Dielectric Dispersion Study of Poly(vinyl Pyrrolidone)–Polar Solvent Solutions in the Frequency Range 20 Hz–1 MHz

Influence of polar solvents environment and polymer concentrations on the electrical properties (complex dielectric constant, ac electrical conductivity, complex electric modulus and complex impedance) of the solutions of poly(vinyl pyrrolidone) (PVP) in polar solvents, namely water, ethyl alcohol, ethylene glycol, diethylene glycol, poly(ethylene glycol), glycerol, dimethyl sulfoxide and dimethyl formamide, have been investigated in the frequency range 20 Hz–1 MHz at 25°C. Comparative analysis of the dielectric dispersion curves confirms that the solvent molecular size and number of its hydroxyl groups, and the solutions viscosity, are the major factors which governs the PVP chain segmental motion. The ionic conduction and electrode polarization phenomena has a dominant influence on the large increase of complex dielectric constant values of the solutions of PVP‐polar solvent in the lower frequency region. The values of relaxation times corresponding to these phenomena are also reported.     

Effect of melt compounding temperature on dielectric relaxation and ionic conduction in PEO–NaClO<Subscript>4</Subscript>–MMT nanocomposite electrolytes

Polymer nanocomposite electrolytes (PNCEs) of poly(ethylene oxide) and sodium perchlorate monohydrate complexes with montmorillonite (MMT) clay up to 20 wt.% MMT concentration of poly(ethylene oxide) (PEO) are synthesized by melt compounding technique at melting temperature of PEO (∼70 °C) and NaClO₄ monohydrate (∼140 °C). Complex dielectric function, electric modulus, alternating current (ac) electrical conductivity, and impedance properties of these PNCEs films are investigated in the frequency range 20 Hz to 1 MHz at ambient temperature. The direct current conductivity of these materials was determined by fitting the frequency-dependent ac conductivity spectra to the Jonscher power law. The PNCEs films synthesized at melting temperature of NaClO₄ monohydrate have conductivity values lower than that of synthesized at PEO melting temperature. The complex impedance plane plots of these PNCEs films have a semicircular arc in upper frequency region corresponding to the bulk material properties and are followed by a spike in the lower frequency range owing to the electrode polarization phenomena. Relaxation times of electrode polarization and ionic conduction relaxation processes are determined from the frequency values corresponding to peaks in loss tangent and electric modulus loss spectra, respectively. A correlation is observed between the ionic conductivity and dielectric relaxation processes in the investigated PNCEs materials of varying MMT clay concentration. The scaled ac conductivity spectra of these PNCEs materials also obey the ac universality law.     

Dielectric spectroscopy and confirmation of ion conduction mechanism in direct melt compounded hot-press polymer nanocomposite electrolytes

Solid-type polymer nanocomposite electrolyte (PNCE) comprising poly(ethylene oxide) (PEO), lithium perchlorate (LiClO₄) and montmorillonite (MMT) nano-platelets were synthesized by direct melt compounded hot-press technique at 70 °C under 3 tons of pressure. The spectra of complex dielectric function, electric modulus and alternating current (ac) electrical conductivity, and complex impedance plane plots of these materials were investigated in the frequency range 20 Hz to 1 MHz at ambient temperature. The variation of electrode polarization and ionic conduction relaxation times with MMT concentration up to 20 wt.% confirms their strong correlation with direct current ionic conductivity. The predominance of exfoliated MMT structures in PEO matrix and their effect on cation conduction mechanism and ion pairing were discussed by considering a supramolecular transient cross-linked structure. The normalized ac conductivity as a function of scaled frequency of these PNCE materials obey the universal time–concentration superposition behaviour alike the disordered solid ionic conductors.     

