Study of the Dielectric Properties of the Perovskite LaMn0.5Co0.5O3–δ

Polycrystalline samples of the charge ordered mixed oxide LaMn_0.5Co_0.5O_3?δ (T_CO = 400 K) have been prepared by the nitrate decomposition method. These samples are biphasic, according to XRPD, and except one, oxygen defficient (δ ≈ 0.04‐0.05). The study of the dielectric properties of these samples reveal that LaMn_0.5Co_0.5O_3?δ displays a high dielectric constant, specially at room temperature and low frequencies. This ε′_r is seen to be strongly dependent on the particle size and not so much on the oxygen defficiency and the best properties are found in the sample with biggest particle size (? = 7 μm) for which ε′_r (300 K) ≈ 10⁵ up to 2x10⁴ Hz. Analysis of the role of the grain size and the electrode contacts on the obtained data reveal that this mixed oxide has an intrinsic dielectric constant that is rather high for this type of compounds (ε′_r,∞ ≈ 30) and that is further enhanced by extrinsic Maxwell‐Wagner effects. We relate such enhanced intrinsic dielectric constant to the electronic process of charge ordering present in this material below 400 K.     

In‐situ monitoring of a film preparation process for hydroxypropyl cellulose cast from isotropic aqueous solution using microdielectrometry

Solid cast films with polydomain textures were prepared on a glass substrate with transparent interdigitated electrodes from an isotropic aqueous solution of hydroxypropyl cellulose via its liquid crystalline phase under the sinusoidal electric field with small amplitude and frequency of 0.05 V µm^?1 and 10⁵ Hz, respectively. The process was monitored using microdielectrometry as well as polarised optical microscopy. The apparent dielectric constant ε_r′ and loss factor ε_r″ sensitively changed with time depending on the process conditions. On the other hand, the logarithmic relation between ε_r″ and ε_r′ showed a single curve, when they were normalised by an effective portion of the electrostatic energy density estimated using each solid‐film thickness. The conversion to the solid film was estimated during the process based on the concentration dependences of ε_r′ and ε_r″. Characteristic times were reported for the onset of the biphasic phase, fully developed cholesteric phase and termination of the process.     

Concentration dependences of dielectric properties at 105 Hz and 106 Hz for aqueous solutions of hydroxypropyl cellulose

The concentration dependences of dielectric properties measured at 10⁵ Hz and 10⁶ Hz are reported for aqueous solutions of hydroxypropyl cellulose. Phase behaviour of the solutions was also observed with a polarizing optical microscope. For solutions with concentrations well above 40 wt %, polydomain textures, including the banded texture, were observed after a prehistory of deformation. No significant discontinuous changes in the dielectric constant, ε_r′, and loss factor, ε_r″, were found at the concentrations around the onset of the isotropic–cholesteric phase transition and in the biphasic region. In contrast, the steeper changes in ε_r′ and ε_r″ were found at the critical concentration for the fully developed cholesteric phase transition with the polydomain textures.     

Some electrical properties of wood pulp

The variation with temperature and frequency of the dielectric constant ε′ and the dielectric loss ε″ for sheet wood pulp and ground wood pulp were measured. Also, the effect of the relative humidity on the dielectric behavior was measured for the ground sample at 25°C. For the dry ground wood pulp, the dielectric constant is larger than that for the dry sheet sample. This may be a result of the increase in the surface area, of the decrease in the size of crystals and/or of the decrease in the degree of crystallinity on grinding of the sheet sample. The variation of ε″ with frequency passes through a maximum. From the shift of this maximum with temperature, it is found that the apparent activation energy ΔH for this relaxation is equal to 7.06 kcal/mole and it is attributed to the polarization of the OH groups in the cellulose molecule. From the relation between the dielectric constant and the specific resistivity R_s, the dissociation energy U₀ for the ground wood pulp was calculated. U₀ for this sample below and above 52% RH is 0.315 and 5.13 × 10^?12 erg, respectively. Also, the dissociation energy of Egyptian Ashmouny cotton was calculated. The variation of the electrical conductivity σ with humidity for different types of cellulosic materials is represented graphically.     

