稀薄细胞悬浊系模型的介电解析法

对稀薄细胞粒子是浊液体系进行了介电模型化,在导出的描述该体系介电行为的理论公式的基础上,确立了从实验观察到的介电参数获得体系相参数的精确解析方法,对该体系可能产生介电弛豫的原因进行了现象论的分析,并以一个微胶囊作为细胞模型进行了介电测量和解析,获得了合理的结果.     

膜/液界面浓度极化现象的介电解析

对由强、弱荷电膜和溶液构成的膜／液非均匀体系，在10－107Hz频率范围进行了介电测量，在直流偏压下，该体系显示了二个显著的介电弛豫．利用具有电导率分布相，即浓度极化相的介电理论对强行电的离子交换膜的结果进行了介电解析，从实验上测得的介电参数求出了反映膜／液界面浓度极化层构造的参数，讨论了该体系产生介电弛像的原因、说明了介电理论的合理性，并提出了膜／液界面体系产生介电弛豫现象的可能机理．     

中相微乳液的介电弛豫谱解析及弛豫机制研究

对由SDS、CTAB、正庚烷、正丁醇和盐水组成的中相微乳体系进行了介电测量,在不同盐度下低频段出现显著的介弛豫现象,它给出了弛豫时间随盐度的变化关系。通过解析介电谱获得了体系内部结构和电性质等信息,几个介电模型和理论公式被用来解释解析的结果。对弛豫时间的计算结果发现,该弛豫是由多种极化机制参与、界面极化为支配的动力学过程。介电解析和模型计算相互验证,结果暗示着体系盐度变化对中相微乳结构变化的影响和可能的转化机制。     

Dynamics of nano-cluster in a new relaxor system: (PbMg1/3Nb2/3O3)/(BiFeO3)

We report the dynamical role of nano-clusters in controlling the physical properties and parameters of a new relaxor complex, (PbMg_1/3Nb_2/3)O₃/(BiFeO₃). This complex shows a gradual structural change from cubic to hexagonal crystal system with increasing BiFeO₃ content. Transmission electron microscopy (TEM) reveals the presence of scattered nano-clusters for (PbMg_1/3Nb_2/3)O₃ relaxor system which starts assembling for increasing value of BiFeO₃. As a consequence of this assembling, a crossover from relaxor to ferroelectric and dielectric peak broadening was observed. Corresponding change in physical parameters such as; Curie–Weiss and Uchino–Nomura parameters i.e., ΔT_cm and diffusivity ‘γ’ was also observed. Vogel–Fulcher (V–F) fitting was employed to calculate the activation energy required to activate the dipolar glasses into a dynamical state or to re-establish a polarization fluctuation around an isolated nano-cluster. V–F fitting shows increased activation energy for increasing cluster size. The suppression in polarization value shows the inability of the total dipole moment to reorient on application of electric field with growth/assembling of nano-clusters.     

Dielectric model and theoretical analysis of cationic reverse micellar solutions in CTAB/isooctane/n-hexanol/water systems

Dielectric relaxation spectra of CTAB reverse micellar solutions, CTAB/isooctane/n-hexanol/water systems with different concentrations of CTAB and different water contents, were investigated in the frequency range from 40 Hz to 110 MHz. Two striking dielectric relaxations were observed at about 10(4) Hz and 10(5) Hz, respectively. Dielectric parameters were obtained by fitting the data using the Cole-Cole equation with two Cole-Cole dispersion terms and the electrode polarization term. These parameters show different variation with the increase of the concentration of CTAB or the water content. In order to explain the two relaxations systematically and obtain detailed information on the systems and the inner surface of the reverse micelles, an electrical model has been constituted. On the basis of this model, the low-frequency dielectric relaxation was interpreted by the radial diffusion of free counterions in the diffuse layer with Grosse model. For the high-frequency dielectric relaxation, Hanai theory and the corresponding analysis method were used to calculate the phase parameters of the constituent phases in these systems. The reasonable analysis results suggest that the high-frequency relaxation probably originated from the interfacial polarization. The structural and electrical information of the present systems were obtained from the phase parameters simultaneously.     

聚吡咯/聚苯乙烯混合膜/电解质溶液体系的介电谱解析电解质种类和浓度对膜透过性的影响

测量了混入聚吡咯粒子的聚苯乙烯混合膜在不同浓度的氯化钠、氯化钾、氯化钙及氯化镁体系的介电谱, 在40 Hz~11 MHz, 发现了显著的双介电弛豫现象(Double-relaxation phenomena). 基于Maxwell-Wagner理论讨论了弛豫产生的机制, 将体系进行了模型化, 并利用Hanai理论方法对介电谱进行了解析, 从获得的内部参数对混合后的膜荷电性质以及混合膜对离子的透过性进行了详细的讨论, 进而利用Donnan平衡理论推导的膜电位的表达式拟合, 获得了混合膜的固定电荷等参数.     

