Dielectric spectroscopy of aminoalcohols and polyethylenepolyamines

Dependences of dielectric permittivity ?(f) and dielectric loss tangents tansδ(f) of aminoalcohols (AAs), polyethylenepolyamines (PEPAs), water, and aqueous solutions of AAs and PEPAs with water concentrations of 1 wt % are investigated in the frequency range of 0.025–1000 kHz. The dielectric relaxation of the liquids under study is investigated. An interrelation between the dielectric parameters and physicochemical properties of AAs and PEPAs is established. Empirical equations that describe this interrelation with a high degree of accuracy of approximation validity are derived. The effect of water on the dielectric characteristics of AAs and PEPAs is shown. It is suggested that we evaluate the energy of affinity of AAs and PEPAs for water using the coefficient of dielectric losses ?″.     

A spectroscopic study on medium polarity in fluorous alcohol

The paper describes the polarities of three fluorous (F) aliphatic alcohols: perfluorinated tert-butanol (F-t-BuOH), n-butanol (F-n-BuOH), and n-heptanol (F-n-HepOH). For the purpose, we conducted absorption and fluorescence spectroscopies of coumarin 153 (C153) and 102 (C102) in three F and 13 non-fluorous (non-F) alcohols and determined their maximum energies: ν^a (absorption) and ν^f (fluorescence). We obtained linear relationships between the Stokes shifts of the dyes (i.e., (ν^a − ν^f)) and a medium polarity parameter for 13 non-F alcohols, f(x): f(x) = [(D_s − 1)/(2D_s + 1) − (n² − 1)/(2n² + 1)], where D_s and n were the dielectric constant and refractive index of a solvent, respectively. By comparing the Stokes shifts of the dyes in three F alcohols with those in 13 non-F alcohols (i.e., (ν^a − ν^f) vs. f(x) plot), the D_s values in F-t-BuOH, F-n-BuOH, and F-n-HepOH were evaluated to be 2.7-3.9, 4.3-5.1, and 4.0-5.2, respectively, while those in the relevant non-F alcohols were 12.5, 17.5, and 12.9, respectively. Thus, the present experiments demonstrated that the polarities of these F alcohols were much lower than those of the relevant non-F alcohols.     

Dielectric loss of neutron-irradiated nanocrystalline silicon carbide (3C-SiC) as a function of frequency and temperature

At the present work, nanocrystalline 3C-SiC has been irradiated by neutron flux (2 × 10¹³ n·cm⁻²s⁻¹) up to 20 h in a TRIGA Mark II type research reactor. The dielectric loss of nanocrystalline 3C-SiC was studied comparatively before and after neutron irradiation. The increased dielectric loss was clearly observed after neutron irradiation in both f(tanδ) ∼ f(f) and f(tanδ) ∼ f(T) plots. Furthermore, slope observed on the f(tanδ) ∼ f(f) plots at certain values of the frequency. Dielectric loss increasing and shifted slope explained by the neutron transmutation, dangling bonds, the formation of the defects or additional charge carriers. Moreover, the mechanism of all effects obtained from the experiments was explained by the polarization approach.     

Dielectric Relaxation and Thermodynamic Studies of Binary Mixtures of 2-Nitrotoluene with Primary and Secondary Alcohols at Different Temperatures

