Broadband dielectric study of dynamics of poly(vinyl pyrrolidone)-ethylene glycol oligomer blends

Broadband dielectric measurements for blends of poly(vinyl pyrrolidone) (PVP) and ethylene glycol oligomer (EGO) from 0 to 40 wt % PVP were carried out at 25 degrees C in the frequency range from 20 Hz to 20 GHz. The EGOs used in this study were ethylene glycol (EG), diethylene glycol (2EG), and PEG400 (MW = 400). For the PVP-EG, -2EG, and -PEG400 blends, relaxation processes caused by the motion of EGO in the GHz range and the micro-Brownian motion of the PVP chain at 10 kHz-1 MHz were observed. Although the PVP-EGO blend is miscible, relaxation processes caused by the molecular motion of EGO and the local chain motion of PVP were observed individually. The relaxation time of the local chain motion of PVP showed a strong PVP concentration dependence and a solvent viscosity dependence, which are similar to those reported so far for the solutions in nonpolar solvents.     

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.     

Synthesis of palladium nanoparticles by sonochemical reduction of palladium(II) nitrate in aqueous solution

The sonochemical synthesis of stable palladium nanoparticles has been achieved by ultrasonic irradiation of palladium(II) nitrate solution. The starting solutions were prepared by the addition of different concentrations of palladium(II) nitrate in ethylene glycol and poly(vinylpyrrolidone) (PVP). The resulting mixtures were irradiated with ultrasonic 50 kHz waves in a glass vessel for 180 min. The UV-visible absorption spectroscopy and pH measurements revealed that the reduction of Pd(II) to metallic Pd has been successfully achieved and that the obtained suspensions have a long shelf life. The protective effect of PVP was studied using Fourier transform infrared (FT-IR) spectroscopy. It has been found that, in the presence of ethylene glycol, the stabilization of the nanoparticles results from the adsorption of the PVP chain on the palladium particle surface via the coordination of the PVP carbonyl group to the palladium atoms. The effect of the initial Pd(II) concentration on the Pd nanoparticle morphology has been investigated by transmission electron microscopy. It has been shown that the increase of the Pd(II)/PVP molar ratio from 0.13 x 10(-3) to 0.53 x 10(-3) decreases the number of palladium nanoparticles with a slight increase in particle size. For the highest Pd(II)/PVP value, 0.53 x 10(-3), the reduction reaction leads to the unexpected smallest nanoparticles in the form of aggregates.     

壳聚糖微球悬浊液的介电谱研究:弛豫机制的解释和内部信息的获得

结合DLVO理论和壳聚糖微球的特点, 提出了适合实验数据的电动力学模型, 并分析了浓厚分散系的界面极化弛豫的微观机制. 进而测量了不同粒径壳聚糖微球悬浊液的介电谱, 发现在10～100 MHz频率范围内均出现明显的介电弛豫现象. 利用上述模型合理解释了该弛豫现象以及微球粒径对界面极化弛豫的影响, 结果也证明了我们提出的模型的适当性. 此外, 利用Hanai方法, 通过介电参数准确计算出了各悬浊液的内部信息, 并且分析了这些实时信息的合理性. 研究结果从实验和理论两方面展示了介电谱方法在即时获取壳聚糖内部信息上的独到优势.     

Dielectric response of a concentrated colloidal suspension in a salt-free medium

In this paper the complex dielectric constant of a concentrated colloidal suspension in a salt-free medium is theoretically evaluated using a cell model approximation. To our knowledge this is the first cell model in the literature addressing the dielectric response of a salt-free concentrated suspension. For this reason, we extensively study the influence of all the parameters relevant for such a dielectric response: the particle surface charge, radius, and volume fraction, the counterion properties, and the frequency of the applied electric field (subgigahertz range). Our results display the so-called counterion condensation effect for high particle charge, previously described in the literature for the electrophoretic mobility, and also the relaxation processes occurring in a wide frequency range and their consequences on the complex electric dipole moment induced on the particles by the oscillating electric field. As we already pointed out in a recent paper regarding the dynamic electrophoretic mobility of a colloidal particle in a salt-free concentrated suspension, the competition between these relaxation processes is decisive for the dielectric response throughout the frequency range of interest. Finally, we examine the dielectric response of highly charged particles in more depth, because some singular electrokinetic behaviors of salt-free suspensions have been reported for such cases that have not been predicted for salt-containing suspensions.     