Enhanced dielectric performance and energy storage of PVDF‐HFP‐based composites induced by surface charged Al2O3

In order to enhance dielectric properties and energy storage density of poly(vinylidene fluoride‐hexafluoro propylene) (PVDF‐HFP), surface charged gas‐phase Al₂O₃ nanoparticles (GP‐Al₂O₃, with positive surface charges, ε’ ≈ 10) are selected as fillers to fabricate PVDF‐HFP‐based composites via simple physical blending and hot‐molding techniques. The results show that GP‐Al₂O₃ are dispersed homogeneously in the PVDF‐HFP matrix and the existence of nanoscale interface layer (matrix‐filler) is investigated by SAXS. The dielectric constant of the composites filled with 10 wt % GP‐Al₂O₃ is 100.5 at 1 Hz, which is 5.6 times higher than that of pure PVDF‐HFP. The maximum energy storage density of the composite is 4.06 J cm^?3 at an electrical field of 900 kV mm^?1 with GP‐Al₂O₃ content of 1 wt %. Experimental results show that GP‐Al₂O₃ could induce uniform fillers’ distribution and increase the concentration of electroactive β‐phase as well as enhance interfacial polarization in the matrix, which resulted in enhancements of dielectric constant and energy storage density of the PVDF‐HFP composites. This work demonstrates that surface charged inorganic‐oxide nanoparticles exhibit promising potential in fabricating ferroelectric polymer composites with relatively high dielectric constant and energy storage. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 574–583     

Effect of ZnO on sintering and microwave dielectric properties of 0.5CaTiO3-0.5 (Li0.5La0.5) TiO3 ceramics

The novel calcium titanate-lithium lanthanum titanate doped with zinc oxide (0.10, 0.30, and 0.50 mol. %) ceramic samples were prepared by solid-state reaction route. The phase formation, microstructure, densification, and microwave dielectric properties were investigated. It was found that the doping with zinc oxide led to a decrease in sintering temperature by 25 ^oC as compared with pure calcium titanate lithium lanthanum titanate due to the liquid phase effect. Also, the calcium titanate lithium lanthanum titanate (10ZCTLLT&30ZCTLLT)) doped with lower zinc oxide (0.10 and 0.30 mol. %) led to higher densification parameter. This was followed by increasing the zinc oxide doping up to (0.50 mol. %) which resulted in a decrease in densification and microwave dielectric properties which may be attributed to increase in porosity and grain growth upon the evaporation of zinc and oxygen vacancy. This led to the increase in dielectric loss (≈10 × 10^?4) value with 50ZCTLLT. Hence, the best result of microwave dielectric characteristics was obtained for 0.5CaTiO₃–0.5(Li_0.5La_0.5)TiO₃ with (0.10 and 0.30 mol. % ZnO) 10ZCTLLT and 30ZCTLLT ceramic samples sintered at 1175 ^oC/2h, with low dielectric constant (ε_r) = 4.4–10.5, very low dielectric loss = 1.07-2.23 × 10^?4 and high quality factor (Q x ?) ≈59-55 × 10⁴ at 8 GHz. Consequently, they can be used not only in wireless satellite communications technology but also can be used in the fifth-generation telecommunication 5G technology construction.     

Piezoelectric and dielectric properties of siloxane elastomers filled with bariumtitanate

Piezoelectric elastomers were prepared from suspensions of bariumtitanate (BaTiO₃) particles in a telechelic polydimethylsiloxane (t-PDMS) by crosslinking the t-PDMS under an electric field. Crosslinking reaction was monitored by measurement of complex dielectric constant ε′ − iε″. Dielectric constant ε′ increased with increasing BaTiO₃ content, and agreed approximately with the theoretical ε′ calculated with the Maxwell–Wagner theory. Piezoelectric constant d₃₃ of the poled elastomers was measured by application of compressions in the direction of the poling field. It was found that d₃₃ was of the order of 10⁻¹¹ C/N and increased steeply with increasing content of BaTiO₃ but became almost independent of composition in the range of BaTiO₃ content from 3 to 14 vol %. To examine the effect of electric field on the aggregation structure of the particles, we observed light scattering of the suspension under an electric field, and found that the scattering pattern became anisotropic. This indicated that the particles are connected like a pearl necklace and are stretched in the direction of the poling field. The dependence of d₃₃ on the volume fraction of BaTiO₃ was explained by a model proposed by Banno. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 3065–3070, 1999     

