Dielectric relaxation study of dipropylsulfoxide/water mixtures

The complex dielectric spectra of dipropylsulfoxide (DPSO)/water mixtures in the whole concentration range have been measured as a function of frequency between 100 MHz and 20 GHz at four temperatures between 298.15 K and 328.15 K. The dielectric parameters, static dielectric constant (ε_s), relaxation time (τ) and relaxation strength (Δε) have been obtained by the least squares fit method. The relaxation in these mixtures can be described by two Debye functions, whereas for pure DPSO Cole-Davidson type is valid. The relaxation times of the mixtures show a maximum at about x(DPSO) ≈ 0.3. In the concentration range where a maximum appears, the interaction of DPSO with water is presumably the result of hydrogen bonding between water and the sulfonyl group of the sulfoxide molecule. The concentration and temperature dependent excess dielectric constant and effective Kirkwood correlation factor of the binary mixtures have been determined. The excess permittivity is found to be negative for all concentrations.     

Dielectric dispersion studies of mixtures of aniline and benzonitrile in benzene solutions

Dielectric behavior of aniline, benzonitrile and their binary mixtures of different concentrations were studied in benzene at 293, 303, 313 and 323 K. The complex permittivity (∈′, ∈″) at microwave frequencies 7.22, 9.1, 19.61 GHz, static permittivity ∈₀ at 455 KHz and high frequency limiting dielectric constant ∈_∞ = n_D² at optical frequency of these molecules and their binary mixtures were measured. The average relaxation time (τ₀), distribution parameter (α) and thermodynamical parameters were determined. The plot of relaxation time (τ₀) against concentration of benzonitrile in the mixtures is nonlinear indicating complex formation.     

Dielectric absorption in mixtures of anisole with some primary alcohols at microwave frequency

Dielectric properties of binary mixtures of anisole with methanol (MeOH), 1-propanol (1-PrOH), 1-butanol (1-BuOH) and 1-heptanol (1-HeOH) over an entire concentration range have been studied at a fixed temperature 40°C. The dielectric constant (ε′) and dielectric loss (ε″) of the binary mixtures of polar liquids have been determined at a microwave frequency of 9.1?GHz. The static dielectric permittivity (ε ₀) of the liquid samples was also determined using a precision LCR meter. Determined values of static dielectric permittivity (ε ₀) and dielectric permittivity (ε*) at 9.1?GHz frequency were used to evaluate relaxation time (τ) and high frequency limit dielectric permittivity (ε _∞). Dielectric parameters were interpreted in terms of molecular interaction between the anisole and alcohol molecules.     

Study of interaction through dielectrics: Behavior of − OH group molecules from 10 MHz to 20 GHz

The complex permittivity spectra for tert-butyl alcohol (TB) with 2-propanol (2P) were determined over the frequency range of 10 MHz to 20 GHz using the time domain reflectometry (TDR) in the temperature range 25 °C to 55 °C for 11 different concentrations of the system. The static dielectric constant (ε₀) and relaxation time (τ) have been determined these spectra using the Debye model. Excess properties and Kirkwood correlation factor of the mixtures have been determined. The excess permittivity is found to be positive in the tert-butyl alcohol rich region and negative in the 2-propanol rich region. However, the excess inverse relaxation time has different trend. The static dielectric constants for the mixtures have also been fitted with the modified Bruggeman model by assuming an additional parameter in the model. It appears that structure of the TB–2P dimer in the TB rich region favors parallel dipole orientation, whereas in the 2P rich region, it favors antiparallel orientation.     

Study of heterogeneous interaction in binary mixtures of 2-methoxyethanol-water using dielectric relaxation spectroscopy

The dielectric relaxation measurements on binary mixtures of 2-methoxyethanol with water have been carried out over entire concentrations and at temperature range of 0 °C to 25 °C using a picosecond time domain reflectometry technique. The complex dielectric permittivity spectra of 2-methoxyethanol/water mixtures were fitted using Havriliak-Negami equation. The static dielectric constant and relaxation time for all concentrations were obtained using least square fit method. The principal relaxation time is small if compared to that of corresponding alcohol/water mixtures this may be due to the hydrogen bonding ether oxygen in the 2-ME-water system. Excess dielectric properties, Kirkwood correlation factor, thermodynamic properties and Bruggeman factor are also determined and the results are interpreted in terms of heterogeneous interactions among the unlike molecules due to hydrogen bonding.     