The dielectric complex spectra of 2-nitrotoluene with primary or secondary alcohol binary mixtures were studied over the frequency range of 10 MHz to 20 GHz for the whole solute mole fraction range at four different temperatures. An unusual suppression phenomenon was observed in the real and imaginary parts of the mixture complex spectrum, which are smaller than those for the pure alcohols, at low solute concentrations. The dielectric constant and dielectric relaxation time values were obtained by fitting the complex dielectric spectrum data to the single Debye model using a non-linear least squares method. The dielectric constant of mixtures decrease with the increasing mole fraction of 2NT in both the primary alcohols and secondary alcohols; the dielectric relaxation time decreases for all the five binary systems. Using the dielectric data, derived dielectric parameters, namely: the excess dielectric constant, excess inverse relaxation time, effective Kirkwood correlation factor, molar activation enthalpy and molar activation entropy, were calculated. The non-linear variation of permittivity (?₀) reveals the change in size and shape of hetero-molecular complex due to intermolecular H-bond interaction. The negative variation of the excess permittivity constant confirms that the dipoles form multimer structures with anti-parallel ordering of unlike dipoles. The molar activation enthalpy was found to be higher at 0.2 mol fraction of 2NT for primary alcohol binary system. To confirm the molecular function group interaction, a FT-IR spectroscopy study was carried out at 298 K. The FT-IR analysis confirmed the formation of hydrogen bonds between the hydrogen atom of hydroxyl groups of the alcohols and the oxygen atom of nitro groups of 2NT in the binary mixtures.     

Lanthanide thermodynamic predictions—V. Stabilities of lanthanide anions in liquid ammonia

The stabilities (as ΔG⁰_f) of monatomic lanthanide anions in liquid ammonia are estimated from a simple electrostatic model. It is shown that the existence of lanthanide anions in this solvent is highly improbable.     

A Study of the Effect of Sintering Conditions of Mg0.95Ni0.05Ti3 on Its Physical and Dielectric Properties

Mg_0.95Ni_0.05TiO₃ ceramics were prepared by traditional solid-state route using sintering temperatures between 1300 and 1425 °C and holding time of 2–8 h. The sintered samples were characterized for their phase composition, micro-crystalline structure, unit–cell constant, and dielectric properties. A two-phase combination region was identified over the entire compositional range. The effect of sintering conditions was analyzed for various properties. Both permittivity (ε_r) and Q factor (Q_f) were sensitive to sintering temperatures and holding times, and the optimum performance was found at 1350 °C withholding time of 4 h. The temperature coefficient of resonant frequency (τ_f) in a range from −45.2 to −52 (ppm/°C) and unit–cell constant were not sensitive to both the sintering temperature and holding time. An optimized Q factor of 192,000 (GHz) related with a permittivity (ε_r) of 17.35 and a temperature coefficient (τ_f) of −47 (ppm/°C) was realized for the specimen sintered at 1350 °C withholding time of 4 h. For applications of 5G communication device (filter, antennas, etc.), Mg_0.95Ni_0.05TiO₃ is considered to be a suitable candidate for substrate materials.     

Predicted stabilities of monatomic anions in water and liquid ammonia at 298.15 K

Critically evaluated experimental and theoretical atomic electron affinities are assembled and used to derive thermodynamic properties of gas-phase monatomic anions throughout the Periodic Table. The stabilities (as ΔG^o_f) of these anions in water and liquid ammonia are calculated by a semiempirical electrostatic model. The predictions are compared with experimental observations where possible.     

Actinide thermodynamic predictions—II. Stabilities of actinide anions in liquid ammonia

The stabilities (as ΔG_f^o) of monatomic actinide anions in liquid ammonia are estimated from a simple electrostatic model. It is shown that, with the possible exception of Md^?, the existence of actinide anions in this solvent is highly improbable.     

Thermo-crosslinkable molecular glasses towards the low k materials at high frequency

Two molecular glasses having allyl side chains and thermo-crosslinkable benzocyclobutene (BCB) groups have been successfully synthesized. These molecules display good solubility in common organic solvents and show a typical glass-forming behavior of having no melting point and keeping a complete amorphous state. The thermally cured molecular glasses exhibit low dielectric constant (D_k) and dielectric loss (D_f) at 10 GHz, as well as low water uptake (Wa) even when they are immersed in boiling water for 72 h. Among them, a fluoro-containing molecule exhibits the best properties, showing D_k of 2.53, D_f of 1.93 × 10^?3 and Wa of 0.19%, respectively, indicating that fluoro groups can efficiently improve the dielectric properties of the molecules. A controlling test indicates that the allyl side chains make the molecules possessing glass-forming properties.     

