Temperature Dependent Dielectric Relaxation Research Articles

Effect of Eu and Mn co-doping on temperature dependent dielectric relaxation behaviour and electric conduction mechanisms of bismuth ferrite

Effect of Eu and Mn co-doping on temperature dependent dielectric relaxation behaviour and electric conduction mechanisms of bismuth ferrite

Temperature dependent dielectric relaxation and current conduction mechanism in Ba and Ti co-doped bismuth ferrite ceramic

Temperature dependent dielectric relaxation and current conduction mechanism in Ba and Ti co-doped bismuth ferrite ceramic

A study on temperature dependent dielectric relaxation behaviour and conduction mechanism of La and Ti co-doped bismuth ferrite

A study on temperature dependent dielectric relaxation behaviour and conduction mechanism of La and Ti co-doped bismuth ferrite

Temperature-dependent dielectric relaxation measurements of (acetamide + K/Na SCN) deep eutectic solvents: Decoding the impact of cation identity via computer simulations.

The impact of successive replacement of K+ by Na+ on the megahertz-gigahertz polarization response of 0.25[fKSCN + (1 - f)NaSCN] + 0.75CH3CONH2 deep eutectic solvents (DESs) was explored via temperature-dependent (303 ≤ T/K ≤ 343) dielectric relaxation (DR) measurements and computer simulations. Both the DR measurements (0.2 ≤ ν/GHz ≤ 50) and the simulations revealed multi-Debye relaxations accompanied by a decrease in the solution static dielectric constant (ɛs) upon the replacement of K+ by Na+. Accurate measurements of the DR response of DESs below 100MHz were limited by the well-known one-over-frequency divergence for conducting solutions. This problem was tackled in simulations by removing the zero frequency contributions arising from the ion current to the total simulated DR response. The temperature-dependent measurements revealed a much stronger viscosity decoupling of DR times for Na+-containing DES than for the corresponding K+ system. The differential scanning calorimetry measurements indicated a higher glass transition temperature for Na+-DES (∼220K) than K+-DES (∼200K), implying more fragility and cooperativity for the former (Na+-DES) than the latter. The computer simulations revealed a gradual decrease in the average number of H bonds (⟨nHB⟩) per acetamide molecule and increased frustrations in the average orientational order upon the replacement of K+ by Na+. Both the measured and simulated ɛs values were found to decrease linearly with ⟨nHB⟩. Decompositions of the simulated DR spectra revealed that the cation-dependent cross interaction (dipole-ion) term contributes negligibly to ɛs and appears in the terahertz regime. Finally, the simulated collective single-particle reorientational relaxations and the structural H-bond fluctuation dynamics revealed the microscopic origin of the cation identity dependence shown by the measured DR relaxation times.

Engineered nanocomposites through embedding of smaller “organic inorganic” nanoparticles in thermoplastic Poly(2-Vinylpyridine) polymer matrix

Polymer nanocomposites (PNCs) are significant for modern and future applications owing to their multifunctionality promoted by morphology and tailored interfaces between the constituents. However, ‘forward’ engineered polymer (host) composites with smaller size nanoparticles (guest) providing desired properties remains challenging as they depend upon nanoparticles aggregation, size, shape, and loading (volume or weight) fraction. This study strategically designs and develops PNCs comprising thermoplastic poly (2-vinylpyridine) (P2VP) polymer matrix impregnated with spherical polyhedral oligomeric silsesquioxane (N-POSS) nanoparticles (diameter ∼2–5 nm) and anisotropic planar nitrogenated graphene nanoribbons (GNR, strip width ∼5–10 nm) commensurate with polymer chain radius of gyration, Rg, (or segment length ∼1.5 nm) and comparable energy scales of electrostatic interaction and attractive hydrogen bonding. We investigated static and dynamic structure and thermophysical properties to correlate with interfacial regions and the results are compared with larger graphene oxide (GO, lateral dimension ∼100–200 nm) nanosheets and silica (SiO2, ∼25–50 nm) particles. While electron microscopy revealed nanoparticle distribution, the lattice bonding, conjugation length, and mechanical properties are determined from micro-Raman spectroscopy and atomic force microscopy, respectively. The differential scanning calorimetry provided a measure of glass transition temperature, Tg, with positive shift of ∼10–18 °C with nanoparticles loading indicating strength of structural relaxation/chain rigidity behavior and thermogravimetric analysis displayed increased thermal stability and conductivity (decreased interfacial resistance). We also measured temperature dependent dc electrical conductivity and dielectric relaxation spectroscopy gaining insights into percolation and dynamic interfacial layer. This study signified understanding of interactions and interfacial regions, key element to demystify the microscopic structure-property relationships.