Microwave dielectric response of binary mixture of N,N-dimethylformamide with propylene glycol using TDR method

Dielectric relaxation study of N,N-dimethylformamide (DMF) has been carried out with propylene glycol (PLG) at different temperatures. Time domain reflectometry (TDR) in reflection mode has been used to measure the reflection coefficient in frequency range of 10 MHz to 20 GHz. The dielectric parameters static dielectric permittivity (? ₀) and relaxation time (τ) have been obtained by Fourier transform and least squares fit methods. The experimental results show nonlinear variation in dielectric permittivity and relaxation time with volume fraction of PLG confirm the structural formation due to the intermolecular interaction between N,N-dimethylformamide and PLG. The variation in excess permittivity (ε ^E), excess inverse relaxation times (1/τ)^E, Kirkwood correlation factors (g ^eff, g ^f), activation enthalpy (ΔH) and entropy (ΔS) are also calculated to study the binary mixture interaction.     

Dielectric relaxation study of poly(ethylene glycols) using TDR technique

Temperature dependent dielectric relaxation and thermodynamic properties of polyethylene glycols HO[CH₂CH₂O)_nH with number average molecular weight 200 (n = 4), 300 (n = 7), 400 (n = 9) and 600 (n = 14) g mol^− 1 have been studied using Time Domain Reflectometry (TDR) in the frequency range 10 MHz to 20 GHz. The frequency dependence of the complex dielectric permittivity is analyzed by the Havriliak-Negami expression. The static permittivity ε₀, high frequency limiting static permittivity ε_∞, average relaxation time τ₀ and thermodynamic energy parameters such as free energy, enthalpy of activation and entropy of activation have been determined. The average free energy of activation ΔF_τ for PEG molecules was found to be in the range 4-5 kcal mol^− 1. The values of entropy ΔS_τ for PEG-200, PEG-400 and PEG-600 molecules were found to be positive while entropy ΔS_τ for PEG-300 molecules was found negative, which confirms that the configuration of PEG-300 involved in the dipolar orientation has an activated state, which is more ordered than the normal state compared to PEG-200, PEG-400 and PEG-600 molecules.     

Structural, dielectric relaxation and piezoelectric characterization of Sr substituted modified PMS-PZT ceramic

Pyrochlore phase free [Pb_0.94Sr_0.06] [(Mn_1/3Sb_2/3)_0.05(Zr_0.53Ti_0.47)_0.95] O₃ ceramics has been synthesized with pure Perovskite phase by semi-wet route using the columbite precursor method. The field dependences of the dielectric response and the conductivity have been measured in a frequency range from 50 Hz to 1 MHz and in a temperature range from 303 K to 773 K. An analysis of the real and imaginary parts of the dielectric permittivity with frequency has been performed, assuming a distribution of relaxation times. The scaling behavior of the dielectric loss spectra suggests that the distribution of the relaxation times is temperature independent. The SEM photographs of the sintered specimens present the homogenous structures and well-grown grains with a sharp grain boundary. The material exhibits tetragonal structure. When measured at frequency (100 Hz), the polarization shows a strong field dependence. Different piezoelectric figures of merit (k_p, d₃₃ and Q_m) of the material have also been measured obtaining their values as 0.53, 271 pC/N and 1115, respectively, which are even higher than those of pure PZT with morphotropic phase boundary (MPB) composition. Thus the present ceramics have the optimal overall performance and are promising candidates for the various high power piezoelectric applications.     

Dielectric losses in statistical mixtures

The specific features of the dielectric spectra of statistical mixtures in the form of heterogeneous systems with spherical particles chaotically arranged in the space have been investigated. The distribution function of relaxation times f(τ) has been restored. It has been established that the relaxation times are continuously distributed within a wide interval [τ₁, τ₂]. Different methods for broadening the relaxation time distribution interval and approximating the relaxation time distribution function f(τ) have been analyzed. It has been demonstrated that f(τ) is a nonmonotonic function with two maxima at the boundaries and a minimum in the vicinity of the midpoint of the interval [τ₁, τ₂]. These features of the relaxation time distribution function are responsible for the large difference between the average relaxation frequencies of the permittivity and the dielectric loss (electrical conductivity).     