Orientation order in monoethanolamine at 25–75°C, according to data from dielcometry

The static permittivity (?_s) of monoethanolamine (MEA) is measured at a frequency of 1 MHz in the temperature range of 20–90°C. The found data were analyzed in the context of the Onsager-Kirkwood-Fröhlich theory. The values of the correlation factor (g) are calculated in the investigated temperature range. Similar calculations using literature data are performed for 3-amino-1-propanol (AP) and N,N-dimethylethanolamine (DMEA) (temperature range, 15–35°C). The difference between the correlation factors of MEA, AP, and DMEA and their temperature dependences are explained by the structures of these amino alcohols and their molecules. A conclusion is drawn on the orientation order in liquid MEA, based on the obtained results made. In addition, the data from our study of the equilibrium dielectric properties of MEA are compared to the similar properties of ethylene glycol (EG), and a conclusion is drawn on features of the structure of amino alcohol relative to diol.     

Effect of plastic deformation on the character of micro-brownian motions in glassy poly(methyl methacrylate)

Glassy PMMA samples are plastically deformed at room temperature in the uniaxial compression regime to residual strains of e _res = 25%. Dielectric spectra of the initial and deformed samples are recorded via the method of broadband dielectric spectroscopy in the frequency range f = (5 × 10^?4) ? 10⁷ Hz. The results are compared with the dynamic mechanical spectra of samples deformed under the same conditions. Dielectric and mechanical spectra are noticeably distorted by deformation. As a result, dielectric permittivity ??? increases, shear modulus G?? decreases, and the intensity of dielectric ?? losses slightly increases, while dielectric and mechanical ?? losses increase appreciably. In addition, the ??anomaly?? of total dielectric ???_tot and total mechanical ??G _tot dispersions (???_tot = ?₀ ? ?_?? ?? ???_?? + ???_?? and ??G _tot = G ₀ ? G _?? ?? ??G _?? + ??G _??) occurs, that is, the polymer is transformed from the state with ???_?? ? ???_?? and ??G _?? < ??G _?? into the state with ???_?? > ???_?? and ??G _?? > ??G _??. The described phenomenon is related to a strong gain in ?? dielectric and mechanical losses in the deformed material. It is found that ?? losses increase owing to an anelastic deformation component arising during glass loading. This component is responsible for an increase in the internal energy of the glass during its anelastic deformation. Possible causes of the observed effects are discussed.     

Synthesis of ethyl zinc fluoroalkoxide complexes and the crystal structure of [EtZn(py){μ-OCH(CF3)2}]2

Fluorinated alkoxide complexes of zinc were synthesized for possible use as precursors to fluorine-doped ZnO films. Diethyl zinc reacted with fluorinated alcohols to form [EtZn(OR_f)]_n (R_f = CH(CF₃)₂, CMe₂CF₃, CMe(CF₃)₂) compounds. The [EtZn(OR_f)]_n compounds reacted with excess pyridine to yield the pyridine adducts [EtZn(py)(μ-OR_f)]₂. The X-ray structure of [EtZn(py){μ-OCH(CF₃)₂}]₂ showed that it has virtual C_i symmetry.     

Dual-frequency excitation: A novel method for probing the nonlinear dielectric properties of biological systems,and its application to suspensions of S. cerevisiae

