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.     

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.     

Time domain response and the data analysis of ferroelectric discharge current

The time domain method is more reliable for the study of nonlinear dielectric response compared with frequency domain analysis. A Tikhonov regularization method, which is widely adopted for ill-posed problem, is described for derivation of the relaxation time distribution function, g(τ), from the ferroelectric discharge current in time domain. The new method allows study of the structure variation and the relaxation behavior of ferroelectrics at different temperatures. For barium stannate titanate ceramics (BTS20), g(τ) has been successfully derived; the relaxation peaks move to shorter times with increasing temperature in the range 20–60°C, which may indicate a space charge thermal activation process. However, g(τ) could not be derived from the discharge current by the regularization method for BTS20 at temperatures above 60°C or for lanthanum-doped lead zirconium titanate transparent ceramic (PLZT), since the data do not satisfy the discrete Picard condition, which is a valid criterion for regularization method.     

Dielectric studies of alkyl acrylates with primary alcohols using time domain reflectometry

Binary polar–polar liquid mixtures of alkyl acrylates (methyl acrylate, ethyl acrylate and butyl acrylate) with primary alcohols (propan-1-ol, butan-1-ol and hexan-1-ol) were subjected to dielectric studies at 303?K for different concentrations using time domain reflectometry (TDR) over the frequency range from 10?MHz to 10?GHz. Static permittivity (ε₀) dielectric constant at high frequency (ε_∞) and relaxation time (τ) were found through dielectric measurements for different concentrations of each system. The Bruggeman dielectric factor, Kirkwood correlation factor and the excess inverse relaxation time were determined and discussed to yield information on the molecular interactions of the systems. Deviations from the linearity of various models suggest molecular association through hydrogen bonding between the ?OH group of alcohols and C=O group of esters. The results also show a dependence of dielectric parameters on the alkyl chain length of both the alcohols and esters.     

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.     

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.     

Dielectric relaxation in NH4HSO4 above room temperature

The dispersion curves of the dielectric response of NH₄HSO₄ show that the corrected imaginary part of permittivity, εʺ, and its real part ε′ versus frequency reveal a dielectric relaxation around 9.1 × 10⁵ Hz at 31 °C, which shifts to higher frequencies (∼ 10⁶ Hz) as the temperatures increases. The relaxation frequency shows an activated relaxation process over the temperature range 31–83 °C with activation energy E_a = 0.14 eV, which is close to that derived from the dc conductivity. We suggest that the observed dielectric relaxation could be produced by the H⁺ jump and SO₄⁻ reorientation that cause distortion and change the local lattice polarizability inducing dipoles like HSO₄⁻.     

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).     

Dielectric studies on binary polar mixtures of propanoic acid with esters

It is interesting to see the nature of intermolecular interactions between associative and non-associative polar liquids. Binary polar–polar liquid mixtures of ethyl acetate, ethyl benzoate, ethyl acrylate, ethyl butyrate, n-butyl acetate and benzyl benzoate, each with propanoic acid were subjected to dielectric studies at temperatures 25 °C, 35 °C and 45 °C. Static permittivity (ε_o) and dielectric constant at high frequency (ε_∞) were found through dielectric measurements for different concentrations of each system. The Bruggeman dielectric factor, Kirkwood correlation factor and the excess permittivity were determined. Deviations from the linearity of various models suggest molecular association through hydrogen bonding between the polar–polar constituents of the mixtures. The formation of cyclic and linear α-multimers in the above systems were identified. The results and their temperature dependence were interpreted accordingly.     

Investigation of the low-and infralow-frequency dielectric response of Ba0.7Sr0.3TiO3 thin films

The low-and infralow-frequency dielectric properties of Ba_0.7Sr_0.3TiO₃ thin films annealed at temperatures of 750 and 900°C are investigated over wide ranges of temperatures (from ?180 to +100°C), frequencies (from 0.1 Hz to 10.0 kHz), and amplitudes of the measuring electric field (from 15 to 255 kV/cm). The samples are found to undergo giant relaxation characteristic of layered heterogeneous structures. It is noted that, at a higher annealing temperature (900°C), the relaxation region is shifted toward lower temperatures (higher frequencies).     

