Molecular dynamics simulation of the response of bi-disperse polyelectrolyte brushes to external electric fields

Langevin dynamics simulations have been performed to investigate the response of bi-disperse and strong polyacid chains grafted on an electrode to electric fields generated by opposite surface charges on the polyelectrolyte(PE)-grafted electrode and a second parallel electrode. Simulation results clearly show that, under a negative external electric field, the longer grafted PE chains are more strongly stretched than the shorter ones in terms of the relative change in their respective brush heights. Whereas under a positive external electric field, the grafted shorter chains collapse more significantly than the longer ones. It was found that, under a positive external electric field, the magnitude of the total electric force acting on one shorter PE chain is larger than that on one longer PE chain, or vice versa. The effects of smeared and discrete charge distributions of grafted PE chains on the response of PE brushes to external electric fields were also examined.     

四臂星型聚电解质刷在外加三价盐离子和电场下的塌缩

本文采用Langevin动力学模拟的方法,研究存在三价盐离子时,接枝在带相反电荷的极板上的部分带电的四个臂星型链呈现出的塌缩现象. 结果表明,在电场作用下,接枝星型链的平均带电分数和盐浓度在带电单体和三价盐离子的竞争性吸附中起关键作用. 对于接枝在带相反电荷的极板上的带电分数较高的星型链,刷子会塌缩到接枝极板上,并会产生极板表面电荷的过度补偿现象. 当带电分数较低时,如果星型链所带电荷数与三价盐离子电荷数相同,即使在很低的盐浓度下,极板对三价盐离子的吸引能力也高于对星型链中的带电单体的吸引. 结果表明,星型链在带电分数较低的情况下,三价盐离子的加入不会导致接枝电极表面电荷的过度补偿. 此外,本文还研究了三价盐离子对电场作用下星型刷的拉伸的影响.     

以能带理论诠释直流聚乙烯绝缘中空间电荷的形成和抑制机理

高压直流塑料交联聚乙烯电缆的研发难点是消除其中的空间电荷效应. 目前, 国内外学者普遍通过添加纳米粒子在聚乙烯体内形成深陷阱捕获电荷的机理来抑制电荷积聚, 但此抑制机理违背了电场的基本理论. 以能带理论全面阐述聚合物介质中空间电荷的形成和抑制机理, 从一级陷阱模型出发, 应用电荷入陷和脱陷动力方程, 推导了聚合物介质中空间电荷的形成过程. 在聚合物介质中引入深陷阱后, 介质Fermi能级位移, 电极与介质之间界面接触由Ohm接触转变为阻塞接触. 考虑到无定形相中大量的陷阱密度, 电荷耗尽区宽度小于100 Å, 电极与介质之间的界面对电子变得透明, 形成中性接触, 在电压作用下, 这种聚乙烯介质中不再可能形成空间电荷. 最后, 在纯聚乙烯和纳米改性后含有深陷阱的聚乙烯两种试样上, 分别测量了电导与电场强度的关系和空间电荷分布曲线, 实验结果符合理论推导. 关键词： 直流绝缘 能带理论 空间电荷 抑制机理     

宏观电偶极子对聚丙烯铁电驻极体膜电荷储存及其动态特性的影响

利用栅控恒压电晕充电组合反极性电晕补偿充电法，研究了孔洞(单元电畴)内分布的空间电荷型宏观电偶极子的形成，及其增长对聚丙烯孔洞膜电极化期间的电流特性及电导率的影响. 借助等温表面电位衰减测量、开路和短路热刺激放电电流谱分析等，讨论了宏观电偶极子及其密度变化时的聚丙烯孔洞驻极体膜电荷储存稳定性及电荷动态特性. 实验结果说明：由电极化形成的宏观电偶极子的自身电场提高了聚丙烯孔洞驻极体膜的电导率，从而降低了驻极体膜电荷储存的稳定性. 对呈现弱极化强度的孔洞驻极体膜，以孔洞为畴结构基本单元内的宏观电偶极子，其两性空间电荷的大部分仅仅分别沉积在透镜状孔洞上下两壁的两端. 外激发脱阱电荷从脱阱位置的输运路径，主要是绕孔洞两边沿介质层迁移；而极化强度较高的样品，其两性电荷则分别分布在上下两壁的宽广区域内，脱阱电荷的大部分在驻极体电场驱动下从脱阱位置通过孔洞层间的介质层迁移并衰减.     