Proton conducting polymer blend electrolytes based on MC: FTIR,ion transport and electrochemical studies

In this work, the free-standing plasticized solid polymer electrolyte films were made utilizing methylcellulose (MC) and dextran (DN) doped with ammonium fluoride (NH₄F) and plasticized with glycerol by a typical solution casting approach. Based on the characterizations, MC-DN-NH₄F electrolyte has been shown to improve the structural, electrical, and electrochemical properties resulting from the dispersion of glycerol plasticizer. The electrochemical impedance spectroscopy (EIS) measurement for the highest inclusion of plasticizer revealed a conductivity of 2.25 × 10^-3 S/cm. The electrical equivalent circuit (EEC) model has established the circuit elements for each electrolyte. The variation trend of dielectric constant and DC conductivity was matched and confirmed by the EIS data. The fourier transform infrared (FTIR) analysis displayed credible confirmation of polymers-ion-plasticizer interactions. The dielectric study is extra highlighted the conductivity behavior. The dielectric constant and loss (ε′ and ε″) quantities were reported to be high at low frequencies. On the other hand, the irregular shape of the imaginary part of modulus (M“) spectra denotes the non-Debye behaviors of relaxation. The ion transference number (t_ion) value for the maximum plasticized system is 0.944, where the ions are the primary components for the charge transfer process. Stability of the highest conducting sample is determined to be 1.6 V, using linear sweep voltammetry (LSV).     

Dielectric properties of some semiconducting polyazophenylenes

The dielectric properties of a series of semiconducting polyazophenylenes were studied as a function of temperature and molecular weight in the temperature range 293–600°K and for molecular weights between 5,100 and 62,800 at a constant frequency of 1 kHz. The compounds studied included poly-2,4-diaminotoluene, poly-2,4-diaminoanisole, and poly-2,5-diaminotoluene. The dielectric properties are presented in the usual way in terms of a complex dielectric constant ε^* = ε′—jε″. Activation energies of relaxation processes were evaluated from the areas and widths of the dielectric loss factor, ε″, against reciprocal temperature at constant frequency. The dielectric activation energies were found to be roughly equal to the activation energies from the DC conductivity. This indicates that the conduction mechanism is based on rotational movements of molecules or parts of molecules.     

X-ray diffraction and dielectric spectroscopy studies on a partially fluorinated ferroelectric liquid crystal from the family of terphenyl esters

The fluorinated compound, (S)-4′′-(6-perfluoropentanoyoxyhexyl-1-oxy)-2′,3′-difluoro-4-(1-methylheptyloxycarbonyl)-[1,1′:4′,1′′]-terphenyl, which exhibits antiferroelectric SmC_A*, ferroelectric SmC* and paraelectric SmA* phases, has been investigated by polarising optical microscopy, differential scanning calorimetry, X-ray diffraction and frequency-dependent dielectric spectroscopy methods. X-ray studies have revealed that the layer thickness remains almost constant in the SmA* phase but within the SmC* and SmC_A* phases it decreases with decreasing temperature, a step jump being observed only at the SmA*–SmC* transition. The tilt angle in the SmC_A* phase decreases from 22.2° to 19.5°, and in the SmC* phase it decreases from 18.8° to 5.5°. Spontaneous polarisation is found to be quite high and varies between 74.1 and 118.7 nC cm^?2. The variation in ε′ and ε′′ with temperature shows a discontinuous change at the transition temperatures. Goldstone mode relaxation is only observed in the ferroelectric and antiferroelectric phases and is found to be of the Cole–Cole type. The soft mode is observed on application of a bias field near the SmC*–SmA* transition. Neither the soft mode nor the anti-phase azimuthal angle fluctuation mode is observed in SmC_A*. Rotational viscosity decreases quite rapidly with temperature but in a different manner in the ferroelectric and antiferroelectric phases. Activation energy for this process is found to be 48.14 kJ mol^?1 in the SmC* phase.     

