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.     

GPS patch antenna performance by modification of Zn(1−x)CaxAl2O4-based microwave dielectric ceramics

This study reports the characterization, fabrication, and performance of global positioning systems (GPS) patch antennas as a function of calcium (Ca) concentration and dielectric constant (? _r ). Zn_(1?x)Ca_xAl₂O₄ (x = 0.00, 0.05, 0.10, 0.20, 0.25, and 0.30) thin films were prepared through a sol–gel method. The effects of added Ca on the nanostructures and dielectric properties of ZnAl₂O₄ ceramics were investigated. The addition of Ca increased the crystallite size, grain size, and surface morphology, thereby increasing the density and dielectric constant. As the Ca content increased, the ? _r values linearly increased. However, the Q _u values decreased (at x = 0.25 to x = 0.25) after achieving the optimum values at x = 0.20. Finally, GPS patch antennas were successfully fabricated using the Zn_(1?x)Ca_xAl₂O₄ material. The patch antenna sizes decreased as ? _r increased from 2.88  × 4.37 cm (? _r  ≈ 8.52) to 2.88  × 4.37 cm (? _r  ≈ 10.16). The performance (return loss analysis) and operating frequencies of the GPS patch antennas were measured using the PNA series network analyzer. Results show that the patch antenna resonates at frequency of 1.570 GHz and produces a return loss bandwidth between ?16.6 and ?27.5 dB. The optimal performance of GPS patch antenna with ? _r  ≈ 9.95, Q _u  ≈ 6,186, and return loss = ?27.5 dB was obtained from specimen using Zn_0.80Ca_0.20Al₂O₄ (x = 0.20) ceramics.     

Synthesis and fabrication of (1 − x)ZnAl2O4–xSiO2 thin films to be applied as patch antennas

Zinc aluminate compounds have been dispersed in silica matrix prepared by sol-gel method with different compositions for (1 ? x)ZnAl₂O₄–xSiO₂. Continuous stirring of ethylene glycol solution contained zinc nitrate, aluminium nitrate and silicon dioxide to produces gel precursor. Structural and morphological studies of (1 ? x)ZnAl₂O₄–xSiO₂ thin films were examined by field emission scanning electron microscopy (FESEM) and X-ray diffractometer (XRD) analysis. The FESEM images showed the spherical structures with porosity for (1 ? x)ZnAl₂O₄–xSiO₂ thin films. XRD analysis indicated that the crystallite size for (1 ? x)ZnAl₂O₄–xSiO₂ increased from 39.79 to 44.34 nm. Fourier transform infra-red analysis showed that the existence of H₂O molecules and the presence of nitrate group within the samples. Dielectric permittivity (ε _r ) of (1 ? x)ZnAl₂O₄–xSiO₂ samples were measured within frequency range from 1 Hz to 1 MHz. The dielectric permittivity, ε _r decreased as frequency was applied to the sample. The performance of the patch antenna can be measured using return loss analysis. The highest result shows that the patch antenna resonated at frequency 3.46 GHz and gives ?14.25 dB return loss bandwidth.     

Analysis of the stability of finite subspaces in density functional theory

We have studied photodissociation of the A state of the H₂S⁺ ion using the quantum-chemical CAS methods, and the 1² A″ (X ² B ₁) and 1⁴ A″ states are involved in photodissociation of the 1² A′ (A ² A ₁) state (the electronic states in dissociation were studied in the C _s symmetry). The CASPT2 S-loss dissociation potential energy curve (PEC) calculations indicate that the 1² A″ and 1² A′ states correlate with the second limit [H₂ + S⁺(² D)] while the 1⁴ A″ state correlates with the first limit [H₂ + S⁺(⁴S)] and that there are a transition state and a local minimum along the 1² A′ PEC and the repulsive 1⁴ A″ PEC crosses the 1² A″ and 1² A′ PECs. The CASPT2 H-loss dissociation PEC calculations indicate that the 1² A″ and 1⁴ A″ states correlate with the first limit [HS⁺(X ³Σ^?) + H] while the 1² A′ state correlates with the second limit [HS⁺(a ¹Δ) + H] and that the repulsive 1⁴ A″ PEC crosses the 1² A′ PEC. For the crossing doublet and quartet states in pairs, we performed CASSCF minimum energy crossing point (MECP) calculations, and the CASSCF spin-orbit couplings and CASPT2 energies at the MECP geometries were calculated. We examined the two previously proposed mechanisms (mechanisms I and II) for dissociation of the A state to the S⁺ ion, based on our calculation results. We suggest processes for dissociation of the A state to the S⁺ ion (processes I and II, based on mechanisms I and II, respectively) and to the SH⁺ ion (process III) and conclude that photodissociation of the A state mainly leads to the S⁺ ion via the most energetically favorable process II: A ² A ₁ (1² A′) (2.38 eV) → barrier at the linearity (2.96 eV) → X ² B ₁ (1² A″) (0.0 eV) → the 1² A″/1⁴ A″ MECP (3.50 eV, large spin-orbit coupling) → H₂ $ (X^{ 1} \Upsigma_{\text{g}}^{ + } ) $  + S⁺(⁴S) (2.92 eV) (the CASPT2 relative energy values to X ² B ₁ are given in parentheses and the largest value is 3.50 eV at the MECP).     