Model of inversion of DNA charge by a positive polymer: fractionalization of the polymer charge

We model one strand of DNA by a one-dimensional lattice (ODL) of negative charges and consider the problem of inversion of its charge by a positive polyelectrolyte (PE). In the neutral state of the ODL-PE complex, each of the ODL charges is locally compensated by a PE charge. When an additional PE molecule is adsorbed by ODL, its charge gets fractionalized into monomer charges of defects (tails and arches) on the background of the perfectly neutralized ODL. Defects spread all over the ODL, eliminating the self-energy of PE. For DNA this fractionalization mechanism leads to a substantial inversion of charge, a phenomenon which is widely used for gene delivery.     

Attenuation of the depolarizing field in a thin film model relaxor

The behavior of the polarization in a microscopic statistical model for a thin film relaxor placed between two metallic electrodes is studied by numerical simulations. Depolarization fields different from zero, due to a non-perfect compensation of surface charges at the metallic electrodes, are taken into account. Different thicknesses and different values of the compositional charge disorder density for the relaxor are considered. Depolarization field is found to be extremely attenuated for large values of the number density of charge carriers in the relaxor. In such a case, field attenuation allows for the existence of a homogeneous ferroelectric ground state.     

Electrofriction and dynamic stern layers at planar charged surfaces

Using dynamic simulations, the electrophoretic mobility of counterions at a substrate with fixed or mobile surface charges under the action of a lateral electric field is studied. The lateral charge inhomogeneity and corrugation of the substrate is taken into account. Because of the pronounced electrofriction between counterions and surface ions, a large fraction of counterions is practically immobilized for highly charged substrates. This explains the experimentally observed saturation of the electrophoretic mobility of charged particles in the limit of high surface charge density.     

聚丙烯孔洞铁电驻极体膜的电极化及其电荷动态特性

根据栅控恒压电晕充电组合反极性电晕补偿充电法的实验结果计算出铁电驻极体的极化强度.结果说明，伴随着薄膜内孔洞气体的Paschen击穿，该铁电体的极化强度随栅压增加而显著上升.利用上述充电方法和热刺激放电(TSD)谱的分析讨论了这类空间电荷型宏观电偶极子，及与其补偿的空间电荷热退极化的电荷动态特性；阐明了这两类俘获电荷的能阱分布，即构成宏观电偶极子的位于孔洞上下介质层内的等值异号空间电荷分别被俘获在深、浅两种能值陷阱内，而位于薄膜表面层的注入空间电荷则被俘获在中等能值陷阱中. 关键词： 反极性电晕补偿充电法 铁电驻极体 充电电流 热刺激放电     

表层氟化聚乙烯中的空间电荷

本文试图简要地汇集近年来与近期我们所取得的关于表面氟化对聚乙烯(PE) 空间电荷行为影响的研究结果, 总结与探讨PE中的空间电荷积累与其氟化层特性和特征间的关联. 这些结果显示在氟化反应气中没有氧存在时一个非常薄的氟化层能产生有效的电荷抑制, 而当氧存在时为达到有效的电荷阻挡、需要一个具有高氟化度的非常厚的氟化层. 在影响空间电荷的诸电学因素中, 氟化层的电荷传导特性比其电荷俘获特性和介电常数或极性对阻止电荷注入材料内部更为重要, 尽管氟化层的高介电常数和被俘获的电荷会降低界面电场、因此减少电荷的电极注入. 氟化层的电荷传导特性密切关联于其自由体积, 反应混合气中存在的氧对减小自由体积、因此对电荷的抑制具有强的负面影响.     

Investigation of the interface between polyethylene and functionalized graphene: A computer simulation study

The effect of surface chemical functionalization of a single graphene layer on its thermodynamic work of adhesion (WA) with polyethylene (PE) chains has been investigated using molecular dynamics (MD) simulation. For this purpose, amine (NH₂), carboxyl (COOH), hydroxyl (OH), and methyl (CH₃) functional groups were distributed randomly throughout the graphene surface using a Monte Carlo (MC) algorithm to achieve graphene functionalized structures with minimized potential energies. The MD simulation results showed that the thermodynamic WA between the PE and the functionalized graphene was larger than that between the PE and the pristine graphene. In fact, the electronegativity of functional groups and Van der Waals forces play influential roles in the thermodynamic WA between the PE and the functionalized graphene. In addition, the amount of thermodynamic WA was increased with increasing the functional group surface density, except for the graphene functionalized with the methyl groups. The segmental density of the PE chains near the single sheet surface was determined based on the density profile calculation. The polymer segments exhibited strong ordering and sharp density variations near the PE/graphene interface. The dynamic of chains was quantitatively characterized by calculating mean square displacement (MSD). Furthermore, the influence of functionality on the glass transition temperature (T_g) of the PE at the PE/graphene interface region was investigated. The results showed that the T_g at the PE/graphene interface was much higher than that of the bulk polymer. In fact, the functionalization of the graphene surface seems to considerably enhance the T_g of the polymer due to lowering the chains mobility.     

