K. Sekine

The number of interfaces and the associated dielectric relaxations in heterogeneous systems

Abstract In heterogeneous systems composed of some phases, mobile electric charges accumulate on the boundary surfaces between the constituent phase under the electric field applied. This charge accumulation, the so-called interfacial polarization, gives rise to dielectric relaxations. By the use of several examples, it is shown theoretically as well as experimentally that the dielectric relaxations are equal to the interfaces in the number. Typical examples of diphase systems are (i) a series combination of a polyethylene film and an aqueous solution, and (ii) water-in-oil emulsions. These systems contain one kind of interfaces, showing one dielectric relaxation. Practical examples of triphase systems are (i) a composite system of a Teflon film sandwiched between two aqueous solutions, and (ii) polystyrene microcapsules. These systems contain two kinds of interfaces, showing two dielectric relaxations. A pentaphase system composed of shell-spheres are discussed theoretically, showing four dielectric rela...

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.

Dielectric observations on polystyrene microcapsules and the theoretical analysis with reference to interfacial polarization

Dielectric measurements were carried out for polystyrene microcapsules which were prepared by means of an interfacial polymer deposition technique. The microcapsules showed a couple of dielectric relaxations termedP for lower andQ for higher frequencies. The frequency profiles were characteristic of the structure that shelled spheres were dispersed in a continuous medium. Gelatin aqueous solutions, cationic polyelectrolyte solutions and distilled water were loaded in the capsule interior to examine the effect of conductivities of the constituent aqueous phases on the dielectric properties. Relaxation frequencies of the relaxationsP andQ observed were directly proportional to the conductivities of the continuous medium and of the capsule interior, respectively. A dielectric theory was proposed for a suspension of shelled spheres in a continuous phase in order to analyze the relaxation data observed for the microcapsules. Volume fraction of the capsules, relative permittivity and conductivity of the capsule interior and thickness of the capsule wall are evaluated from the dielectric observations by use of the theoretical formulas derived. The dielectric behavior observed for the polystyrene microcapsules are interpreted quantitatively in terms of the dielectric theory proposed.

Dielectric approach to polystyrene microcapsule analysis and the application to the capsule permeability to potassium chloride

A method of numerical analysis is proposed to determine the phase parameters from dielectric observations of polystyrene microcapsules by using the conductivity at intermediate frequencies between two dielectric relaxations observed. The method was more feasible for the analysis of the microcapsule observations than the method by which the calculation is performed by use of the permittivity at lower frequencies. The method was applied to the dielectric observations of the KCl-loaded microcapsules to obtain the permittivity and the conductivity of the capsule interior, the thickness of the capsule wall, the volume fraction of the suspended capsules and the conductivity of the surrounding aqueous phase. The conductivity of capsule interior was found to be unchanged with time for as long as 3 months. From the results it is concluded that the microcapsules are impermeable to KCl.

Dielectric study of poly(methyl methacrylate) microcapsules in particular reference to the effect of the frequency dependence of the permittivity of the capsule wall

The dielectric behavior of poly(methyl methacrylate) (PMMA) microcapsules was analyzed theoretically by taking account of the frequency dependence of the relative permittivityɛs and the electrical conductivityχs of the capsule wall. For comparison, similar analysis was applied to polystyrene (PS) microcapsules which have frequency-independentɛs andχs. The behavior ofɛs andχs of the PMMA microcapsules was assumed to be represented by a dielectric relaxation of them-th power type on the basis of dielectric data on underwater PMMA films. By means of a theory of the interfacial polarization, some consideration was carried out regarding the effect of the frequency dependence ofɛs andχs on the dielectric behavior of the PMMA microcapsules. The consideration led to predictions that the frequency dependence ofɛs andχs causes (i) the variation in the relaxation intensity with the change in the conductivity of suspending medium, (ii) the frequency dependence of the permittivity at low frequencies and (iii) the frequency dependence of the conductivity at high frequencies. The theoretical prediction (i) was verified by observed data, (ii) and (iii) remaining unverified owing to the experimental difficulty.

Dielectric analysis of PMMA microcapsules containing an aqueous KCl solution to derive a distribution function of the release rate of KCl

Release of KCl from a batch of PMMA microcapsules containing an aqueous 3 mM KCl solution was studied with the following two methods: 1) dielectric measurements of suspensions of the microcapsules in distilled water. The electrical conductivity of capsule interior was estimated with this method. 2) Measurements of the conductivity of suspending medium of the microcapsule suspensions. These two kinds of experiments provided us with information about the amount of KCl remaining in the capsules and that diffused outside. Results of these experiments showed that the microcapsules varied in their release rate of KCl. A distribution function of the release rates was derived from the results of the dielectric measurements. That distribution function was successful in explaining the results of the measurements of the conductivity of suspending medium. Furrther examination revealed that the release rate increased with the increase in the thickness of capsule wall.

THEORETICAL STUDY OF DIELECTRIC BEHAVIOR OF MICROCAPSULE SUSPENSIONS WITH DISTRIBUTED DRUG RELEASE RATE

Theoretical consideration is made concerning the dielectric behavior of aqueous suspensions of W/O-type microcapsules containing aqueous electrolyte solutions, especially concerning distribution effects of the electrolyte release rate on the dielectric behavior.It is shown at first that the distribution of the release rate causes electrical conductivity of the capsule interior. Next, it is deduced, in the light of a theory of the interfacial polarization, that the distribution characteristics of the capsule interiors electrical conductivity are closely related to those of the relaxation time for a dielectric relaxation exhibited by the suspensions. Several formulas are derived to describe the relation between the distribution characteristics of the release rate and those of the relaxation time.

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.