Microwave‐assisted synthesis of nanocomposites from polyimides chemically cross‐linked with functionalized carbon nanotubes for aerospace applications

Polymer‐carbon nanotube nanocomposites are extensively investigated for microelectronics and aerospace applications. In this study, novel polyimide/f‐MWCNT nanocomposites made from 2,4‐bis(4‐aminophenylamido)‐6‐chloroquinazoline, pyromellitic dianhydride and functionalized‐Multi Walled Carbon Nanotubes (f‐MWCNT) by an efficient microwave assisted method were investigated. The structure of the prepared diamine monomer was confirmed by FT‐IR, ¹H‐NMR, and ¹³C‐NMR spectral techniques. The prepared nanocomposites (T_g values from 338°C to 375°C) show improved thermal property as indicated by differential scanning calorimetry and thermogravimetric analysis. Polyimide/f‐MWCNT nanocomposites were found to have higher dielectric constant, and the limiting oxygen index values of prepared nanocomposites are in the range of 29.5 to 35.5, indicating a high flame retardancy. Additionally, the morphological studies were conducted by X‐ray diffraction and scanning electron microscopy. Overall, it is observed that chemically connected polyimide‐functionalized carbon nanotube nanocomposites could be used for aerospace and microelectronics applications that require high T_g, dielectric constant and high flame retardancy.     

Microstructure and dielectrical responses of pure and cobalt-doped CaCu3Ti4O12 ceramics by sol鈥揼el synthesis route

Cobalt-doped CCTO (CaCu₃Ti₄O₁₂) ceramics were prepared by a conventional sol–gel synthesis method and the effects of Cobalt doping on the microstructures and dielectrical properties were investigated. The phase composition and microstructure were studied by means of X-ray diffraction (XRD) and high resolution scanning electron microscopy (HRSEM). Efficient crystalline phase formation accompanied by Cobalt induced lattice constant expansion was confirmed through XRD studies. HRSEM results show that doping effectively enhanced grain growth or densification. A compositional study reveals the variation of Cobalt diffusion in CCTO structure by the reduction of Ti presence according to the doping ratio. The dielectric constant reached a value as high as (ε_r?=?25,400 at 1,000 and ε_r?=?111,000 at 1,050?°C) at a cobalt-doping concentration of x?=?0.2 at low frequency (50?Hz). The dielectrical constant and dielectric loss of the pure and cobalt-doped CCTO ceramics was measured for different concentrations and discussed in detail.     

Mg2MTaO6 (M=Nd or La): a group of new pyrochlore oxides

Preparation of two novel mixed metal oxide ceramic materials, namely magnesium neodymium tantalum oxide (Mg₂NdTaO₆) and magnesium lanthanum tantalum oxide (Mg₂LaTaO₆) by conventional solid-state reaction method is reported in this paper. The crystal structure of these new compounds, were studied by indexing the X-ray diffraction patterns, powder pattern calculation and profile fitting. They were found to have a defective cubic pyrochlore structure, with the A site being randomly occupied by Mg and La/Nd, while, Ta and Mg are randomly distributed at the B site. The formula assigned were (MgNd)(MgTa)O₆ and (MgLa)(MgTa)O₆. The variation of dielectric constant, dielectric loss and conductivity of sintered pellets of these materials with applied frequencies in the range of 30 Hz-1 MHz were studied at room temperature. These room temperature studies at 1 MHz gave dielectric constant values of 24.8 and 25.35; conductivity values of 7.75×10⁻⁶ and 8.27×10⁻⁶ S/m as well as dielectric loss values of 0.0055 and 0.006 for Mg₂NdTaO₆ and Mg₂LaTaO₆, respectively. These new pyrochlore compounds were found to have dielectric constant, dielectric loss and conductivity values in the range suitable for possible electronic ceramic applications.     

Giant dielectric constant response of the composites in ternary system CuO-TiO2-CaO

The subsolidus phase relations of the ternary system CuO-TiO₂-CaO sintered at 950 °C in air have been determined by powder X-ray diffraction method. Only one ternary compound CaCu₃Ti₄O₁₂ was found in this system. From room-temperature dielectric property mapping at 10 kHz, a giant dielectric constant (ε_r>10⁴) was observed for most of the ceramic composites in the CuO-rich region and in the region along the CaO-CuO binary line. The composites in the CaCu₃Ti₄O₁₂-rich region were found to give a comparable giant dielectric constant when sintered at 1050 °C. The particular microstructure of larger grains with predominant phase surrounded by smaller grains with the secondary phases was found in such composites with a high dielectric constant. The relations between structures and dielectric properties were investigated. An internal barrier layer capacitance effect is the most probable mechanism to explain this particular dielectric behavior.     