Dielectric analysis of sheep erythrocyte ghost. Examination of applicability of dielectric mixture equations

The purpose of this study is to confirm the applicability of dielectric mixture equations in dielectric analysis of biological cell suspensions. Two dielectric mixture equations, the Pauly-Schwan (P-S) equation and the Hanai-Asami-Koizumi (H-A-K) equation were tested using sheep erythrocyte ghosts whose internal solution is identical with the external solution. Dielectric measurements were carried out for the ghost suspensions over a frequency range 10 kHz to 100 MHz; a single dielectric relaxation was found between 100 kHz and 10 MHz. From the dielectric relaxation, the conductivity and permittivity of the ghost interior and the capacitance of the cell membrane were calculated following the P-S and H-A-K equations. When the H-A-K equation was employed (and as expected from the property of the ghosts), the estimated internal conductivity was in good agreement with the external conductivity at volume fractions up to about 0.7. With the P-S equation, on the other hand, the same results as above were obtained but only at low volume fractions below about 0.3. In addition, the H-A-K equation provided a better simulation for the observed relaxation curves than did the P-S equation, especially at high volume fractions. It is, therefore, concluded that the H-A-K equation is applicable to a wider range of volume fraction than is the P-S equation.     

Dielectric relaxations of ionic thiol-coated noble metal nanoparticles in aqueous solutions: electrical characterization of the interface

The radiowave dielectric properties of organothiol monolayer-protected Au and Ag metallic nanoparticles have been investigated in the frequency range of 10 kHz to 2 GHz, where a dielectric relaxation, due to the polarization of the ionic atmosphere at the aqueous interface, occurs. The simultaneous measurement of the particle size, by means of dynamic light scattering technique, and of the particle electrical charge, by means of laser microelectrophoresis technique, allow us to describe the whole dielectric behavior at the light of the standard electrokinetic model for charged colloidal particles. Au and Ag metallic nanoparticles experience a large charge renormalization, in agreement with the counterion condensation effect for charged spherical colloidal particles. The value of the effective valence Z(eff) of each nanoparticle investigated has been evaluated thanks to the dielectric parameters of the observed relaxation process and further confirmed by direct current electrical conductivity measurements. All in all, these results provide support for the characterization of the electrical interfacial properties of metallic nanoparticles by means of dielectric relaxation measurements.     

The effect of the concentration of dispersed particles on the mechanisms of low-frequency dielectric dispersion (LFDD) in colloidal suspensions

There are two mechanisms which are currently used to explain the low-frequency (kHz range) dispersion of the dielectric permittivity of suspensions in electrolyte solutions (LFDD). The first, the surface diffusion mechanism (SDM), associates the LFDD with the diffusion of bound ions along the particle surface caused by the applied electric field. The second, the volume diffusion mechanism (VDM), follows from the generalization for alternating fields of the classical theory of the relaxation effect in electrophoresis and associates the LFDD with the diffusion of free ions in the diffuse double layer. It has been found that VDM is much more strongly dependent on particle concentration than SDM, opening new possibilities for the investigation of each of these two mechanisms separately. The reason is that when the concentration of particles in suspension increases, the characteristic length for the propagation of volume diffusion processes decreases together with the decrease of the free electrolyte volume, whereas the characteristic length for the surface diffusion remains constant. Correspondingly, when particle concentration is raised, the relaxation time of the VDM effect must decrease, whereas it must remain constant for the SDM mechanism. Thus, by varying the concentration of particles in suspension, one can separate the dispersion curves of SDM and VDM. A simple model is elaborated which can be useful to predict the volume fraction dependence of the parameters of LFDD; in particular, its amplitude and critical frequency. The results are compared with experimental data obtained with polymer latex dispersions of volume fractions ranging from 3 to 16%. It is found that the dielectric behaviour (the volume fraction dependence of both the amplitude and critical frequency of LFDD) of the dispersions is reasonably well explained with our model, thus demonstrating that VDM prevails in the systems studied. Experimental data previously found by other authors are also discussed in the light of the model presented.     

Liquid-phase synthesis of barium acetatotitanyl and barium oxalatotitanyl as intermediates for preparing nanosized barium titanate

Liquid-phase methods (an oxalate process in aqueous solution and a semialkoxide sol-gel process in anhydrous acetic acid) were used to prepare barium acetatotitanyl (BAT) and barium oxalatotitanyl (BOT), which are potential fillers for electrorheological liquids, and to prepare barium titanate during heat treatment of the aforementioned intermediates at 1200°C. The materials were characterized using electron microscopy, FTIR spectroscopy, and thermal analysis. The particle size was 80 to 100 nm for BAT powders and 20 to 50 nm for BOT powders. X-ray spectra of the powders dried at 120°C contain reflections from a barium titanate phase. The dielectric spectra of the materials synthesized were studied for suspensions in PMS-20 silicone oil over the frequency range from 25 to 10⁶ Hz up to 4 kV/mm. The dielectric parameters of BOT suspensions decrease hyperbolically with rising alternate current frequency, whereas BAT suspensions give rise to a relaxation dielectric spectrum with relaxation times on the order of 10⁻³ s.     