Counterion release and electrostatic adsorption

The effective charge of a rigid polyelectrolyte (PE) approaching an oppositely charged surface is studied. The cases of a weak (annealed) and strongly charged PE with condensed counterions (such as DNA) are discussed. In the most interesting case of the adsorption onto a substrate of low dielectric constant (such as a lipid membrane or a mica sheet) the condensed counterions are not always released as the PE approaches the substrate, because of the major importance of the image-charge effect. For the adsorption onto a surface with freely moving charges, the image-charge effect becomes less important and full release is often expected.     

线性低密度聚乙烯中空间电荷陷阱的能量分布与空间分布的关系

使用激光感应压力波法和热刺激放电技术,系统地研究了直流高压作用下线性低密度聚乙烯(LLDPE)半导性电极试样中空间电荷的形成和演变及电荷陷阱分布和退极化过程.在直流高压作用下试样中空间电荷的分布明显地表现为两电极同极性电荷快速对称注入的特征,半导性电极与LLDPE的界面近乎呈现欧姆接触特征.LLDPE中的电荷陷阱分布表现出体内为浅陷阱、表层为深陷阱的特征.半导性电极与LLDPE薄片间的压合条件或电极材料对LLDPE表层的掺杂显著地影响表层陷阱的能量分布,导致表层中较深陷阱的深度和密度减小、较浅陷阱的密度增大.在整个短路退极化过程中,试样中正、负电荷的中心分别向距它们较近的电极迁移,而在开路退极后期则表现为与短路时不同的行为、被表层深陷阱再俘获的电荷脱阱后向背电极迁移. 关键词： 线性低密度聚乙烯 空间电荷 陷阱分布 热刺激放电     

Analysis on surface charging of insulator prior to flashover in vacuum

Prior to the flashover across an insulator in vacuum, the insulator surface is usually charged. It is of great importance to investigate the charging phenomena for better understanding the flashover characteristics. It is considered that there are two kinds of mechanisms closely related to the surface charging of insulator i.e., the secondary electron emission occurred over an insulator, and while employing a perfect electrode contact ahead of electron emission into vacuum, the charge injection and accumulation occurred inside the surface layer of an insulator. Based on the rigorous analysis of the kinetic processes of both primary and secondary electrons, the related surface charges were theoretically deduced. Involving the detrapping of charges trapped and the recombination of charges injected, the charging process due to charge injection and accumulation was analyzed. Some formulas were given to express the density of surface charges.     

Adsorption of hydrophobic polyelectrolytes onto oppositely charged surfaces

We present a scaling theory for the adsorption of a weakly charged polyelectrolyte chain in a poor solvent onto an oppositely charged surface. Depending on the fraction of charged monomers and on the solvent quality for uncharged monomers, the globule in the bulk of the solution has either a spherical conformation or a necklace structure. At sufficiently high surface charge density, a chain in the globular conformation adsorbs in a flat pancake conformation due to the Coulombic attraction to the oppositely charged surface. Different adsorption regimes are predicted depending on two screening lengths (the Debye screening length monitored by the salt concentration and the Gouy-Chapman length monitored by the surface charge density), on the degree of ionization of the polymer and on the solvent strength. At low bulk ionic strength, an increase in the surface charge density may induce a transition from an adsorbed necklace structure to a uniform pancake due to the enhanced screening of the intra-chain Coulombic repulsion by the counterions localized near the surface. Received 12 April 2001     

Prediction of uncompensated polarity in ultrathin films

Relying on first principles simulations of stoichiometric MgO, ZnO, and NaCl (1x1) ultrathin (111) films, we demonstrate the existence of a critical thickness below which polarity is uncompensated: the surface charges are bulklike, and the total dipole moment and the formation energy grow linearly with thickness. This study reveals novel facets of the problematics of polarity akin to the nanoscopic size of the objects and opens stimulating perspectives on polar nanostructures with surface properties and reactivity unaffected by charge compensation as in macroscopic samples.     