We have recently described the construction of a dual-cell, nonlinear dielectric spectrometer, and its application to the study of cell suspensions of S. cerevisiae (A.M. Woodward and D.B. Kell, Bioelectrochem. Bioenerg., 24 (1990) 83). Substantial, odd harmonics were generated by these cells when stimulated by very modest sinusoidal electrical fields, within fairly sharp voltage-and frequency windows (ca. 0.8–2.5 V cm⁻³, 1–50 Hz). Resting cells were found to generate only odd-numbered harmonics. In the present work, we have simultaneously applied two sinusoidal frequencies which were individually of unsuitable frequency and/or amplitude for the generation of harmonics when applied to suspensions of S. cerevisiae. Strong “sidebands” or “beat frequencies” were observed which were the (odd-numbered) sums and differences of the exciting frequencies (viz.f₁±2f₂, f₂±2f₁). The generation of these beat frequencies was strongly inhibited by low concentrations of sodium metavanadate, suggesting that they may be ascribed largely to the H⁺-ATPase present in the plasma membranes of these cells. We show that the ability of dc fields to inhibit the manifestation of nonlinear dielectric behaviour by these cells is explicable in terms of their ability to act as a field of zero Hz, forcing the excitation out of the amplitude window. When the cells were allowed to glycolyse, beat frequencies of even order (f₁±2f₂, f₁±3f₂)) were observed. The present approach provides a novel and powerful approach to the registration of nonlinear dielectric spectra, which, due to the greater precision inherent in the discrimination of frequencies rather than voltages may be expected to provide a more sensitive means of detecting nonlinear dielectric properties in biological systems. If the transduction of exogenous electrical field energy recorded by this method is representative of the natural turnover of the H⁺-ATPase in vivo, it may be calculated that the efficiency of the capture of electric field energy by this enzyme is some 3%.     

Fabrication and characterization of cerium doped barium titanate/PMMA nanocomposites

The cerium doped barium titanate (BaTiO₃:Ce)/poly methyl methacrylate(PMMA) polymer nano-composites (PNC) were successfully fabricated via solvent evaporation method with microwaves (2.4 GHz) heating. The X-ray diffraction measurements confirm the formation of barium titanate (BT) with crystallite size ranges from 55 to 62 nm. Differential scanning calorimetry study shows that the glass transition temperature (T_g) directly affected by microwaves heat treatment and particle size of filler. The broadband dielectric spectroscopy was employed to investigate the frequency and temperature dependence of the dielectric properties of the nanocomposites in a frequency range from 75 kHz to 5 MHz and temperature range 80–400 K. The introduction of different BT fillers in PMMA enhance the dielectric constant of PNCs drastically and give a smooth response in frequency range mentioned above. The loss factor of the composite can be suppressed by using cerium doped barium titanate filler rather than pure barium titanate filler.     

AC Electrical Properties of Plasma Polymerized <Emphasis Type="Italic">o</Emphasis>-Methoxyaniline Thin Films

Alternate current (ac) electrical properties of the plasma polymerized o-methoxyaniline (PPOMA) thin films synthesized in the glow discharge plasma using a capacitively coupled reactor are studied. Measurement revealed that the ac electrical conductivity varies with frequency ω as ω ⁿ , where the exponent n is less than unity in the range 0.1 to 2.0 kHz, indicating the Debye type conduction mechanism in the PPOMA thin films, while above this frequency range the exponent is become greater than unity indicating non-Debye type conduction. At low frequencies the conduction is considered to be due to hopping of carriers between the localized states. The PPOMA thin films of thicknesses 100?250 nm possesses dielectric constant <10, which remains static in the range 0.1?10 kHz, and decreases at higher temperature due to the orientation polarization. The dielectric loss increases with the increase in frequency having a peak around or above 10 kHz for all the PPOMA films of different thicknesses. Cole-Cole plot between the real and imaginary dielectric constant exhibits single relaxation mechanism in the PPOMA thin films.     

Catalytic asymmetric borane reduction of prochiral ketones by the use of diazaborolidine catalysts prepared from chiral β-diamines

The catalytic asymmetric borane reduction of prochiral ketones was examined in the presence of chiral diazaborolidine catalysts prepared in situ from chiral β-diamines and borane. Chiral secondary alcohols were obtained with modest to high enantiomeric excesses (up to 92% ee) using (S)-2-[(4-trifluoromethyl)anilinomethyl]indoline 2f.     