First-principles and experimental study of structural, electronic, and enhanced dielectric response in Bi2Ca1.95Sm0.05CoO6 nanoparticles

In this study, we synthesized Bi2Ca1.95Sm0.05CoO6 (BCSCO) by the Co-precipitation route. X-ray diffraction was used for structural analysis, which confirmed the monoclinic structure with space group P21/m. Here, we employ the CASTEP (Cambridge Serial Total Energy Package) approach, we conducted a theoretical investigation of the structure, electronic, and optical properties of BCSCO double perovskites. FTIR spectra, BCSCO presents three absorption bands that correspond to the Bi(Ca)-O, O-Co-O, and Co-O. The morphological study showing the agglomeration phenomenon has occurred in the synthesized sample. The AC conductivity and dielectric response have also been studied as a function of frequency (100 Hz-3 MHz) at different temperatures (100 °C-600 °C). Temperature-dependent dielectric relaxation was investigated, and employing the non-linear Debye fitting to determine the spreading factor and relaxation time. The maximum value of the dielectric constant is 2.4 × 106 at 600 °C. AC conductivity is examined at (100 °C-600 °C) using Jonscher’s power law. The model fitting shows the Overlapping Large Polaron Tunneling conduction mechanism for BCSCO. In order to explore the impact of grain barriers and interior, the Nyquist plot was utilized, and the results are inter-connected.

Temperature dependent dielectric relaxation spectroscopy of amyl acetate-xylene solutions – An approach to molecular and co-operative dynamics

Dielectric relaxation parameters of AMA-Xylene solutions have been investigated thoroughly to discern the associativeness as well as heterogeneous behavior among the hetero molecules in the solutions such that dielectric constant (εo) and relaxation time (τ) of solutions has been determined. Complex permittivity spectra (CPS) for Amyl Acetate (AMA)-Xylene solutions were measured in 10 MHz–50 GHz frequency range using Time domain reflectometry (TDR) technique. It is exciting to explore the cooperative nature and association between AMA-Xylene. With co-operative domains (CDs), dynamics in AMA-AMA and AMA-Xylene molecules have been explicated while Kirkwood validates CDs with diverse exchanges through bonding. The experimental values of εo are compared with theoretical values obtained from the molecular parameters suggested by the Luzar. Thermodynamic parameters for AMA-Xylene show positive values of Enthalpy and Entropy for all concentrations, indicating that the system is endothermic and less ordered. Gibbs free energy decreases with increase in volume fraction of amyl acetate (VAMA).

Dynamic memory tuned by frequency in a homologous thermotropic liquid crystal.

With scaling of dynamic RAM and NAND memory technologies reaching a limit, there is a need for dynamic memory with high density. In this work, an investigation on existence of dynamic memory feature in a frequency tuned homologous series of thermotropic liquid crystals has been carried out. A homologues series of five thermotropic liquid crystalline compounds comprising of 4-butyl benzoic acid and various alkyloxy benzoic acids are prepared, and all these mesogens exhibit only nematic phase. Liquid crystal dynamic memory storage setup consists of a conducting transparent glass cell with two indium tin oxide coated transparent glass plates acting as electrical electrodes in which the selected thermotropic liquid crystal is filled by capillary action. The temperature dependent dielectric relaxation studies enable to elucidate the relaxation frequency of each of these mesogens in nematic phase. The liquid crystal at different temperatures is excited with the relaxation frequency at various chosen fields, and the dielectric hysteresis is recorded. The magnitude of the hysteresis loop is directly proportional to the memory storage capacity. The main objective of this work is observation of dynamic memory storage in liquid crystals exhibiting nematic phase, at different frequencies in a thermotropic liquid crystal as the ingredient in a conducting polyamide buffed glass cell excited by an external electrical dc stimulus. The variation of the hysteresis loop with varying field; temperature and frequency are also studied and reported in this work.

The Nature of the Low-Temperature Crossover of Water in Hard Confinement.