Dielectric analysis of chitosan gel beads suspensions: influence of low crosslinking agent concentration on the dielectric behavior

Dielectric measurements were carried out for the suspensions of chitosan gel beads (CGB) crosslinked with glutaraldehyde (GA), ranging in crosslinking time from 1 to 180 min at six fixed low GA concentrations over a frequency range from 40 to 110 MHz. The distinct dielectric relaxations observed in the frequency range of 10(4)-10(5) Hz were explained by the effects of the interfacial polarization. By fitting the experimental data with Cole-Cole equation the dielectric parameters of the suspensions were obtained, and the phase parameters were calculated using Hanai's method. The influence of crosslinking on the dielectric spectra of CGB was investigated by viewing the crosslinking time dependencies of conductivity increment (Deltakappa), relaxation frequency (f(0)), permittivity of CGB (epsilon(i)), conductivity of CGB (kappa(i)) and conductivity of continuous media (kappa(a)) at six fixed GA concentrations. Some information were gained, such as, thinner electric double layer, particle with rougher surface and more compact gel backbone with increasing crosslinking time. The basic information obtained can provide valuable references for the preparation of CGB and the application to more extensive fields such as controlled-release technology of medicament.     

Dielectric analysis on phase transition and micelle shape of polyoxyethylene trisiloxane surfactant in dilute aqueous solution

The cloudy Silwet L-77 aqueous solution on the concentration range from 0.5%to 50%was investigated by dielectric relaxation spectroscopy.The concentration dependence of phase microstructure was confirmed by means of analyzing the dielectric parameters of bulk solution.The relaxation behavior was assigned to the interfacial polarization between the micelle and the medium,and the relaxation distribution parameter was used to figure the shape transition from sphere to ellipsoid with the concentration increasing.The synchronous reduction of permittivity and conductivity indicated the formation of the lamellar phase. As compensation,the quantity of the surfactant liquid phase gradually decreased,whose shape constantly kept ellipsoidal.     

Transition from dilute to concentrated electrokinetic behavior in the dielectric spectra of a colloidal suspension

Dielectric spectroscopy is used to measure the complex permittivity of 200 and 100 nm diameter polystyrene latex suspended in potassium chloride (KCl) solutions over the frequency range 10(4)-10(7) Hz as a function of particle volume fraction (?) and ionic strength. Dilute suspension dielectric spectra are in excellent agreement with electrokinetic theory. A volume fraction dependence of the dielectric increment is observed for low electrolyte concentrations (0.01, 0.05, and 0.1 mM) above ? ≈ 0.02. This deviation from the dilute theory occurs at a critical frequency ω* that is a function of volume fraction, particle size, and ionic strength. The dielectric increment of suspensions at the highest salt concentration (1 mM) shows no volume fraction dependence up to ? = 0.09. Values of ω* are collapsed onto a master curve that accounts for the length and time scales of ion migration between neighboring particles. The measured conductivity increment is independent of volume fraction and agrees with theory after accounting for added counterions and nonspecific adsorption.     

The electrorheological efficiency of polyaniline particles with various conductivities suspended in silicone oil

Electrorheological (ER) behavior of silicone oil suspensions of particles of polyaniline protonated to various doping levels with ortho-phosphoric and tetrafluoroboric acids has been studied. The dynamic yield stress obtained by extrapolation of shear stress to zero shear rate using Herschel–Bulkley equation was used as a criterion of the ER efficiency. At a same molar concentration of doping acids, various protonation effects appeared and the dependences of the yield stress on the acid concentration differed. The comparison of the yield stresses with dielectric characteristics calculated from the Havriliak–Negami equation revealed that the particle conductivity, in contrast to particle permittivity, dominates the polarization process especially at higher protonation degrees. Consequently, particle conductivity or dielectric relaxation time proved to be the parameters providing the common dependences of the yield stress regardless of the way of polarization.     