Dielectric characterization of semiconducting ZnPc films sandwiched between Gold or Aluminum electrodes

The dependencies of complex dielectric functions (the dielectric constant, ε ₁, and the dielectric loss, ε ₂), on frequency and temperature of zinc phthalocyanine (ZnPc) thin films sandwiched between either gold or aluminum Ohmic-electrode contacts have been investigated in the temperature range of 93–470 K and frequency range 0.1–20 kHz. It is found that both values of ε ₁ and ε ₂ decrease with increasing frequency and increase with decreasing temperature. The rate of change depends greatly on the temperature and frequency ranges under consideration. Around room temperature, neither ε ₁ nor ε ₂ show any appreciable change through the whole range of frequencies. Thus, the dielectric dispersion is found to include of both dipolar and interfacial polarizations. The dependencies of both dielectric functions on frequency at different temperatures were found to follow a universal power law of the form ω ⁿ , where the index 0<n≤?1. This indicates that the correlated barrier hopping (CBH) model is a suitable mechanism to describe the dielectric behavior in ZnPc films. Furthermore, the results of the dielectric response indicate that polarization in these films could be in the form of non-Debye polarization. However, the Debye polarization can be traced below room temperature. The obtained results of the relaxation-time, τ, dependency on temperature have shown that a thermally-activated process may be dominated in ZnPc thin films conduction at high temperatures. Partial phase transition (from α- to β-phase) has been observed around 400 K in molecular relaxation-time, τ, and optical dielectric constant, ε _∞. Arrhenius behavior has been observed for all the dielectric loss and conductivity relaxation-times above room temperature and their activation energies are explained and reported. The optical dielectric constant ε _∞ was found to increase with temperature.     

Investigation of Relaxation Process of Nylon 1212 Using Dielectric Relaxation Spectroscopy

The relaxation processes of α-form nylon 1212 from 50°C up to 160°C were studied by dielectric relaxation spectroscopy (DRS) in a wide frequency range of 63 Hz to 5 MHz. The α relaxation, the electrode relaxation, and the conductivity relaxation of nylon 1212 were observed and analyzed in detail using permittivity and modulus formalism. Electrode polarization and dc conductivity were the origin of high dielectric permittivity values at low frequencies and high temperatures. The strength of the imaginary part of the electric modulus of conductivity relaxation M″ _max was nearly independent of temperature. The distribution of local conductivity and relaxation time became broader with decreasing temperature.     

Dielectric relaxation study of sulfolane in carbon tetrachloride solution from microwave absorption data

The dielectric constant (ɛ′) and dielectric loss (ɛ″) for dilute solutions of sulfolane in carbon tetrachloride solution have been measured at 9.885 GHz at different temperatures viz. 25°C, 30°C, 35°C and 40°C by using standard microwave techniques. Following the single frequency concentration variational method, the dielectric relaxation time (τ) and dipole moment (μ) have been calculated. It is found that dielectric relaxation process can be treated as the rate process, just like the viscous flow. Based on the above studies, monomer structure of sulfolane in carbon tetrachloride has been inferred. Energy parameters (ΔH _g , ΔF _g , ΔS _g ) for dielectric relaxation process of sulfolane in carbon tetrachloride at 25°C, 30°C, 35°C and 40°C have been calculated and compared with the corresponding energy parameters (ΔH _η , ΔF _η , ΔS _η ) for the viscous flow.     

Dielectric relaxation in benzotrihalides at microwave frequencies

The permittivity and dielectric loss of benzotrifluoride and benzotrichloride in benzene and decalin solution have been measured at four microwave frequencies viz., 30.25, 24.50, 18.26 and 9.83 GHz and also at 1 MHz and optical frequency at 35°C. The permittivity and dielectric loss at different frequencies have been plotted against concentration in wt. fraction. The slopes of these straight lines have been used for complex plane plots (a″ vs a′. The dispersion locus for the main dispersion region for both compounds in benzene and decalin are Debye semicircles. The values of relaxation times for overall rotation (τ ₁) and group rotation (τ₂) have been found out and reported. Whereas τ₁ is found to be viscosity dependent, τ₂ is practically independent of viscosity. The relaxation time for group rotation has been found to vary with the frame to which it is attached. Dipole moments of the compounds in both benzene and decalin have been reported.     

Piezoelectric activity and phase transitions in (PMN)0.69(PT)0.31 single crystal

Piezoelectric and dielectric investigations have been performed on a (PMN)_0.69(PT)_0.31 single crystal. Low frequency (100?Hz) dielectric permittivity measurements revealed distinct anomaly at 129°C (T _εmax) corresponding to the structural transformation from the tetragonal to cubic phase. Two other anomalies have been detected at 90 and 96°C. After preliminary polarization in the d.c. electric field, switched on above T _εmax and switched off inside the tetragonal phase, the piezoelectric activity has been observed in function of temperature. Values of the piezoelectric resonance frequencies changed markedly at 96°C (on cooling) and 124°C (on heating) showing clear softening of the elastic properties near these temperatures. Values of the piezoelectric and electromechanical coupling coefficients obtained were respectively of the order of 800?pCN^?1 (d ₃₁) and 0.35?(k ₃₁). Piezoelectric activity was detected tens of degrees above the temperature T _εmax and disappeared at temperature at which the dispersion of the dielectric permittivity due to the presence of polar nanoregions is negligible. It was found that strong softening of the elastic properties accompanies phase transitions to the tetragonal and monoclinic phase.     