Dielectric Relaxations and Structures of Nanoclay in Solution Cast Poly(Ethylene Oxide)– Montmorillonite Clay Nanocomposites

The relative complex dielectric function, electric modulus and alternating current electrical conductivity spectra and complex impedance plane plots of aqueous solution cast poly(ethylene oxide)–montmorillonite clay (PEO–MMT) nanocomposite films were investigated over the frequency range 20 Hz to 1 MHz at ambient temperature. The intercalated and exfoliated structures of nanoclay dispersed in PEO matrix were recognized by the significant change in real part of dielectric function with clay concentration in the range 0%–20 wt%. The relaxation times corresponding to PEO chain segmental motion and ionic conduction relaxation processes were used to explore the interactions compatibility between PEO molecules and the dispersed MMT clay nanoplatelets and their effect on PEO chain dynamics. Real part of conductivity spectra of these nanocomposites over five decades of frequency has nonlinear behavior, which is influenced by the MMT clay concentration. The complex impedance plane plots confirm the bulk properties of these nanocomposites over the experimental frequency range.     

Conductivity and dielectric relaxation of Li salt in poly(ethylene oxide) and epoxidized natural rubber polymer electrolytes

Two types of polymer electrolytes were studied: poly(ethylene oxide) (PEO) and epoxidized natural rubber (ENR) both filled with lithium perchlorate. Universal dielectric behavior and impedance relaxation were investigated at room temperature over a wide range of salt concentration. Complex impedance plots exhibit one semicircle in some cases (PEO polymer electrolytes) with an extended spike at low frequencies. This implies a double layer capacity strongly influences conductivity at low frequencies. In the ENR–salt system, semicircles can be obtained only at very high concentrations. This points towards stable resistor dominated networks only develop at very high salt concentrations for this system. Centers of the semicircles lie below real axis indicating non-Debye dielectric relaxation. The relaxation peak broadens and shifts to higher frequencies with increasing salt content. It indicates that the relaxation time of polarization relaxations decreases with ascending salt content. Relaxations occur at extremely low salt concentrations in PEO and only at very high salt concentrations in ENR. Hence, conductivity of ENR–salt is one to two orders of magnitude lower as for PEO–salt.     

Dielectric properties and fluctuating relaxation processes of poly(methyl methacrylate) based polymeric nanocomposite electrolytes

Solid polymer nanocomposite electrolytes (SPNEs) consisted of poly(methyl methacrylate) (PMMA) and lithium perchlorate (LiClO₄) of molar ratio C=O:Li⁺=4:1 with varying concentration of montmorillonite (MMT) clay as nanofiller have been prepared by classical solution casting and high intensity ultrasonic assisted solution casting methods. The dielectric/electrical dispersion behaviour of these electrolytes was studied by dielectric relaxation spectroscopy at ambient temperature. The dielectric loss tangent and electric modulus spectra have been analyzed for relaxation processes corresponding to the side groups rotation and the segmental motion of PMMA chain, which confirm their fluctuating behaviour with the sample preparation methods and also with change of MMT concentration. The feasibility of these relaxation fluctuations has been explained using a transient complex structural model based on Lewis acid–base interactions. The low permittivity and moderate dc ionic conductivity at ambient temperature suggest the suitability of these electrolytes in fabrication of ion conducting electrochromic devices and lithium ion batteries. The amorphous behaviour and the exfoliated/intercalated MMT structures of these nanocomposite electrolytes were confirmed by X-ray diffraction measurements.     

Effects of plasticizer and nanofiller on the dielectric dispersion and relaxation behaviour of polymer blend based solid polymer electrolytes