Detection of collective motions in dielectric spectra and the meaning of the generalized Vogel-Fulcher-Tamman equation

Based on the reduction property of dielectric spectra associated with the power-law function [∼(jωτ)^±ν] that appears in the frequency domain, one can develop an effective procedure for detection of different reduced motions (described by the corresponding power-law exponents) in temperature domain. If the power-law exponent ν is related to characteristic relaxation time τ by the relationship ν=ν₀ ln(τ/τ_s)/ln(τ/τ₀) (here τ_s, τ₀ are the characteristic times characterizing a movement over fractal cluster that is defined in Ref. [Ya.E. Ryabov, Yu. Feldman, J. Chem. Phys. 116 (2002) 8610]) and the simple temperature dependence of τ(T)=τ_A exp(E/T) obeys the traditional Arrhenius relationship, then one can prove that any extreme point figuring in the complex permittivity ε(jω) spectra (characterized by the values [ω_m, y(ω_m)]) obeys the generalized Vogel-Fulcher-Tamman (VFT) equation. This important statement confirms the existence of the ‘universal’ response (UR) (discovered and classified by Jonscher in frequency domain) and opens new possibilities in the detection of the ‘hidden’ collective motions in temperature region for self-similar (heterogeneous) systems. It gives also the extended interpretation of the VFT equation and allows one to differentiate collective motions passing through an extreme point. This differentiation, in turn, allows one to select the proper fitting function containing one or two (at least) relaxation times for the fitting of the complex permittivity function ε(jω) in the limited frequency domain. This conclusion can allow for the classification of dielectric spectroscopy as the spectroscopy of the reduced (collective) motions, which are described by different power-law exponents on the mesoscale region. The verification of this approach on available DS data (poly(ethylene glycol)-based-single-ion conductors) completely confirms the basic statements of this theory and opens new possibilities in general classification of different motions that can be detected in the analysis of the different dielectric permittivity spectra.     

The study of dielectric relaxation and glass forming tendency in Cd-Se-Te glassy system

The dielectric relaxation spectroscopes of Cd_xSe_70−xTe₃₀ (where x = 0, 5, 7, 10) alloy have been investigated in the temperature range 298-373 K and in the frequency range 100 Hz to 100 kHz near the percolation threshold. The frequency and temperature dependence on the dielectric constant showed a Debye dielectric relaxation process. Using Debye relation, the dielectric constant (?′), the most probable relaxation time (τ) and the barrier height (W) were estimated for binary ternary chalcogenide systems.In addition, the analysis of the results suggests that the effect of Cd content on electronic conduction of the system. The experimental results support to some extent the above criterion in the case of Cd-Se-Te ternary alloy.     

Dielectric parameters in Se70Te30 and Se70Te28Zn2 chalcogenide glasses

Temperature and frequency dependence of dielectric constant (ε′) and dielectric loss (ε″) are studied in glassy Se₇₀Te₃₀ and Se₇₀Te₂₈Zn₂. The measurements have been made in the frequency range (8-500 kHz) and in the temperature range 300 to 350 K. An analysis of the dielectric loss data shows that the Guintini's theory of dielectric dispersion based on two-electron hopping over a potential barrier is applicable in the present case.No dielectric loss peak is observed in glassy Se₇₀Te₃₀. However, such loss peaks exist in the glassy Se₇₀Te₂₈Zn₂ in the above frequency and temperature range. The Cole-Cole diagrams have been used to determine some parameters such as the distribution parameter (α), the macroscopic relaxation time (τ₀), the molecular relaxation time (τ) and the Gibb's free energy for relaxation (ΔF).     

Life-time resolved emission spectra in CdI2 crystals

The emission spectrum of CdI₂ is composed of ultraviolet (UV), green (G) and yellow (Y and Y′) bands peaking at 3.38, 2.50, 2.16 and 2.25 eV, respectively. In order to determine the initial states of the Y- and G-luminescence, decay curves have been measured at 6 and 80 K by varying emission energy. The observed decay curves are composed of two or three exponential components. These decay components were named τ₁, τ₂, τ₃, τ_3′ and τ₄. The emission spectrum for each decay component, i.e., the life-time resolved emission spectrum, was constructed from the observed decay curves. At 6 K, three bands at 2.12, 2.49 and 2.64 eV are obtained for τ₁, τ₂ and τ₃ components, respectively. At 80 K, a dominant band for the τ₄ component and a weak band for the τ_3′ component appear on the same energy position at 2.25 eV. The origin of each emission band in the life-time resolved emission spectra will be briefly discussed.     