Dielectric analysis of macroporous anion-exchange resin beads suspensions

Dielectric measurements were carried out for suspensions of D354 anion-exchange beads dispersed in electrolyte solutions at different concentrations, and distinct Maxwell-Wagner dielectric relaxations were observed around 10(6) Hz. Through fitting the experimental data we obtained the dielectric parameters of the suspensions, and then we calculated the phase parameters from the dielectric parameters and the measured volume fractions by Hanai's method. In light of the present understanding of the interfacial properties, and with the information obtained from the phase parameters, we satisfactorily interpreted the concentration dependences of the dielectric parameters. It is concluded that Hanai's method is an effective tool for obtaining the properties of dispersed particles; the properties of the electrical double layer, which are mainly decided by the properties of the electrolyte solution, predict the dielectric behavior of suspensions with conducting particles. The dielectric relaxation spectroscopy (DRS), based on the M-W mechanism, is also a very sensitive tool for probing the properties of the liquid/solid interface.     

Dielectric relaxation behavior of SDS/β-CD organized self-assembly in dilute aqueous solution

Dielectric relaxation behavior of SDS/β-CD self-organized with mass concentrations from 1% to 7% was investigated. The phase microstructure of SDS/β-CD aqueous solution was confirmed by analyzing the dielectric parameters. The dielectric relaxation behavior was attributed to the interfacial polarization between vesicle and medium, and the relaxation distribution parameter can indicate the shape transition from vesicles to microtubules with increasing concentration. Dielectric relaxation provided a new method to study surfactant organized self-assembly.     

Measurement of the dielectric relaxation property of water-ion loose complex in aqueous solutions of salt at low concentrations

Electrolytes and their dissociated ions are thought to form positive or negative hydration layers around them. In this study, we have developed a method to determine the volume and the dielectric relaxation property (relaxation frequency f c, dispersion intensity delta) of the water hydrating ions in salt solutions. The method consists of four steps: (1) By use of a high-resolution microwave dielectric spectroscopy technique, the dielectric spectra of sample salt solution and bulk water are measured in pair. (2) The dielectric spectrum of solutes (ions) with water layers for a given volume fraction varphi is then calculated from each pair of dielectric spectra of a sample salt solution and reference water according to the Hanai mixture theory. (3) Each spectrum of solutes with water layers at a given varphi is decomposed into a few Debye relaxation functions and the bulk water component. (4) The volume fraction varphi is operationally decreased from 0.5, and steps (2) and (3) are repeated at each varphi until the bulk water component vanished. Then the volume fraction of the hydrated solutes (ions) in solution is determined. The method was applied to NaF and NaCl solutions. As a result the different spectral intensity was nearly proportional to the salt concentration below 0.2 M in the frequency range of 3-26 GHz. The hydration number N h and the dielectric relaxation property of the hydration layer for each salt solution was successfully determined as ( f c1, delta 1, N h)= (18.7, 44.9, 27.9) for NaCl and ( f c1, delta 1, f c2, delta 2, N h) = (26.0, 6.70, 5.64, 19.2) for NaF.     

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．     

Dynamic structure of poly(vinyl pyrrolidone)/ethyl alcohol mixtures studied by time domain reflectometry

Dielectric studies of poly(vinyl pyrrolidone)/ethyl alcohol (PVP–E) binary mixtures with concentration variations were carried out in the frequency range of 10 MHz to 10 GHz by time domain reflectometry at 15, 25, 35, and 45 °C. One relaxation process, corresponding to ethyl alcohol molecules in the poly(vinyl pyrrolidone) (PVP) matrix, was observed in this frequency range for all the mixtures. The static dielectric constant of the PVP–E mixtures decreased linearly with an increase in the weight fraction of PVP. The observed anomalous increase in the value of the relaxation time (τ) of these mixtures was interpreted by the consideration of the variation in the local structure of self‐associated ethyl alcohol molecules and also the PVP behavior as a geometric constraint for the rotational motion of ethyl alcohol molecules. Furthermore, the τ values of these mixtures were independent of the viscosity. The energy parameters for the dielectric relaxation process (the free energy, enthalpy, and entropy of activation for the dipolar orientation) were determined to confirm the transient behavior of the heterogeneous species due to the breaking and re‐forming of hydrogen bonds with the internal rotation of ? OH groups in the ordered structure of the PVP–E mixtures. On the basis of the evaluated dielectric parameters, the formation of supermolecular structure in the PVP–E mixtures in dynamic equilibrium was sketched and examined by the consideration of the hydrogen bonding between the terminal hydroxyl groups of self‐associated ethyl alcohol flexible chains and the carbonyl groups of monomer units of PVP coiled chains. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1134–1143, 2005     

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.