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.     

A study of thermal and dielectric behavior of melaminium perchlorate monohydrate single crystals

Single crystals of melaminium perchlorate monohydrate (MPM) have been grown from aqueous solution by slow solvent evaporation method at room temperature. X-ray powder diffraction analysis confirms the title crystal crystallizes in the triclinic (P-1) structure and the calculated lattice parameters are a = 5.6275 ± 0.0780 Å, b = 7.6926 ± 0.1025 Å, c = 12.0878 ± 0.2756 Å, α = 103.89 ± 1.01°, β = 94.61 ± 0.92°, γ = 110.22 ± 0.81°, and V = 468.95 Å³. The thermal decomposition behavior of MPM has been studied by means of thermogravimetric analysis at three different heating rates 5, 10, and 20 °C min^?1. The values of effective activation energy (E _a), pre-exponential factor (ln A) of each stage of thermal decomposition for all heating rates were calculated by model free method: Kissinger, Kim–Park, and Flynn–Wall method. A significant variation of effective activation energy (E _a) with conversion (α) indicates that the process is kinetically complex. The linear relationship between the A and E _a values was established (compensation effect). Dielectric study has also been carried out and it is found that both dielectric constant (ε′) and dielectric loss (ε″) decreases with increase in frequency.     

Crystal structures, magnetic, dielectric and ferroelectric properties of two copper(II) complexes with m-nitrobenzoic acid

Reactions of CuCl₂, m-nitrobenzoic acid (HNBA) and NaOH with 2,2′-bipyridine (bpy) or 1,10-phenanthroline (phen) in aqueous ethanol afforded two Cu(II) complexes Cu(bpy)(NBA)₂, 1, and [Cu(phen)(H₂O)₂(NBA)](NBA), 2. The monomolecular Cu(bpy)(NBA)₂ moieties are both bridged by hydrogen bonding interactions and interlayer π ^*–π ^*stacking interactions to form a 3D (3,4,6)-connected supramolecular architecture with the Schäfli symbol of (4⁴·6²)(4⁴·6⁶·8⁵)(6³)₂. Complex 2 crystallizes in a noncentrosymmetric space group P2₁ where all molecules show the same orientation along the polar b axis. Preliminary investigations suggest that 2 exhibits ferroelectric hysteresis loops at room temperature with remanent polarization (P _r) of ca. 0.09 μC cm^?2 and coercive electric fields of 2.53 kV cm^?1, respectively. It may be a potential ferroelectric with a relatively large spontaneous polarization (P _s) of 0.22 μC cm^?2. Furthermore, permittivity property measurements reveal a dielectric constant (ε _r) of 6.36. Variable-temperature (2–300 K) magnetic susceptibility measurements showed the presence of weak ferromagnetic interactions between the Cu(II) ions for both 1 and 2.     

Novel conducting poly(3,4-ethylenedioxythiophene) – Graphene nanocomposites with gigantic dielectric properties and narrow optical energy band gap

Novel nanocomposites, consisting of conducting poly(3,4-ethylenedioxythiophene) [PEDOT] and graphene nanoplatelets [GNPs], were successfully synthesized by in-situ chemical-oxidative polymerization of 3,4-ethylenedioxythiophene [EDOT] using ammonium peroxydisulfate as an oxidizing agent. The formation of PEDOT and its incorporation onto the surface of GNPs were confirmed by scanning electron microscopy, Fourier-transform infrared-spectroscopy, and X-ray diffraction. The optical energy band gap, E_g^opt, was determined by UV–Vis spectroscopy. Dielectric constant and loss as well as AC electrical conductivity, σ_AC, were determined in the frequency range from 10 Hz to 8 MHz. The PEDOT-GNP nanocomposites were found to have extremely large dielectric constant, ε′, significantly high σ_AC, and narrow E_g^opt values. In particular, PEDOT-GNP nanocomposite with 10 wt% GNP has a gigantic dielectric constant of the order of 9 × 10⁵ at 1 kHz and a narrow optical energy band gap of 1.26 eV. The ε′ values (10⁸ to 10⁵ in the frequency range from 10 Hz to 5 MHz) of PEDOT-10 wt% GNP are the highest among those reported in the literature for carbon based polymer nanocomposites. The massive quantity of micro-capacitors formed in the nanocomposites, prior to the creation of conductive networks, leads to the gigantic dielectric properties. The ε′ and σ_AC values of PEDOT-10 wt% GNP nanocomposite were about 90 and 400 times larger than those of pure PEDOT. Our method should be particularly promising in the development of new materials for high energy storage applications.     