The dynamics of water confined in mesoporous MIP (2-3 nm pores in size) with silica gel (secondary silica; further, the abbreviation SG will be used) and MAP (10-35 nm pores in size) without SG borosilicate glasses have been studied by broadband dielectric spectroscopy (BDS), nuclear magnetic resonance (NMR), and differential scanning calorimetry (DSC). MIP samples contain secondary silica inside the pores and provide a confinement size of about 2-3 nm, whereas MAP samples are free of secondary silica and provide a confinement size of about 10-35 nm. It is shown by BDS and NMR techniques that water exhibits a dynamic crossover of around 180 K when it is confined in MIP samples. By contrast, water confined in larger pores (MAP) does not exhibit any changes in its relaxation behavior. It is also shown that the crossover temperature depends on the hydration level (the higher the hydration level, the lower the crossover temperature). Below the crossover temperature, we find that water reorientation is isotropic (NMR) and that the temperature-dependent dielectric relaxation strength (BDS) follows the tendency expected for a solid-like material. In contrast, water reorientation is related to long-range diffusion above the crossover temperature, and the dielectric relaxation strength follows the tendency expected for a liquid-like material. Furthermore, the calorimetric results are compatible with crossing a glass transition near 180 K. Finally, the results are discussed within the Gibbs-Thomson model. In this framework, the crossover could be related to ice crystals melting.

Small polaron hopping transport mechanism, dielectric relaxation and electrical conduction in NiAl2O4 electro-ceramic spinel oxide

In this study, the frequency and temperature dependent dielectric relaxation and electrical conduction mechanisms in NiAl2O4 spinel oxide ceramic have been explored in a frequency range of over a measured temperature from 163–283 K. The polycrystalline NiAl2O4 was synthesized via solid state reaction route and sintered at 1000 °C. The room temperature x-ray powder diffraction pattern confirmed the formation of NiAl2O4 spinel phase with Fd3m space group. The surface morphology of the sample was investigated by scanning electron microscopy and chemical properties by Fourier transform infrared spectroscopic analysis. Complex impedance studies revealed the presence of relaxation time distribution and charge carriers were found to be thermally activated. The Nyquist plots exhibited depressed semicircles and their fitting by an equivalent circuit model with configuration (RGCG)(RGBCGB) resolved the contributions of grains and grain-boundaries to the electrical transport properties of the material. Electrical conductivity analysis followed the Jonscher’s power law behavior and the frequency exponent suggested small polaron hopping as the governing transport mechanism in NiAl2O4 spinel oxide. Non-Debye type nature of dielectric relaxation was confirmed by the complex modulus analysis whereas dielectric constant and tangent loss analysis verified that the hopping mechanism was thermally activated.

Formation of silver particles in [PVA:CS:PEG]-AgNO3 based biopolymer electrolyte membranes: Structural and electric transport properties study

[Chitosan (CS)-poly(vinyl) alcohol (PVA)-polyethylene glycol (PEG-200)]+xwt% silver nitrate (AgNO3) (x = 0, 10, 20, 30, 40) based biopolymer blend electrolytes (BPBEs) were prepared using solution casting method. FTIR results show the interaction of Ag+/NO3− with the constituents of polymers CS/PVA. XRD results reveal that the amorphousness increases with increasing AgNO3 concentration. Optical morphological (OM) images show that the silver, Ag(o) particles are agglomerated on the surface of the membrane. Temperature dependent dc conductivity (σdc) and dielectric relaxation frequency (fr) for BPBEs follow the Arrhenius type behavior and the sample containing 30 wt% salt has optimum dc conductivity, σdc∼1.7×10−4 S/cm at 30oC with lowest activation energy∼ 0.16 eV. The ac conductivity spectra follow the Jonscher's power law (JPL) with power law exponent, s > 1. The scaling of AC conductivity and loss tangent (tanδ) spectra were performed with respect to temperatures/concentrations of salt. The dielectric permittivity study reveals that the electrode polarization effect predominates at low frequencies. The Ionic Transference Number (ITN) measurement was used to determine the nature species of charge carrier, either ionic or electronic. The linear sweep voltammetry (LSV), result shows that 30% AgNO3containing sample has the electrochemical stability window (ESW) ∼+1.5 to -1.5 V.

Effect of CoFe2O4 on Dielectric and Conduction Behavior Pb0.75La0.25TiO3 Based Composites

(1-x) (Pb0.75La0.25TiO3)-x (Co2FeO4) where x = 0.50 & 0.60 Ceramic Composites have been successfully synthesized via mechanical mixing method. The substitution of CoFe2O4 with La3+ modified Lead Titanate (Pb0.75La0.25TiO3) in above mentioned stoichiometric proportions on has been explored for temperature dependent electrical properties. The both real and imaginary parts of dielectric permittivity decreases with increasing both temperature as well as ferrite content. The real part of impedance decreases with increasing temperature as well as Co2FeO4 content whereas maxima in imaginary part reveals the presence of temperature dependent dielectric relaxation. Both conductivity as well as dielectric loss increases with increase in Co2FeO4 content in stoichiometric proportion.