N, O-ligand accelerated zinc-catalyzed transesterification of alcohols with vinyl esters

N-Phenyldiethanolamine (1f) is an efficient ligand for zinc-catalyzed transesterification of alcohols with vinyl acetate (R³ = Me) at room temperature. In the case of using other vinyl esters (R³ = Et, n-Pr, Ph), the corresponding products were easily obtained in the presence of pyridine-type ligand 2 instead of aminoalcohol 1f.     

Identification of relaxation processes in pure polyethylene oxide (PEO) films by the dielectric permittivity and electric modulus formalisms

The ac‐impedance of bulk‐like films of pure polyethylene oxide (PEO) polymer was measured as a function of frequency f in the range 0.1 to 10⁷ Hz at various constant temperatures T (155 − 330 K ). The as‐measured data were analyzed by electric permittivity and modulus formalisms to unveil which dielectric and conductive relaxation processes were responsible for their relaxation behavior below/above glass transition temperature T_g of pure PEO polymer. At T > T_g , none of the α ‐, β ‐, or γ ‐relaxations could be inferred for studied pure PEO films from frequency variation of measured imaginary part ε′′(f, T) of complex dielectric permittivity , as low‐frequency losses masked real dielectric contribution to the measured ε′′(f, T) at low frequencies and high temperatures. However, at T < T_g , a broad, relaxation process has been observed in the high‐frequency part of their isothermal ε′′(f, T) − f spectra, which can be related to the β ‐ or γ ‐dielectric relaxation process. Nonlinear regressions of the measured ε′′(f, T) − f data for T < T_g yielded moral fits to a simple addition of a Havriliak‐Negami function, and a Bergman‐loss Kohlrausch‐Williams‐Watts‐type function, with the relaxation time τ_max(T) obtained from Havriliak‐Negami‐fitting parameters, was found to follow a thermally activated Arrhenius‐like relaxation behavior. Conversely, representation of the imaginary part M′′(f, T > T_g) − f spectra of complex electric modulus was found to depict 2 overlapped relaxation processes, which were detached well by a nonlinear regression of a simple superposition of 2 different M′′(f)  expressions having the form of the universal Bergman loss function, where it was found that the relaxation time is also thermally activated.     

An interferometric spectrum analyzer with high dynamic range

The dynamic range improvement and realization of the acousto-optic spectrum analyzer are reported. When two RF signals of equal strengths and frequencies f₁ and f₂ are applied simultaneously to the signal Bragg cell, the analyzer demonstrates a dynamic range of 50 dB and frequency resolution 10 kHz.     

Optical and dielectrical properties of azo quinoline thin films

In this study, the optical and dielectrical properties of a novel series of quinoline azodyes (5-(4′-derivatives phenyl azo)-8-hydroxy-7-quinolinecarboxaldehyde) (AQL₁–AQL₅) were investigated and the obtained results were analyzed. The X-ray diffraction (XRD) patterns of AQL_n show that the materials in the powder form are a mixture of amorphous and crystalline structure, while the thermally deposited thin films are completely amorphous. The optical constants such as the refractive index, n, the absorption index, k and the absorption coefficient, α, were determined using spectrophotometric measurements of transmittance (T) and reflectance (R) in the wavelength range 200–2500 nm. According to the single oscillator model (SOM), some related parameters such as oscillation energy (E_o), the dispersion energy (E_d), the optical dielectric constant (ε_∞), the lattice dielectric constant (ε_L) and the ratio of free carrier concentration to its effective mass (N/m*) are estimated. The emission spectra of azo quinoline ligands (AQL_n) exhibit dual fluorescence peaks in the region 512–580 nm. This finding reveals the formation of two stoichiometric hydrogen-bonding in the ground and excited state. The dielectrical properties and alternating current conductivity (σ_AC) are investigated in temperature range 298–483 K and frequency range 0.1–100 KHz.