Investigation on crystalline structure and dielectric relaxation behaviors of hot pressed poly(vinylidene fluoride) film

The dielectric relaxation behaviors of hot pressed poly(vinylidene fluoride) (PVDF) film have been studied using dielectric spectroscopy in the frequency domain from 20 Hz to 5 MHz at temperatures between 20 °C and 200 °C. Crystalline/amorphous interphase is suggested with methods of FTIR, XRD, and DSC. Frequency and temperature dependence of dielectric spectroscopy reveals the relaxation behavior and structural dynamics of the samples, and three types of relaxation processes are suggested, α_Ac relaxation process contributed by the hopping transport process near the periphery of conduction band or valence zones at Fermi energy, α_c relaxation process related to the structure change of crystal lattice trapped dipoles in crystalline regions, and α_a relaxation process arising from segmental dipole rearrangement of interphases in amorphous regions. Cole-Cole and Havriliak-Negami experimental equations were utilized to analyze these relaxation processes, and differences of Arrhenius parameters for α_Ac and α_c relaxation processes obtained from Cole-Cole and Havriliak-Negami equations were discussed in detail. Activity energy of different relaxation processes obtained from Arrhenius equation and VFT equation indicates non-single thermal activation mechanism for hot pressed PVDF film.     

DC conductivity and dielectric properties of maize starch/methylcellulose blend films

The transient current, electrical conductivity, dielectric constant (ε′), and dielectric loss factor (ε″) of starch and methylcellulose homopolymers and their blends with various compositions were studied under different conditions. The x-ray diffraction pattern was obtained for individual polymers and 50:50 wt/wt% blend sample to identify both the structure and degree of crystallinity. From transient current, the ionic and electronic transfer number as well as charge carrier density and drift mobility were determined. The values of activation energy in the temperature range 30–90 °C indicate that the conduction mechanism is due to combined electronic and ionic processes, while in the temperature range 100–160 °C, electronic contribution is predominant. The complex dielectric data of the present samples in an extended frequency and temperature range appear as different relaxation processes, which are connected with polymer dynamics.     

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.     

On the electric properties of ice doped with NH4F

Measurements of the dielectric constant and the electric conductivity of ice doped with about 10^?2N NH₄F led to an activation energy of the relaxation time of 0.10 eV=2.4 kcal/Mol. Despite the fact that the relaxation times of pure and doped ice are about the same at temperatures close to ?10°C, the statement ofDengel et al. [1], that NH₄F doping does not affect the dielectric relaxation, cannot be maintained in view of the large difference in activation energies.     

Enhanced energy storage in polyvinylidenefluoride (PVDF) + BaZrO<Subscript>3</Subscript> electroactive nanocomposites

PVDF + BaZrO₃ electroactive nanocomposite thin film has been prepared by solution casting method. The structural analysis was carried out by using x-ray diffraction pattern and atomic force microscopy (AFM). Generally, the performance of dielectric capacitors toward higher energy density and higher operating temperatures has been drawing increased interest. In this regard, the present study was focussed on the fabrication and characterization of PVDF + BaZrO₃ electroactive nanocomposites in view of enhancing the energy density at elevated temperature. Cole-Cole plot is an agreement with multiple relaxation process in electroactive nanocomposites. Dielectric energy storage performance is assessed for PVDF nanocomposites with different wt% of BaZrO₃ at different frequencies and temperature. It has been observed that with increase of temperature, the permittivity increased while the energy density slightly decreased but significantly higher than pure polymer PVDF. A high energy density of 6.88 J/cm³ was obtained for BaZrO₃ electroactive nanocomposites at 50 °C and 5.06 J/cm³ at 70 °C. Overall, the testing results indicate that using nanocomposites of PVDF and BaZrO₃ as a dielectric component is promising for implementation to preserve high energy density values up to temperatures of 70 °C.The enhancement of dielectric permittivity and the energy density is attributed due to increase of interracial charge density. The effect of BaZrO₃ nanoparticles in energy density of PVDF is first time reported.