Solid polymer electrolytes consisted of poly(ethylene oxide) (PEO) and poly(methyl methacrylate) (PMMA) blend (50:50 wt/wt%) with lithium triflate (LiCF₃SO₃) as a dopant ionic salt at stoichiometric ratio [EO + (CO)]:Li⁺ = 9:1, poly(ethylene glycol) (PEG) as plasticizer (10 wt%) and montmorillonite (MMT) clay as nanofiller (3 wt%) have been prepared by solution cast followed by melt–pressing method. The X–ray diffraction study infers that the (PEO–PMMA)–LiCF₃SO₃ electrolyte is predominantly amorphous, but (PEO–PMMA)–LiCF₃SO₃–10 wt% PEG electrolyte has some PEO crystalline cluster, whereas (PEO–PMMA)–LiCF₃SO₃–10 wt% PEG–3 wt% MMT electrolyte is an amorphous with intercalated and exfoliated MMT structures. The complex dielectric function, ac electrical conductivity, electric modulus and impedance spectra of these electrolytes have been investigated over the frequency range 20 Hz to 1 MHz. These spectra have been analysed in terms of the contribution of electrode polarization phenomenon in the low frequency region and the dynamics of cations coordinated polymer chain segments in the high frequency region, and also their variation on the addition of PEG and MMT in the electrolytes. The temperature dependent dc ionic conductivity, dielectric relaxation time and dielectric strength of the plasticized nanocomposite electrolyte obey the Arrhenius behaviour. The mechanism of ions transportation and the dependence of ionic conductivity on the segmental motion of polymer chain, dielectric strength, and amorphicity of these electrolytes have been explored. The room temperature ionic conductivity values of the electrolytes are found ∼10⁻⁵ S cm⁻¹, confirming their use in preparation of all-solid-state ion conducting devices.     

The conductivity and dielectric studies of solid polymer electrolytes based on poly (acrylamide-co-acrylic acid) doped with sodium iodide

Solid polymer electrolyte thin films based on polyacrylamide-co-acrylic acid (PAAC) doped with sodium iodide (NaI) with different ratios of polymer and salt added with fixed amount of additive of propylene carbonate (PC) were prepared by using solution casting method. The PC was added to the mixture of the solution to provide more flexibility to the polymer film by increasing the plasticity of the thin film membrane. The conductivity and dielectric studies were carried out on these thin films to understand the ion transport properties of the polymer electrolytes. The highest conductivity obtained was 1.88?×?10^?5 S cm^?1 for the 30% NaI salt-doped polymer electrolyte system at room temperature. The temperature-dependent conductivity agrees with Arrhenius relationship which shows that hopping mechanism of ions in the polymer matrix. The dielectric properties especially the loss tangent used to analyze the segmental relaxation of the polymer chain as more concentration of salt was incorporated. The electric modulus was studied to understand the electrical relaxation processes to overcome electrode polarization effect.     

ZnO nanoparticles dispersed PVA–PVP blend matrix based high performance flexible nanodielectrics for multifunctional microelectronic devices

Polymer nanocomposite (PNC) films based on the blend matrix of poly(vinyl alcohol) (PVA) and poly(vinyl pyrrolidone) (PVP) (50/50 wt%) incorporated with zinc oxide (ZnO) nanoparticles (i.e., (PVA–PVP)–x wt% ZnO; x = 0, 1, 3 and 5) were prepared by solution-cast method. The behaviour of polymer-polymer and polymer-nanoparticle interactions in the PNC films was ascertained by employing X-ray diffraction, energy dispersive X-ray, and Fourier transform infra-red spectroscopies. Scanning electron microscopy and atomic force microscopy were performed for the morphological characterization, whereas the thermal and optical properties of the PNC films were investigated by using differential scanning calorimetry and ultraviolet–visible spectroscopy, respectively. The dielectric and electrical behaviour of these PNC materials were determined by employing the dielectric relaxation spectroscopy over the frequency range from 20 Hz to 1 MHz. The influence of ZnO concentration on the degree of PVA crystalline phase and the crystallite size, surface morphology and roughness of the films, the glass phase transition and melting phase transition temperatures, direct and indirect optical energy band gap, refractive index, complex permittivity, electrical conductivity, activation energy and the structural dynamics of these PNC materials were explored. The investigated properties of the PNC films were credited to an innovation and engineering of novel high performance flexible nanodielectrics in the area of advanced functional materials for their promising applications especially in the next generation optoelectronic, gas sensor and microelectronic devices.     