Effect of CoFe2O4 on Dielectric and Conduction Behavior Pb0.75La0.25TiO3 Based Composites

(1-x) (Pb0.75La0.25TiO3)-x (Co2FeO4) where x = 0.50 & 0.60 Ceramic Composites have been successfully synthesized via mechanical mixing method. The substitution of CoFe2O4 with La3+ modified Lead Titanate (Pb0.75La0.25TiO3) in above mentioned stoichiometric proportions on has been explored for temperature dependent electrical properties. The both real and imaginary parts of dielectric permittivity decreases with increasing both temperature as well as ferrite content. The real part of impedance decreases with increasing temperature as well as Co2FeO4 content whereas maxima in imaginary part reveals the presence of temperature dependent dielectric relaxation. Both conductivity as well as dielectric loss increases with increase in Co2FeO4 content in stoichiometric proportion.

Impact and structure of water in aqueous octanol mixtures: Hz-GHz dielectric relaxation measurements and computer simulations

Temperature (283 ≤ T/K ≤ 323) dependent dielectric relaxation (DR) measurements of aqueous binary mixtures of octanol at three different water mole fractions (XH2O = 0.05, 0.10, 0.20) were performed employing two different frequency windows: 0.00002 ≤ν/MHz≤ 10 and 0.2 ≤ν/GHz≤ 50. In addition, DR measurements were carried out for pure octanol and water saturated octanol at 298 K. All these measurements showed, irrespective of solution temperature, a small decrease of the static dielectric constant (εs) upon addition of water in octanol. Two-step relaxation process with time constants ∼ 3–0.3 ns and ∼ 120–40 ps characterized the measured DR spectra with no signature of bulk water-like DR time constant (∼10 ps). Differential scanning calorimetric (DSC) measurements of octanol + water mixtures reflect only water concentration dependent depression of octanol freezing temperature. Our computer simulations of aqueous octanol mixtures with SPC/E water suggests a dramatic decrease of the average number of water-water H-bonds 〈NHBw-w〉 per water molecule and a spectacular increase of water populations possessing OOO angles distributed over 0°≤θ≤ 60°. Consequently, a negative value for the average tetrahedral order parameter (〈Q〉) and an εs as low as ∼ 2 for water have been predicted. A severe damage to the global tetrahedrality of water in these mixtures has been predicted and the angle distributions corresponding to negative and positive Q values explicitly shown. These simulation results therefore explain the microscopic origin for small effects of water at low mole fractions on εs of octanol + water binary mixtures.

Temperature-dependent dielectric relaxation and hydrophobicity of aqueous alanine using time domain reflectometry

Physical, chemical and microbiological stability of the materials is affected by the rotational and translational mobility of free and hydrated water. The role of water in areas such as protein hydration and enzyme activity, food technology, lyophilization and polymers hydration is, therefore, important and can be well understood in terms of dielectric relaxation spectroscopy. Concentration and temperature-dependent hydrophobicity of amino acid is reflected in their tendencies to appear in appropriate positions in proteins. Therefore, to gain more insights on the temperature and concentration dependence of hydrophobicity and structural properties of amino acid, dielectric relaxation of aqueous alanine have been studied in the temperature region 303.15 K to 278.15 K. Time domain spectroscopy have been used in the frequency range of 10 MHz to 30 GHz and in the concentration range 0.18708 ≤ c/M ≤ 0.74831. Two relaxation processes namely the low-frequency relaxation (l) and the high-frequency relaxation (h) has been detected for the aqueous alanine. Dielectric parameters such as static dielectric constant (εj ), relaxation time (τj ) dipole moments (û) and correlation factor (g) have been studied to investigate molecular interaction between alanine and water. The number of water molecules irrotationally bond by the solute molecules (Z ib) was also determined to examine the hydrophobicity of alanine which was found more hydrophobic towards low temperatures and concentrations. Thermodynamic parameters calculated are also supported well for the hydrophobic behaviour of alanine towards low temperatures and concentrations. Communicated by Ramaswamy H. Sarma

Temperature Dependent Dielectric Relaxation Studies of 2-Nitrotoluene-DMSO mixture using Time Domain Relectometry from 10MHz to 50GHz