Antiferroelectric phase transition in pyrochlore-like (Dy1− xCax)2Ti2O7 − δ (x = 0, 0.1) high temperature conductors

Low-temperature ordering transitions in polycrystalline high temperature conductors (Dy_1 − xCa_x)₂Ti₂O_7 − δ (x = 0, 0.1) prepared using co-precipitation, mechanical activation and solid-state reactions at 1400 or 1600 °C have been studied by impedance spectroscopy at low frequencies and thermal mechanical analysis (TMA). The dielectric permittivity and loss tangent of the ceramics obtained have been measured as a function of temperature at low frequencies (0.5−500 Hz). The results provide evidence for the relaxation of point defects, most likely oxygen vacancies, at 500−600 °C and an antiferroelectric low-temperature phase transition of the second order, associated with re-arrangement process in the oxygen sublattice of pyrochlore structure. The temperature of the antiferroelectric transition is 700 to 800 °C, depending on the synthesis procedure and ceramic composition. Calcium doping of Dy₂Ti₂O₇ leads to the formation of additional oxygen vacancies and, in the case of the samples prepared via co-precipitation, increases the peaks in permittivity due to the relaxation process and ordering transition by three or six times, respectively.     

Electron hopping mechanism in hematite (α-Fe2O3)

The frequency dependence of the real (?′) and imaginary (?″) parts of the dielectric constant of polycrystalline hematite (α-Fe₂O₃) has been investigated in the frequency range 0-100 kHz and the temperature range 190-350 K, in order to reveal experimentally the electron hopping mechanism that takes place during the Morin transition of spin-flip process. The dielectric behaviour is described well by the Debye-type relaxation (α-dispersion) in the temperature regions T<233 K and T>338 K. In the intermediate temperature range 233 K<T<338 K a charge carrier mechanism takes place (electron jump from the O²⁻ ion into one of the magnetic ions Fe³⁺) which gives rise to the low frequency conductivity and to the Ω-dispersion. The temperature dependence of relaxation time (τ) in the −ln τ vs 10³/T plot shows two linear regions. In the first, T<238 K, τ increases with increasing T implying a negative activation energy −0.01 eV, and in the second region T>318 K τ decreases as the temperature increases implying a positive activation energy 0.12 eV. The total reorganization energy (0.12-0.01) 0.11 eV is in agreement with the adiabatic activation energy 0.11 eV given by an ab initio model in the literature. The temperature dependence of the phase shift in the frequencies 1, 5, 10 kHz applied shows clearly an average Morin temperature T_Mo=284±1 K that is higher than the value of 263 K corresponding to a single crystal due to the size and shape of material grains.     

Electrical analysis of a newly synthesized rare earth double perovskite oxide: Sr2CeNbO6

A polycrystalline rare earth double perovskite oxide, strontium cerium niobate, Sr₂CeNbO₆ (SCN) is synthesized by solid state reaction technique for the first time. Impedance spectroscopy is employed to determine the electrical parameters (resistance (R), capacitance (C) and relaxation time (τ)) of SCN in a temperature range from 303 to 703 K and in a frequency range from 100 Hz to 1 MHz. The spectrum of imaginary part of complex impedance (Z″) at each temperature exhibits one relaxation peak. The modified Cole-Cole equation is used (experimental data is fitted with this model) to describe these relaxation peaks. Scaling behaviour of Z″ suggests that the relaxation describes the same mechanism at the entire temperature range. Impedance data of SCN that have capacitive and resistive components is represented by Nyquist diagram. The experimental impedance data is fitted using equivalent RC circuit at various temperatures. The grain conduction and τ follow an Arrhenius law associated with activation energy 0.87 and 0.88 eV, respectively.     