Development of a Ruthenium(II) Complex Based Luminescent Probe for Imaging Nitric Oxide Production in Living Cells

A unique ruthenium(II) complex, bis(2,2′‐bipyridine)(4‐(3,4‐diaminophenoxy)‐2,2′‐bipyridine)ruthenium(II) hexafluorophosphate ([(Ru(bpy)₂(dabpy)][PF₆]₂), has been designed and synthesized as a highly sensitive and selective luminescence probe for the imaging of nitric oxide (NO) production in living cells. The complex can specifically react with NO in aqueous buffers under aerobic conditions to yield its triazole derivative with a high reaction rate constant at the 10¹⁰ M ^?1 s^?1 level; this reaction is accompanied by a remarkable increase of the luminescence quantum yield from 0.13 to 2.2 %. Compared with organic probes, the new Ru^II complex probe shows the advantages of a large Stokes shift (>150 nm), water solubility, and a wide pH‐availability range (pH independent at pH>5). In addition, it was found that the new probe could be easily transferred into both living animal cells and plant cells by the coincubation method, whereas the triazole derivative was cell‐membrane impermeable. The probe was successfully used for luminescence‐imaging detection of the exogenous NO in mouse macrophage cells and endogenous NO in gardenia cells. The results demonstrated the efficacy and advantages of the new probe for NO detection in living cells.     

Dielectric relaxations in PEEK by combined dynamic dielectric spectroscopy and thermally stimulated current

The molecular dynamics of a quenched poly(ether ether ketone) (PEEK) was studied over a broad frequency range from 10^?3 to 10⁶ Hz by combining dynamic dielectric spectroscopy (DDS) and thermo-stimulated current (TSC) analysis. The dielectric relaxation losses ε′′_KK has been determined from the real part ε′_T(ω) thanks to Kramers–Kronig transform. In this way, conduction and relaxation processes can be analyzed independently. Two secondary dipolar relaxations, the γ and the β modes, corresponding to non-cooperative localized molecular mobility have been pointed out. The main α relaxation appeared close to the glass transition temperature as determined by DSC; it has been attributed to the delocalized cooperative mobility of the free amorphous phase. The relaxation times of dielectric relaxations determined with TSC at low frequency converge with relaxation times extracted from DDS at high frequency. This correlation emphasized continuity of mobility kinetics between vitreous and liquid state. The dielectric spectroscopy exhibits the α_c relaxation, near 443 K, which has been associated with the rigid amorphous phase confined by crystallites. This present experiment demonstrates coherence of the dynamics of the PEEK heterogeneous amorphous phase between glassy and liquid state and significantly improve the knowledge of molecular/dynamic structure relationships.     

Synthesis,crystal structure and properties of a quaternary oxide with a new structure type,BiGaTi4O11

A new quaternary oxide, BiGaTi₄O₁₁ (bismuth gallium tetratitanium undecaoxide), was prepared by heating a mixture of the binary oxides at 1373 K in air. BiGaTi₄O₁₁ melts at 1487 K and prismatic single crystals were obtained from a sample melted at 1523 K and solidified by furnace cooling. The structure of BiGaTi₄O₁₁ was analyzed using single‐crystal X‐ray diffraction to be of a new type that crystallized in the space group Cmcm. A Bi³⁺ site is coordinated by nine O^2? anions, and three oxygen‐coordinated octahedral sites are statistically occupied by Ga³⁺ and Ti⁴⁺ cations. A relative dielectric constant of 46 with a temperature coefficient of 57 ppm K^?1 in the temperature range 297–448 K was measured for a polycrystalline ceramic sample at 150 Hz–1 MHz with a dielectric loss tan δ of less than 0.01. Electrical resistivities measured at 1073 K by alternating‐current impedance spectroscopic and direct‐current methods were 1.16 × 10^?4 and 1.14 × 10^?4 S cm^?1, respectively, which indicates that electrons and/or holes were conduction carriers at high temperature. The optical band gap estimated by the results of diffuse reflectance analysis was 2.9–3.0 eV, while the band gap obtained from the activation energy for electrical conduction was 3.5 eV.     