The dielectric relaxation properties of 2-Nitrotoluene (2-NT) with DMSO for 11 different concentrations has been studied in the frequency range from 10 MHz to 50 GHz using time domain reflectometry (TDR) method. In this frequency range Dielectric relaxation spectra of 2-NT-DMSO mixtures shows Debye type behavior. The temperature dependent static dielectric constant and relaxation time have been determined from 20oC to 5oC. Effective Kirkwood correlation factor is calculated to determine the effect of strong directional forces such as microwaves on heterogeneous molecules under different temperatures. The excess permittivity and excess inverse excess relaxation time is found to be negative for 2-NT-DMSO system with weak molecular interactions. The activation enthalpy have been calculated to find the energy required to rotate the molecules

Study of Thermodynamic and Dielectric Parameters of Xylene and Its Isomers Using Time Domain Dielectric Spectroscopy

Raw complex permittivity data of pure aromatic hydrocarbons such as Xylene, O-Xylene (O-X), M-Xylene (M-X), and P-Xylene (P-X) have been measured for different temperatures in 10 MHz to 50 GHz frequency range using Time Domain Dielectric Spectroscopy (TDDS). Dielectric relaxation for above systems has been characterized by the Debye type spectral relaxation. The dielectric parameters such as static dielectric constant, relaxation time, Kirkwood correlation factor have been determined using the non-linear least square fit method. Effect of O-, M-, and P- substitution of CH3 group in xylene causes variation in static dielectric constant values and spectacle deviation in relaxation time with respect to temperature. The temperature dependent dielectric relaxation gives expected Arrhenius behavior.

Dielectric relaxation and scaling of AC conductivity observed in mixed valence perovskite Eu2CoMnO6

Monophasic and polycrystalline double perovskite Eu2CoMnO6 has been synthesized, and its structural characterization, frequency and temperature-dependent dielectric relaxation have been studied. Observed thermally activated dielectric relaxation was explained using the empirical Havriliak–Negami (HN) dielectric relaxation function with an estimated activation energy [Formula: see text] [Formula: see text] 0.22 eV and attempt frequency [Formula: see text] [Formula: see text] 2.46 × 109 Hz. The frequency-dependent AC conductivity data, over a wide range of temperature (100–325 K), followed the empirical universal power law behavior ([Formula: see text], [Formula: see text] is the constant exponent) showing two different frequency exponents, respectively, in the high- and low-temperature regions. The high-temperature ([Formula: see text] 275 K) conductivity data followed the continuous time random walk (CTRW) approximation model proposed by Dyre. However, this model failed to reproduce the observed conductivity spectra in the low-temperature side ([Formula: see text] 200 K). Interestingly, both the high- and low-temperatures’ conductivity data can be scaled to the master curve with suitably chosen scaling parameters.

Dielectric relaxation study of 1-pentanol–ethanol binary mixtures at 10 MHz–50GHz frequency range using TDR technique

ABSTRACT The dielectric measurements have been executed by making the use of time domain reflectometry (TDR) technique for 1-pentanol and ethanol in the pure form and for their binary liquid mixture in the frequency interim of 10 MHz–50 GHz at varying temperatures, respectively. The complex permittivity spectra studied show Debye behaviour and plotted as the function of frequency. The temperature-dependent dielectric constant and relaxation time values were estimated. The Kirkwood correlation factor (g eff) has also been studied to determine the alignment of dipole moments in mixture. The thermodynamic parameters and temperature-dependent behaviour of relaxation time, i.e. Arrhenius plot, have been studied.

Temperature dependent Broadband dielectric relaxation study of Aqueous Polyvinylpyrrolidone (PVP K-15, K-30 & K-90) using a TDR

ABSTRACT Temperature-dependent dielectric relaxation studies of different viscosity grade Polyvinylpyrrolidones (PVP), PVP K-15, PVP K-30 and PVP K-90 having molecular weight 10,000 gmol−1, 40,000 gmol−1 and 360,000 gmol−1 respectively has been done in the frequency region 10 MHz to 50 GHz using Time domain reflectometry (TDR) technique. The frequency-dependent complex dielectric permittivity spectra have been explored by the Havriliak-Negami expression and is explained by the single relaxation model. The PVP molar concentration comprises the concentration domain of 0.0017 ≤ c/M ≤ 0.0176 for PVP-water system. The values of static dielectric constant (ε0), relaxation time (τ) and the empirical parameter (β) have been determined using non-linear least squares fit method along with the thermodynamic properties (activation enthalpy, entropy and free energy) of aqueous solutions of polymers.