生长速度快、电树枝形状具有多样性；起始于绝缘外侧的电树枝不仅引发时间长、生长速度极慢，而且电树枝形状(结构)比较单一.并对这两个位置电树枝的引发和生长机理进行了探讨. 关键词： 电树枝 结晶状态 统计规律 内侧和外侧绝缘层     

不同晶化工艺对非晶PZT纳米薄膜形核取向生长机理的影响

射频磁控溅射法室温下在Pt/Ti/SiO2/Si上制备非晶Pb(Zr048Ti052)O3薄膜，非晶PZT薄膜分别经常规炉退火(CFA)处理和快速热退火(RTA)处理晶化为（100），（111）不同择优取向的多晶薄膜. 采用x射线衍射测定了薄膜相组分、择优取向度；用原子力显微镜和压电响应力显微镜观察了薄膜表面形貌，以及对应区域由自发极化形成的铁电畴像，观察了不同取向薄膜的电畴分布特征. 结果表明，RTA晶化过程钙钛矿结构PZT结晶主要以PZT/Pt界面处的PtPb化合物为成核点异质形核并类似外延的结晶生长，沿界面结晶速率远大于垂直膜面结晶速率，而CFA晶化样品成核发生在膜内杂质缺陷处，以同质成核为主. 不同的成核机理导致了不同晶面择优取向生长. 关键词： PZT薄膜 结晶 形核 力显微技术     

硅橡胶电树枝老化过程的实验及模拟研究

在交流高电场下研究了硅橡胶的老化过程,通过显微镜观察到了硅橡胶老化后产生的具有分形特征的电树枝结构,并对不同电压下获得的电树枝进行了形态以及分形维数方面的描述.基于修正的DLA模型和球状生长模型分别构建了相应的模拟算法,并对电树枝结构的生长过程进行了数值模拟,获得了较好的电树枝模拟结果.同时,也分析了不同模型下的模拟结果与实验结果在形态以及分形维数上的差异.     

(PbBa)(Zr,Sn,Ti)O_3反铁电/弛豫型铁电相界陶瓷的相变与介电、热释电性质

通过对(Pb087Ba01La002)(Zr06TixSn04-x)O3(004≤x≤020)固溶体的介电和偏压热释电性质的研究发现,当Ti含量004≤x≤007时,材料是反铁电四方相,而当009≤x≤020时,材料向弛豫型铁电体转化.在温度Ti含量相图中,x=009附近形成了反铁电铁电顺电三相共存点(Ttr).该点的相变温度最底;对于004≤x≤007的反铁电四方相,低温下呈现介电弛豫特征,并可被外电场诱导为亚稳铁电态,温度升高时,亚稳铁电→反铁电相变,反铁电→顺电相变引起两个热释电流峰,偏置电场下峰位和峰强均发生移动,在温度电场相图中也形成了铁电反铁电顺电三相点.从复杂化合物纳米相分离的观点和晶格动力学出发,讨论了相变与电学性能随Ti含量(x)和外电场(E)变化的物理机理. 关键词： 反铁电/弛豫型铁电相界 介电性能 偏压热释电性质 铁电-反铁电-顺电三相点     

同步扫描光谱方法研究聚合物结晶动力学过程

固体表面反射光与其折射指数之间存在余弦函数关系,而折射指数的均方起伏又和固体表面的密度和浓度起伏有关。因此从反射光的变化可以反映材料内部结构的一些变化。基于此理论指导,本文利用同步扫描光谱(SSS)方法,即荧光光谱仪的同步扫描模式进行反射光的检测,成功地监测了聚己内酯(PCL)薄膜在铜片上的熔融和非等温结晶过程。PCL薄膜的SSS谱图出现了两个明显的荧光光谱仪的光源峰(467和473 nm),利用这两个峰的信息可以表征聚合物的熔融和结晶过程中分子链结构的变化。采用SSS方法表征分析得到了PCL的热动力学和结晶动力学参数,其结晶Avrami exponent n为2.8～3.2,平均值为3.1,表明PCL的非等温结晶遵循异相成核、三维球晶生长机理。这些与差示扫描量热仪(DSC)得到的参数一致。研究结果表明SSS方法是一种简单、有效的原位测试聚合物熔融和结晶动态过程的方法。此外,SSS方法是一种基于荧光光谱仪的具有普适性的光谱方法,对发光和不发光固态聚合物均可以检测研究。     