Dielectric relaxation behavior of colloidal suspensions of palladium nanoparticle chains dispersed in PVP/EG solution

Dielectric measurements were carried out on colloidal suspensions of palladium nanoparticle chains dispersed in poly(vinyl pyrrolidone)/ethylene glycol (PVP/EG) solution with different particle volume fractions, and dielectric relaxation with relaxation time distribution and small relaxation amplitude was observed in the frequency range from 10(5) to 10(7) Hz. By means of the method based on logarithmic derivative of the dielectric constant and a numerical Kramers-Kronig transform method, two dielectric relaxations were confirmed and dielectric parameters were determined from the dielectric spectra. The dielectric parameters showed a strong dependence on the volume fraction of palladium nanoparticle chain. Through analyzing limiting conductivity at low frequency, the authors found the conductance percolation phenomenon of the suspensions, and the threshold volume fraction is about 0.18. It was concluded from analyzing the dielectric parameters that the high frequency dielectric relaxation results from interfacial polarization and the low frequency dielectric relaxation is a consequence of counterion polarization. They also found that the dispersion state of the palladium nanoparticle chain in PVP/EG solution is dependent on the particle volume fraction, and this may shed some light on a better application of this kind of materials.     

压力驱动膜过程中浓差极化的介电模型

提出了电导率呈指数型分布的浓差极化层的介电模型. 利用传递方程研究了压力驱动膜过程的介电谱, 并导出层内电导率分布与宏观测量的电容和电导之间定量关系的理论表达式, 得到介电谱高低频特征值与浓差极化模数之间的关系. 计算结果表明, 较之线性分布电导率, 指数型分布电导率能更好地描述浓差极化层的介电谱. 研究表明, 介电谱及其特征值和弛豫强度随浓差极化模数和层厚度显著变化. 对由分离膜、主体溶液和浓差极化层组成的复合体系的介电谱进行了数值模拟, 发现电导较之电容其频率依存关系对浓差极化模数的变化更为敏感, 上述研究为利用介电谱在线监测膜分离过程提供了有价值的理论参考.     

Analysis of dielectric observations of KCl-charged poly(methyl methacrylate) microcapsules using a two-component model consisting of KCl-permeable and KCl-impermeable capsules

Dielectric measurements were carried out on aqueous suspensions of poly(methyl methacrylate) microcapsules charged with KCl solutions to examine the KCl permeability of the microcapsules. The specimens exhibited three kinds of dielectric relaxation. Two kinds of dielectric relaxation were observed immediately after washing the specimens with distilled water. These overlapped each other when the specimen was left standing in the measuring cell for a long time. Their relaxation frequencies were affected by the KCl concentration of the suspending medium in which the specimen was kept before washing. Another relaxation was observed distinctly when the spepcimens were washed thoroughly with distilled water. Its relaxation frequency was affected by the KCl concentration of the charged solution. These results were explained by assuming that the specimens were mixtures of KCl-permeable and KCl-impermeable capsules. The theoretical analysis procedure was devised in the light of dielectric theory of interfacial polarization to estimate the parameters which characterize the structure of the specimens.     

Theory of dielectric relaxations due to the interfacial polarization for two-component suspensions of spheres

A theoretical formula of dielectric relaxation in a form of complex relative permittivity is derived for dilute suspensions of spherical particles of two kinds on the basis of the Maxwell-Wagner theory of interfacial polarization. Another theoretical formula is derived further for concentrated suspensions of spheres of two kinds on condition that the formula derived above holds for the infinitesimally increasing process in concentration of the dispersed spheres. Furthermore a theoretical formula is derived for concentrated suspensions of shelled spheres of two kinds as the extension of the formula for concentrated suspensions. By use of the theoretical formulas proposed, values of the permittivities and the conductivities of the two-component suspensions were calculated for some examples with different sets of phase parameters. Results of the numerical calculation demonstrates dielectric relaxation profiles full of variety and characteristic of the suspensions containing two kinds of spheres covered with or without shells.     

Effect of pore water and adsorbed moisture on the dielectric properties of green river oil shale

Moisture and pore water are found to have appreciable effects on the dielectric parameters of Green River oil shale. A regular decrease in the relative dielectric constant, ε′, and dielectric loss, ε″, with decreasing amount of adsorbed moisture and pore water is observed at 24°C for oil shale samples ranging in oil yields from ～6-～100 gallons per ton. The weak dependence of ε′ and ε″ on shale richness at frequencies in the range 50 Hz-1 MHz effectively rules out the application of dielectric techniques as an assay tool. The results are discussed in terms of interfacial polarization effects arising from the presence of adsorbed moisture and pore water in the oil shale matrix.     