New experimental measurements and theoretical analysis of the collision-induced absorption in N2-H2 pairs

We present new experimental data on the collision-induced fundamental absorption in N₂-H₂ mixtures at room temperature and at low enough pressures so that the binary contribution is dominant. Previous measurements have been made at pressures where the ternary and possibly higher absorption coefficients are significant, and this makes it difficult to obtain accurate values for the binary absorption enhancement coefficient. To obtain the enhancement spectrum from the measurements of the mixture, it is necessary to subtract out both the spectra of pure H₂ and N₂, along with some CO₂ impurities thus increasing the experimental uncertainty. Nevertheless, we obtain a value for the integrated intensity of 1.15×10⁻⁴ cm⁻² amagat⁻² that is in good agreement with the previous value of 1.38×10⁻⁴. We also discuss how one can scale this result to high temperatures for application to brown dwarf or methane dwarf atmospheres.     

Dielectric relaxation study of ascorbic acid solutions in pure dimethylsulfoxide (or diethylsulfoxide) and in dimethylsulfoxide (or diethylsulfoxide)/water mixtures

The complex dielectric spectra of ascorbic acid solutions in pure dimethylsulfoxide (or diethylsulfoxide) and in dimethylsulfoxide (or diethylsulfoxide)/water mixtures have been measured at frequencies between 100 MHz and 20 GHz at 298.15 K.Two kinds of dielectric relaxation processes were observed in each solution. The low frequency relaxation (Debye term) is assigned to solute. The high frequency relaxation (Cole-Davidson term) is ascribed to practically unaffected solvent.From the results obtained it follows that relaxation time and relaxation strength in DESO containing solutions (i.e. binary AA/DESO and ternary AA/DESO/water systems) are greater than those in DMSO containing solutions.     

High-temperature dielectric properties of Gd2CuO4 ceramics

A sample of Gd₂CuO₄ (GCO) has been prepared through the solid state reaction technique. Dielectric properties of this material have been measured in detail as functions of temperature (between 285 and 450 K) and frequency (20 Hz-10 MHz). A step-like increase below 330 K and a broad peak around 360 K were observed in the real part of the permittivity (ε′) which were found to be originated from the oxygen vacancy hopping motions that cause a dipolar relaxation, followed by a Maxwell-Wagner relaxation as the hopping carriers are blocked by the interfaces and surfaces of the sample.     

A comparative study of non-polar solvents effect on dielectric relaxation and dipole moment of binary mixtures of mono alkyl ethers of ethylene glycol and of diethylene glycol with ethyl alcohol

Dielectric relaxation and dipole moment of binary mixtures of homologous series of mono alkyl ethers of ethylene glycol and of diethylene glycol, i.e., mono methyl, mono ethyl and mono butyl ethers of ethylene glycol (ROCH₂CH₂OH) and mono methyl, mono ethyl and mono butyl ethers of diethylene glycol (ROCH₂CH₂OCH₂CH₂OH) with ethyl alcohol (C₂H₅OH) of different concentrations were studied in dilute solutions of benzene, dioxane and carbon tetrachloride at 35 °C. Permittivity (ε′) and loss (ε″) at 10.1 GHz, static dielectric constant ε_o at 1 MHz and high frequency limiting dielectric constant ε_∞ = n_D² at optical frequency of these molecules and their binary mixtures at different concentration were measured in dilute solutions of non-polar solvents. The average relaxation time τ_o, relaxation times corresponding to overall molecular reorientation τ₁ and group rotations τ₂ were determined using Higasi's single frequency measurement equations for dilute solutions. The evaluated values of relaxation times and free energy of activation ΔF were used to explore the solvent effect on molecular dynamics of these polar binary systems in non-polar solvents. The excess inverse relaxation time and excess free energy of activation were determined to confirm the existence of hydrogen-bonded heterogeneous cooperative domains of the ethers and alcohol molecules at different concentration their binary mixtures in non-polar solvents. The dipole moment of the binary mixtures was evaluated using Higasi's and Guggenheim's equation for dilute solutions. The evaluated values of dipole moments and computed dipole moment values using a simple mixing equation of the polar molecules binary mixture were used to explore the effect of non-polar solvent environment on heterogeneous molecular interactions between ethers and alcohol molecules. The effect of number of carbon atoms in the molecular structure of these homologous series molecules was also considered for the interpretation of various evaluated dielectric parameters.