Investigation of the effect of gamma rays on electrical properties of chlorinated poly (vinyl chloride)

Dielectric constant, dielectric loss and AC conductivity were measured, in the frequency range 100 Hz to 5 MHz in chlorinated poly (vinyl chloride) (CPVC) before and after exposure to gamma irradiation at doses between 5.0 KGy and 50.0 KGy. The frequency dependencies of ε′, ε″ and σ_AC at 30 °C were investigated. A relaxation peak in the dielectric loss and a corresponding step in the dielectric constant have been observed, in the frequency ranges 10³ Hz to 10⁴ Hz. The dielectric constant ε′, dielectric loss ε″ and AC conductivity σ_AC are also found to increase at heating up to 100 °C. In addition the effect of gamma irradiation on the frequency dependencies of ε′, ε″ and σ_AC was measured at room temperature. The gamma irradiation leads to an increase in the efficiency of soft segments. Furthermore, the DC electrical conductivity of both the irradiated and non-irradiated samples was investigated. The induced electrical conductivity and the activation energy were measured, at various temperatures, as a function of gamma dose. It was found that the gamma radiation has a definite effect on the DC conductivity of the CPVC polymer.     

Dielectric relaxation in PEO-based polymer electrolytes

Dielectric properties of cross-linked poly(ethylene oxide) (PEO) with different mesh sizes, doped with lithium salt lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), have been studied in frequency region between 0.1 and 10⁷ Hz and in broad temperature range. Results were compared with linear PEO of 1000 g/mol. Dielectric responses of the systems are dependent on frequency and thermally activated. Systems exhibit different responses in semi-crystalline and molten state. Increase of temperature promotes polarization; whereas, increase of frequency lessens it. In other words, polarization is thermally activated and local conductivity reduced. Generally, one observes enhanced dc conductivity in linear PEO as compared to cross-linked PEO at high temperature and the opposite at low temperature. Resonance responses are observed in low-molecular cross-linked PEO and in linear PEO at low temperature. These responses lead to splitting of polarization relaxation at frequencies beyond low-frequency range. Salt-comprising systems display only relaxation-type dielectric response. Imaginary parts of response spectra show distribution of relaxation times. It turns out that this distribution is independent of temperature in the low-frequency range, but depends on concentration of salt in the cross-linked polymer. In both systems, neat cross-linked and linear polymer of low-molecular mass, one observes coexistence of non-local and local motions of charged entities even at very low temperature.     

Dielectric relaxation in poly(ethylene oxide) complexed with alkali metal perchlorates

Audio frequency complex admittance measurements over the temperature range 5.5–350 K have been performed on poly(ethylene oxide) (PEO) complexed with lithium and sodium perchlorates. No evidence of an α_a relaxation was seen in any sample. In the Li-complexed material, the γ relaxation occurs at about 174 K and 1000 Hz which is the same as for pure PEO. In the Na-complexed materials, there appear to be more than one peak in this region, and the relative peak heights are concentration dependent. The result is that at the 8:1 doping level, there is a broad, skewed relaxation whose peak occurs at about 203 K and 1000 Hz, while at 4.5:1 NaClO₄ the relaxation appears much closer to a normal peak with a maximum at 185 K for the 1000 Hz data. Combined with previous results for thiocyanate complexed PEO, these results show that distortions in the polymer chain depend on both the cation and anion. Next, two new relaxations are observed at low temperatures. The first, occuring at 60–100 K is very weak and is common to all PEO samples. The second occuring at very low temperatures, is only found for perchlorate complexed PEO and is attributed to the localized motion of perchlorate-induced defects on the exterior of the chains. The high temperature electrical conductivity for PEO₈:NaClO₄ is found to be larger than PEO_4.5:NaClO₄ in agreement with the trend observed by other workers for PEO complexed with different alkali metal salts.     