Dielectric polarization of a partially neutralized poly(methacrylic acid) in dilute aqueous solutions: Conformational transition

Dielectric permittivity ε′ (at a frequency of 1 MHz) of aqueous solutions of a partially neutralized poly(methacrylic acid) Na-PMAA was studied with varying the degree of ionization α_i from 0 to 0.78 and concentrations w ₂ (g/g) from 1.25 × 10^?4 to 6 × 10^?3 at 25°C. It was shown that the concentration dependence of ε′ for Na-PMAA aqueous solutions at all α_i values contains two regions corresponding to different changes in ε′, and the above regions are separated by the crossover point w*₂. In the first region, ε′ increases with the increasing concentration Δε′/Δw ₂ > 0; in the second region, ε′ decreases with the increasing concentration Δε′/Δw ₂ < 0. The sign inversion of Δε′/Δw ₂ is explained by different structures of water and mechanisms of hydration in regions I and II. In the region corresponding to the ascending branch of the ε′-w ₂ curve, the dipole moments of macromolecules per repeating unit, μ = (〈M ²〉/N)^1/2, were calculated according to the Buckingham theory. The μ value is high; as a macromolecule is saturated with ionized units, this value nonmonotonically changes from ～10 D at α_i = 0 to ～18 D at α_i ～ 0.24. This dependence peaks at ～30 D at α_i ～ 0.1. As is assumed, (〈M ²〉/N)^1/2 depends on the vector sum of partial dipole moments of hydrated nonionized monomer units (μ ～10 D) and fluctuation-induced dipole moments of ionized monomer units. The profile of μ as a function of the degree of ionization of Na-PMAA indicates the occurrence of the conformational transition in an individual macromolecule. This transition takes place at the degree of ionization α_i ～ 0.1. An analysis of molecular interactions in the (ionized coil)-solvent system explans the conformational transition in Na-PMAA.     

Chain orientation and anisotropies in optical and dielectric properties in thin films of stiff polyimides

Thin films of poly(p-phenylene biphenyltetracarboximide) (BPDA-PDA), prepared by thermal imidization of the precursor poly(amic acid) on substrates, have been investigated by optical waveguide, ultraviolet-visible (UV-VIS), infrared (IR), and dielectric spectroscopies. The polyimide films exhibit an extraordinarily large anisotropy in the refractive indices with the in-plane index n_∥ = 1.806 and the out-of-plane index n_⊥ = 1.589 at 1064 nm wavelength. No discernible effect of the film thickness on this optical anisotropy is found between films of ca. 2.1 and ca. 7.8 μm thickness. This large birefringence is attributed to the preferential orientation of the biphenyltetracarboximide moieties with their planes parallel to the film surface, coupled with the strong preference of BPDA-PDA chains to align along the film plane. The frequency dispersion of the in-plane refractive index n_∥ is consistent with the results calculated by the Lorentz–Lorenz equation from the UV-visible spectrum exhibiting several absorption bands in the 170–500 nm region. The contribution from the IR absorption in the range 7000–400 cm,^?1 computed by the Spitzer-Kleinmann dispersion relations from the measured spectra, adds ca. 0.046 to the in-plane refractive index n_∥. Tilt-angle–dependent polarized IR results indicate nearly the same increase for the out-of-plane index n_⊥. Application of the Maxwell relation then leads to the out-of-plane dielectric constant ε^⊥ ? 2.7 at 1.2 × 10¹³ Hz, as compared with the measured value of ca. 3.0 at 10⁶ Hz. Assuming this small difference to remain the same for the in-plane dielectric constants ε_∥, we obtain a very large anisotropy in the dielectric properties of these polyimide films with the estimated in-plane dielectric constant ε_∥ ? 3.4 at 1.2 × 10¹³ Hz, and ε_∥ ? 3.7 at 10⁶ Hz. © 1992 John Wiley & Sons, Inc.