Dielectric analysis of a nanoscale particle in an aqueous solution of low electrolyte concentration

The dielectric spectra of aqueous suspensions of nanoscale silica particles (8 and 24 nm) with low electrolyte concentrations were investigated as a function of the particle concentration. Obvious dispersions observed in the frequency range of 10-10(5) kHz are explained by the multiple effects of the interfacial polarization and the polarization of counterions by using a two-step model and the corresponding dielectric analytical method arising from the combination of Hanai's method and O'Konski's theory. The phase parameters, which reflect the inner properties of constituent phases of the system, are calculated and discussed in detail. The validity of the two-step model was tested in terms of the standard electrokinetic model deduced from pure theories.     

反渗透膜UTC-70在水溶液中的介电谱及其解析

根据平面层状体系介电弛豫理论研究了反渗透膜UTC-70在各种浓度氯化钠和氯化钾溶液中的介电弛豫行为.利用计算机拟合的方法得到膜/溶液体系的介电参数,并由此计算得到了UTC-70膜相和水溶液相的相参数,获得了反映反渗透膜UTC-70荷电情况的信息及其与电解质溶液浓度的关系,介电解析的结果解释了介电弛豫的产生机制.     

沸石及核壳结构聚合物粒子分散系的介电解析── 粒子排列模式对体积分数的解释

在40 Hz～110 MHz频率范围对NaA沸石堆积体系和聚苯乙烯-聚吡咯悬浮液进行了介电测量. 两类体系分别在105和107 Hz表现出因界面极化产生的弛豫. 利用Hanai理论解析两类体系的介电谱, 发现解析体积分数与实测体积分数之间存在与体系的浓度相关的明显差异. 通过分析Wagner原始模型阐明了差异的原因, 指出了分散相粒子相互作用力与差异程度间的内在联系, 从介电角度为胶体分散系中粒子统计排列方式的确定提供了判定依据: 当分散系浓度高于临界值时, 其最可取粒子统计排列模式为六方最密型; 低于临界值后, 排列模式随浓度的降低逐渐向简单立方型转变.     

Dielectric study on membrane adsorption and release: Relaxation mechanism and diffusion dynamics

Dielectric monitoring of the adsorption or release process of salicylic acid (SA) by chitosan membrane shows that the dielectric spectra of the chitosan membrane/ SA solution systems change regularly in the adsorption or release process. By analyzing the regularity, a new mechanism for the relaxations is proposed. The concentration polarization layer (CPL) caused by SA adsorption or release is confirmed to be essential for the dielectric relaxations. The changes of the spectra with time are explained by account of the relationship between CPL properties and dielectric strength. Based on this relaxation mechanism, a theoretical method can be established to calculate dynamical parameters of inner structure of the adsorption or release systems from their dielectric spectra. Therefore, dielectric spec- troscopy is demonstrated to be a promising method for estimating interfacial distribution of ionic sub- stances and their binding to membrane in a non-invasive way.     

High-frequency dielectric and conductometric properties of poly-l-lysine aqueous solutions at the crossover between semidilute and entangled regime

The dielectric and conductometric properties of poly-l-lysine aqueous solutions have been investigated in the frequency range from 1 MHz to 1.8 GHz, where micro-Brownian dynamics and internal motion of side-chain polar groups result in a well-defined relaxation process, intermediate between that caused by counterion polarization (characteristic of the polyelectrolyte nature of the polyion investigated) and that associated with the orientational polarization of the aqueous phase. The polymer concentration has been varied in a wide interval in order to investigate the influence of different chain conformations on the dielectric parameters as a consequence of the different concentration regimes occurring in these systems. With the help of polymer scaling theories, scaling relations for the dielectric strength and the relaxation time are presented, predicting, as the polymer concentration is increased, a transition from semidilute-unentangled to semidilute-entangled regimes. We compare these predictions with the experimental findings over the whole concentration range investigated, with a qualitative agreement. Deviations from the scaling behavior related to a crossover regime between unentangled and entangled regions are briefly discussed. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 3123–3130, 1999     