Electrical relaxation in pure and alkali metal thiocyanate complexed poly(ethylene oxide)

Audio frequency complex admittance and DSC studies have been performed on pure poly(ethylene oxide) (PEO) and PEO complexed with alkali metal thiocyanates over the temperature range 5.5–380K. The dielectric constant of the complexed materials is found to be greater than for pure PEO. A discontinuity in the conductivity is found which increases in temperature as the size of the cation increases. In every case, the discontinuity is associated with a feature in the DSC results. Next, some evidence is given that water may enhance the formation of amorphous complexed PEO. In pure PEO, α_a and γ relaxations are observed in good agreement with previous work. A thermal anomaly is found corresponding to α_a. In addition, α_c is identified in pure PEO. Very little difference is found for the γ relaxation between pure PEO and PEO-LiSCN and PEO-NaSCN. For PEO-KSCN, three distinct peaks are found in the γ relaxation region. These results are consistent with a tg⁺t ? tg^-t transition interpretation for γ where the cations reside within the helical channels at low temperatures.     

Characterization of electrochemically synthesized poly(2-fluoroaniline) film and its application to glucose biosensor

Poly(2-fluoroaniline) has been electrochemically deposited on ITO coated glass plates in the form of thin films using 4 M perchloric acid as electrolyte. These polymeric films have been spectroscopically characterized by FT-IR and UV-visible spectrophotometric methods. Room temperature electrical conductivity of the polymeric films was measured and found to be lower than that of polyaniline films. The SEM studies show the blunt needle like surface morphology of the polymeric film.Glucose oxidase (GOX) has been immobilized on to these electrochemically deposited conducting poly(2-fluoroaniline) films by physical adsorption method. The redox characterization of poly(2-fluoroaniline) and poly(2-fluoroaniline)/GOX films has been carried out by cyclic voltammetry technique. Amperometric detection of β-glucose was carried out by using the above enzyme immobilized polymeric film as a working electrode and Ag/AgCl as a reference electrode at a bias voltage of 0.2 V over a physiological range. The electrode carrying GOX was found to be stable up to 32 days.     

Conductance study of poly(ethylene oxide)- and poly(propylene oxide)-based polyelectrolytes

The ionic conductivity of poly(ethylene oxide) and poly(propylene oxide) in pure solution form, individually complexed with salts of Na⁺ and Li⁺, with and without plasticizer (propylene carbonate) and in blended form with individual salt with and without plasticizer, was studied. The conductance measurements were made at various concentrations of salt polymer complexes and at different temperatures. The effects of temperature and plasticizer concentration were measured from Arrhenius conductance plots. It is shown that the addition of salts in pure PEO increases conductance many times. The plasticizer has also same effect. The blending of PEO with PPO gives enhanced conductivity as compared to pure PEO. The activation energies were determined for all the systems which gave higher values for pure PEO and the value decreases with the addition of Li and Na salts and further decreases with the addition of plasticizer. The blending has also lowered the activation energy values which mean that incorporation of PPO in PEO has decreased crystallinity and the amorphous region has increased the local mobility of polymer chains resulting in lower activation energies.     

Chain length effect on dynamical structure of poly (vinyl pyrrolidone)-polar solvent mixtures in dilute solution of dioxane studied by microwave dielectric relaxation measurement

Dielectric relaxation study of the binary mixtures of poly(vinyl pyrrolidone) (PVP) (Mw=24000, 40000 and 360000 g mol⁻¹) with ethyl alcohol (EA) and poly(ethylene glycol)s (PEGs) (Mw=200 and 400 g mol⁻¹) in dilute solutions of dioxane were carried out at 10.1 GHz and 35°C. The relaxation time of PVP-EA mixtures was interpreted by the consideration of a wait-and-switch model in the local structure of self-associated ethyl alcohol molecules and also the PVP chain length as a geometric constraint for the reorientational motion of ethyl alcohol molecules. The formation of complexes and effect of PVP chain length on the molecular dynamics, chain flexibility and stretching of PEG molecules in PVP-PEG mixtures were explored from the comparative values of dielectric relaxation time. Further, relaxation time values in dioxane and benzene solvent confirm the viscosity independent molecular dynamics in PVP-EA mixtures but the values vary significantly with the non-polar solvent environment.     