表层氟化温度对聚乙烯中空间电荷积累的影响

在实验室反应釜中于不同的温度(35 ℃, 55 ℃和70 ℃) 下, 以氟气体积浓度为12.5%的氟/氮混合气对热压制备的聚乙烯(PE) 片状试样(厚约0.8 mm) 进行了相同时间(2 h) 的表层氟化改性. 利用压力波法研究了氟化温度对PE中空间电荷积累的影响. 结果显示, 随着氟化温度的提高直流高压作用下的氟化试样中的空间电荷积累明显减少, 这个70 ℃的氟化试样中几乎没有空间电荷. 衰减全反射红外分析表明, 氟化引起了试样表层化学组成的本质变化及氟化度随氟化温度的明显提高. 接触角测量与表面能计算间接地表明了这些氟化层有显著增大的介电常数. 开路热刺激放电电流测量进一步揭示了这些氟化层 不同的电荷捕获特性, 及随着氟化温度的提高氟化层对化学杂质从半导性电极向PE扩散的增强的阻挡特性, 因此表明氟化层中自由体积的相应减小. 表层自由体积的减小对抑制空间电荷的积累, 比介电常数的增大和电荷陷阱的变化起到更加显著的作用.     

Interaction of charged dust particles in clouds of thermodynamically equilibrium charges

The solution of the Poisson-Boltzmann equation for a cloud of charges surrounding two charged dust particles treated as Debye atoms forming a Debye molecule is investigated numerically using Cassini coordinates. The electric force exerted on a dust particle by the other dust particle was determined by integrating the electrostatic pressure on the surface of the dust particle. It is shown that attractive forces appear when the following two conditions are satisfied. First, the Debye radius (corresponding to the electron density at half the mean distance between the dust particles) must be approximately equal to half the mean distance between the dust particles. Attraction between the dust particles emerges at a distance equal approximately to half the mean distance between the dust particles. Second, attraction takes place when like charges are concentrated predominantly on the dust particles. If the particles carry a small fraction of charge of the same polarity, repulsion between the particles takes place at all distances.     

Calculation of the detonation velocity of porous water-containing RDX-based charges

A nomographic method for predicting the detonation velocity of a porous explosive mixture prepared from RDX powder and water is proposed. It is shown that, in contrast to the existing calculation methods for predicting the detonation velocity, the use of the proposed nomogram greatly simplifies the procedure and requires knowledge of only two parameters: the mass fraction of RDX and the density of the mixture in the charge. At the same time, the nomogram is a coordinate system that enables to place and to compare on one field experimental data obtained at different parameters of the charge. It is shown that RDX powder-water hand-prepared charges can have a detonation velocity of 6–8 km/s. The detonation velocity of cylindrical water-containing charges 10–36 mm in diameter and 120–1000 mm in length with RDX mass fractions of 0.6–1.0 is measured.     

一个非晶InGaZnO薄膜晶体管线性区陷阱态的提取方法

非晶InGaZnO(a-IGZO)薄膜在制备过程中形成的缺陷和弱键以陷阱态的形式非均匀分布在a-IGZO的带隙中, 这些陷阱态会俘获栅压诱导的电荷, 影响a-IGZO薄膜晶体管线性区迁移率、沟道电子浓度等, 进而影响线性区的电学性能. 本文基于线性区沟道迁移率与沟道内的自由电荷与总电荷的比值成正比, 分离出自由电荷以及陷阱态电荷. 由转移特性和电容电压特性得到自由电荷以及陷阱态电荷对表面势的微分, 分离出自由电子浓度和陷阱态浓度. 通过对沟道层与栅绝缘层界面运用泊松方程以及高斯定理, 考虑了沟道表面势与栅压的非均匀性关系, 得出自由电子浓度以及陷阱态浓度与表面势的关系, 最后通过陷阱态浓度与表面势求导得到线性区对应的态密度.     

Numerical computer calculation of distribution of similar point charges at the dielectric surface

Results of numerical calculation of the distribution of similar point charges over a uniformly charged dielectric plane are presented for different surface charge densities and surface temperatures. It is shown that, in the case of the surface charge density ranging from 2 × 10⁻⁶ to 7 × 10⁻⁵ C/m² and temperatures ranging from 300 to 800 K, the Lindemann criterion is fulfilled for the average deviation of the point charge from the equilibrium position, and the collection of point charges at the dielectric surface can be regarded as a 2D Coulomb crystal.