聚吡咯微粒掺入的聚苯乙烯膜在电解质溶液中的介电弛豫谱及其解析

在40 Hz～11 MHz频率范围测量了聚苯乙烯膜以及混入聚吡咯粒子的聚苯乙烯膜和电解质溶液构成的体系的介电谱, 发现了特异的弛豫现象: 纯的和掺入导电性聚吡咯后的聚苯乙烯膜分别显示出单一弛豫和双弛豫的不同模式的介电谱. 在Maxwell-Wagner界面极化概念基础上解释了该弛豫机制: 高、低频弛豫分别由膜-液界面极化和膜相本身的不均一性引起的. 将体系进行了模型化, 并利用Hanai理论方法对谱进行了解析, 获得了内部电性质的诸多参数. 对不同聚吡咯掺入量的膜/溶液体系的介电测量和解析结果表明, 电解质溶液的种类、浓度以及膜中混入聚吡咯的量都影响着膜相的介电响应. 这些结论为利用加入导电粒子改善绝缘高分子聚合物的电性质的研究以及制备既具有导电功能又使基体的力学性能得到提高的高分子复合物提供了重要的线索.     

Dielectric properties of emulsions

Summary Dielectric constants of O/W emulsions were measured over a wide range of concentration and at frequencies ranging from 20 cps. to 3 mc. No dielectric dispersion due to the interfacial polarization was observed in the experimental range of frequency, while the electrode polarization was observed below 100 kc. Experimental results were compared with theoretical values for spherical dispersions. It was concluded that the dielectric constants of O/W emulsions were expressed best byBruggeman's equation over the whole range of concentration.

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Zusammenfassung Die DK von ?l/Wasser-Emulsionen wurden über einen weiten Konzentrationsbereich und für Frequenzen zwischen 20 Hz und 3 MHz gemessen. Es war keine dielektrische Dispersion verursacht durch Oberfl?chenpolarisation innerhalb des experimentellen Frequenzbereiches zu beobachten. Dagegen wurde unterhalb 100 kHz Elektrodenpolarisation bemerkbar. Die experimentellen Ergebnisse wurden mit den theoretischen Darstellungen der Misch-DK für Dispersionen mit kugligen Teilchen verglichen. Der Verlauf der DK der ?l/Wasser-Emulsion wird am besten und über den ganzen Konzentrationsbereich durch die Gleichung vonBruggeman dargestellt.

     

Exploring the applicability of density functional tight binding to transition metal ions. Parameterization for nickel with the spin-polarized DFTB3 model

In this work, we explore the applicability and limitations of the current third order density functional tight binding (DFTB3) formalism for treating transition metal ions using nickel as an example. To be consistent with recent parameterization of DFTB3 for copper, the parametrization for nickel is conducted in a spin-polarized formulation and with orbital-resolved Hubbard parameters and their charge derivatives. The performance of the current parameter set is evaluated based on structural and energetic properties of a set of nickel-containing compounds that involve biologically relevant ligands. Qualitatively similar to findings in previous studies of copper complexes, the DFTB3 results are more reliable for nickel complexes with neutral ligands than for charged ligands; nevertheless, encouraging agreement is noted in comparison to the reference method, B3LYP/aug-cc-pVTZ, especially for structural properties, including cases that exhibit Jahn–Teller distortions; the structures also compare favorably to available X-ray data in the Cambridge Crystallographic Database for a number of nickel-containing compounds. As to limitations, we find it is necessary to use different d shell Hubbard charge derivatives for Ni(I) and Ni(II), due to the distinct electronic configurations for the nickel ion in the respective complexes, and substantial errors are observed for ligand binding energies, especially for charged ligands, d orbital splitting energies and splitting between singlet and triplet spin states for Ni(II) compounds. These observations highlight that future improvement in intra-d correlation and ligand polarization is required to enable the application of the DFTB3 model to complex transition metal ions. © 2018 Wiley Periodicals, Inc.     

Analysis of dielectric relaxations of w/o emulsions in the light of theories of interfacial polarization

An attempt is made to apply dielectric theories of interfacial polarization to observations of dielectric relaxations for W/O emulsions. Approximate formulas for disperse systems in a W/O type were derived from the two theories: one proposed by Maxwell and Wagner for dilute disperse systems of spherical particles, and the other developed by Hanai for concentrated disperse systems. Dielectric measurements were carried out on concentrated W/O emulsions prepared from kerosene and distilled water or KCl aqueous solutions by minimal use of emulsifiers. Marked dielectric relaxations were observed with the emulsions, the dielectric parameters having been determined to characterize the relaxation data. Phase parameters such as relative permittivity, electric conductivity and volume fraction of the disperse phase were evaluated from the dielectric parameters by use of the approximate formulas of the respective theories. The phase parameters evaluated and the frequency dependence of complex permittivity of the W/O emulsions deduced from the theory for concentrated disperse systems are in excellent agreement with the observed data in comparison to that for dilute disperse systems. It is concluded that the dielectric relaxations due to the interfacial polarization of disperse systems of spheres are explained satisfactorily by the theory for concentrated disperse systems.