Investigations on the effect of complexation of NaF salt with polymer blend (PEO/PVP) electrolytes on ionic conductivity and optical energy band gaps

Sodium ion conducting polymer blend electrolyte films, based on polyethylene oxide (PEO) and polyvinyl pyrrolidone (PVP) complexed with NaF salt, were prepared using solution casting technique. The complexation of the salt with the polymer blend was confirmed by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and UV-vis spectroscopy. Electrical conductivity of the films was measured with impedance analyzer in the frequency range of 1 Hz to 1 MHz and in the temperature range of 303-348 K. It was observed that the magnitude of conductivity increased with the increase in the salt concentration as well as the temperature. UV-vis absorption spectra in wavelength region of 200-800 nm were used to evaluate the optical properties like direct and indirect optical energy band gaps, optical absorption edge. The optical band gaps decreased with the increase in Na⁺ ion concentration. This suggests that NaF, as a dopant, is a good choice to improve the electrical properties of PEO/PVP polymer blend electrolytes.     

Effect of fillers on magnesium–poly(ethylene oxide) solid polymer electrolyte

A solid polymer electrolyte (SPE) film consisting of poly(ethylene oxide) (PEO) with magnesium chloride as electrolytic salt and B₂O₃ as the filler has been prepared by solution casting technique. The polymeric film was flexible and self-standing with proper mechanical strength and studied for application in a solid-state rechargeable magnesium battery. The interactions between the filler and PEO chains are studied by differential scanning calorimeter and Fourier transform infrared techniques. Composition of SPE is optimized, and maximum conductivity is obtained at 2 wt% B₂O₃. Filler seems to increase the number of free magnesium cations by decoordinating the bond between magnesium cations and ether oxygen of PEO. Cyclic voltammetry results show the reversible capability of magnesium electrode. Solid-state magnesium cell employing magnesium anode, SPE, and manganese oxide was assembled, and its open circuit voltage is found to be 1.9 V.     

Structural, vibrational, thermal, and conductivity studies on proton-conducting polymer electrolyte based on poly (N-vinylpyrrolidone)

The proton-conducting polymer electrolytes based on poly (N-vinylpyrrolidone) (PVP), doped with ammonium chloride (NH₄Cl) in different molar ratios, have been prepared by solution-casting technique using distilled water as solvent. The increase in amorphous nature of the polymer electrolytes has been confirmed by XRD analysis. The FTIR analysis confirms the complex formation of the polymer with the salt. A shift in glass transition temperature (T _g) of the PVP/NH₄Cl electrolytes has been observed from the DSC thermograms which indicates the interaction between the polymer and the salt. From the AC impedance spectroscopic analysis, the ionic conductivity of 15?mol% NH₄Cl-doped PVP polymer complex has been found to be maximum of the order of 2.51?×?10^?5?Scm^?1 at room temperature. The dependence of T _g and conductivity upon salt concentration has been discussed. The linear variation of the proton conductivity of the polymer electrolytes with increasing temperature suggests the Arrhenius type thermally activated process. The activation energy calculated from the Arrhenius plot for all compositions of PVP doped with NH₄Cl has been found to vary from 0.49 to 0.92?eV. The dielectric loss curves for the sample 85?mol% PVP:15?mol% NH₄Cl reveal the low-frequency ?? relaxation peak pronounced at high temperature, and it may be caused by side group dipoles. The relaxation parameters of the electrolytes have been obtained by the study of Tan?? as a function of frequency.     

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.