管状铝质材料的等离子体电解沉积行为研究

对管状铝质材料的等离子体电解沉积行为进行了研究.测试了不同工作电压和不同电极放置模式条件下铝管内部不同位置的电位分布，并通过显微分析观察，对比了不同电极放置模式对铝管内外壁陶瓷沉积层生长情况的影响.结果表明，不同的电极放置模式下，铝管内外壁陶瓷沉积层生长情况有很大差异.这是因为不同的电极放置模式对铝管内的电场分布具有很大影响，进而影响到铝管内外壁陶瓷层的沉积过程.只有外电极时，由于电场屏蔽作用，不能在铝管内壁形成均匀陶瓷层；在铝管内部加入辅助中心电极后，铝管内部产生均匀电场，这有利于在其内壁形成均匀的陶瓷层. 关键词： 等离子体电解沉积 铝管 表面改性 陶瓷层     

聚丙烯/抗老化剂复合体系的γ-射线辐照降解研究

研究了聚丙烯(PP)及含有受阻酚类抗氧剂和受阻胺类光稳定剂复合体系的PP复合物经过γ-射线辐照后发生的结构变化及抗老化剂所起作用。实验利用红外光谱(FTIR)和示差扫描量热法(DSC)对PP的结构变化进行了系统表征。研究结果表明,当辐照剂量较小(50 kGy)时,纯PP及其复合物体系均未发生明显降解;当辐照剂量较大(≥50 kGy)时,PP及其复合物的羰基指数迅速提高,二者的结晶温度和熔融温度大幅度降低,说明PP发生了严重降解。在相同γ-射线辐照剂量条件下(≥50 kGy),PP复合物的羰基指数高于纯PP,而结晶温度以及熔融温度低于纯PP,表明高辐照剂量下抗老化剂复合物的存在不但没有阻止聚丙烯的降解,反而加快了降解的速率。     

Nucleating Efficiency of Organic Phosphates in Polypropylene

Organic phosphates used as nucleating agents can remarkably promote the stiffness and crystallization rate of polypropylene homopolymer and ethylene–propylene copolymer. In this article, the nucleating activity of 2,2′-methylene-bis(4,6-di-tert-butylphenyl) phosphoric acid and its derivatives for isotactic polypropylene (iPP) were investigated with a differential scanning calorimeter (DSC) and polarized light microscope (PLM), and their influence on mechanical properties of polypropylene was also studied. The results showed that the sodium salt (NA7) and the glyceride ester (NA8) of the organic phosphoric acid were of high nucleating efficiency. If 0.4 wt% of NA7 or NA8 was added to PP, the crystallization peak temperature of PP was raised 15°C or 11°C, respectively, the amount of crystallinity was increased by 3 to 6%, and the crystallization rate was enhanced significantly. The nucleating activity is thermally stable when the mixture of iPP and a nucleating agent was melted and crystallized repeatedly in the DSC. The nucleating agents mentioned above could increase the modulus of the polymer by 20 to about 30% and could increase the flexural strength by 10 to about 20%. However, a number of other organic phosphates tested have little nucleating effect.     

Structure characteristics of electrical treeing in XLPE insulation under high frequencies

Electrical tree structure is one of the most important influencing factors for electrical treeing characteristics in polymers. In this paper, we focused on the structure characteristics of electrical treeing in cross-linked polyethylene (XLPE) insulation under high-frequency voltages. The tree structure characteristics include structure distribution characteristics and structure conversion characteristics. The influences of voltage, frequency, and pin-plane spacing on tree structure characteristics were analyzed based on the experimental results. It can be concluded that tree structures regularly change with the local electric field and frequency. The electric field in a very small zone near the needle tip is an important influencing factor for the formation of bush-like trees, and the lowest frequencies for the observed pure-vine-like trees increased with voltage. For double-structure trees, the local electric field at the transition location of the two structures remained almost unchanged with voltage and pin-plane spacing, but obviously increased with frequency. In order to investigate the relations of the growth rate and fractal dimension with tree structure characteristics, a new parameter, the energy threshold W_t, has been introduced and calculated for different tree structures.     

Dielectric breakdown phenomena in Al2O3 filled DGEBA/MDA/SN composite system

Dielectric breakdown phenomena by electrical treeing deterioration was investigated in the new epoxy resin system DGEBA/MDA/SN filled with Al₂O₃. As the filler content increased, the maximum electric field at breakdown increased and then decreased with increase of defects such as voids, impurities and delamination or peeling between filler and matrix. As the electrode separation increased, the breakdown voltage increased, but the breakdown strength decreased and then saturated to 17 kV/mm. Also, the maximum electric field at the tip when the system was failed increased. The electrical tree initiated from the side of the needle electrode was not from the tip where the reinforced field is the highest. The electrical tree was blocked by the filler. The interface condition of filler and polymer matrix played an important role in the electrical treeing resistance. The final breakdown phenomena showed fan-type crack as observed in the non-filled system.     

Mie散射研究聚合物合金相结构的形成及相尺寸分布

本文应用Mie散射理论研究了聚丙烯 /尼龙 1 0 1 0合金的相结构与形态 ,计算了相尺寸分布。其结果与电子显微镜及Rayleigh散射结果进行了比较。     

Structure and Properties of Polypropylene/Polyolefin Elastomer/Organic Montmorillonite Nanocomposites

The crystallinity, mechanical properties, and thermal stability of polypropylene (PP)/organic montmorillonite (OMMT) and PP/polyolefin elastomer (POE)/OMMT composites, with polypropylene-g-maleic anhydride/styrene (PPMS) as a compatibilizer for both, were compared. The results showed that the strong interaction between the clay platelets and compatibilizer, which were generated by the maleic anhydride (MAH), improved the compatibility of the polymer matrices with the OMMT. A unique lamellar, flocculated structure of OMMT was formed after introduction of the POE. The highly dispersed clay layers could act as nucleating agents, resulting in smaller spherulites and higher crystallization temperatures. Compared with pure PP, the PP/OMMT nanocomposite showed enhanced mechanical properties and thermal stability; however, the PP/POE/OMMT had the best impact toughness.     

Effect of Interfacial Structure on Crystallization Behavior of Polypropylene/Polyolefin Elastomer/Barium Sulfate Ternary Composites

In this paper, interfacial structure induced development of crystallization behavior of polypropylene (PP)/polyolefin elastomer (POE)/barium sulfate (BaSO₄) ternary composites was studied by DSC. Two kinds of PP (copolymer and homopolymer) were used. The compatibility between PP and POE had a distinct influence on nucleation and crystal growth of PP in PP/POE binary composites. The crystallization rate of PP homopolymer increased because of the heterogeneous nucleation by POE, while the crystallinity of PP homopolymer decreased because of an inhibition effect of the hexane side chains in POE. BaSO₄ particles acted as heterogeneous nucleating agents of PP in ternary composites. The dispersion of BaSO₄, controlled by interfacial design, had a distinct influence on the nucleation activity of BaSO₄ in ternary composites. Interfacial structure had the same effect on nucleation activity of BaSO₄ particles and crystallization rate of PP matrix in PP copolymer ternary composites as those in PP homopolymer ternary composites.     

Induction time as a measure for heterogeneous spherulite nucleation: Quantitative evaluation of early-stage growth kinetics

A theory is proposed indicating that the induction time characterizes the nucleation process in polymer crystallization. A microscopic method has been developed to monitor early stages of the spherulite growth. Using the method, based on photometric measurement of the depolarized light intensity during isothermal crystallization from the melt, nonzero nucleation induction time values were found for polypropylene (PP). From comparison of the theory with the experimental results obtained from polypropylene crystallization, it follows that the formation of PP crystal nuclei on admixtures is affected both by the formation of the first crystalline layer and by the size of the critical nucleus.