Investigation of the effects of graphite flake alignment on thermal emissivity by applying a magnetic field during coating of an aluminum sheet

In this study we investigated the effects of graphite flake alignment on thermal emissivity by applying a magnetic field during coating of aluminum sheets with graphite. The coating paste was prepared by ball milling graphite flakes with an organic binder. The graphite flake content was 9.1, 13.0, 16.7, 20.0, or 23.1 wt.%. After coating of aluminum sheets with the paste by dipping, a magnetic field was applied vertically to the coated aluminum sheet by use of neodymium magnets. It was observed that the graphite flakes were aligned at an angle to the surface by application of the magnetic field. In contrast, in the absence of the magnetic field the graphite flakes were aligned horizontally on the aluminum sheets. The surface roughness of specimens prepared by use of a magnetic field (MF; R _a = 10.172–14.654 μm) was more than twofold that of specimens for which no magnetic field was applied (NMF; R _a = 4.564 μm). The thermal emissivity of MF9 (9.1 wt.% graphite; ε = 0.80) was higher than that of NMF9 (9.1 wt.% graphite; ε = 0.77). The thermal emissivity of MF20 (20.0 wt.% graphite) was 0.91, the highest in this study. It was shown that flakes aligned at an angle to the surface contribute to enhanced thermal emissivity. Well aligned graphite flakes are therefore expected to enable high thermal dissipation from electronic components.     

Thermal behavior of BST//PVDF ceramic–polymer composites

In this paper, we report the results of a study of microstructure and thermal behavior of ceramic–polymer composites composed of barium strontium titanate Ba_0.6Sr_0.4TiO₃ (BST60/40) and polyvinylidene fluoride (PVDF). The Ba_0.6Sr_0.4TiO₃ ceramic powder was prepared by the sol–gel method. Thermal evolution of the dried gel as well as ceramic powder was studied by simultaneous thermal analysis. The composite BST60/40//PVDF was obtained by hot pressing method for volume fraction of BST60/40 ceramic powder c _v = 50 %. The morphology of BST60/40//PVDF composite powder was observed by transmission electron microscopy and the morphology of BST60/40//PVDF composite sample was observed by scanning electron microscopy. Temperature dependence of dielectric constant and dielectric loss factor of BST60/40//PVDF composites was measured in the frequency range of f = (10 × 10³–1 × 10⁶) Hz. Dynamic mechanical properties of BST60/40//PVDF composites were measured by dynamic mechanical thermal analysis DMTA.     

Effect of Tb content on microstructure and ferroelectric properties of Bi4−x Tb x Ti3O12 thin films grown by sol–gel method

The effects of Tb substitution on the structural and electrical properties of ferroelectric Bi₄Ti₃O₁₂ (BTO) thin films grown on Pt/TiO₂/SiO₂/Si substrates by a sol–gel process have been reported. X-ray diffraction indicated A-site Tb substitutions did not change the polycrystalline bi-layered Aurivillius structure of the BTO, but a lattice distortion was observed. The leakage current behavior at room temperature of the films was studied and it was found that the leakage current density decreased from 10^?2 to 10^?4 A/cm² with the increase of x under 150 kV/cm. The remnant polarization (2P _r ) and dielectric constant (ε _r) increase firstly and then decreases with the increase of the Tb content. We observed a substantial increase in the remnant polarization (2P _r ) with Tb substitution and obtained a maximum value of~60 μC/cm² at an applied electric field of 500 kV/cm for x = 0.4. Moreover, this BTT-0.4 capacitor did not show fatigue behaviors after 1.0 × 10¹⁰ switching cycles, suggesting an anti-fatigue character.     

Study of (1−x)ZnAl2O4–xSiO2 spinel structures as microwave dielectric materials

Sol–gel method was used to synthesize zinc aluminate (ZnAl₂O₄) dispersed into silica matrix with different compositions of x. Morphological structure of (1?x)ZnAl₂O₄–xSiO₂ samples were investigated by field emission scanning electron microscope (FESEM) and X-ray diffractometer (XRD). The FESEM images showed spherical structures and agglomerated particles occurred inside the samples. XRD analysis indicated the cubic phase formation of the samples. The crystallite size, D was calculated and it was found that the crystallite size are slightly increased from 8 to 17 nm. FTIR spectra analysis shows that the water presence in the samples and also the presence of nitrate group. The dielectric properties have been measured, ε _r value was found to be around 13.0. The S₁₁ parameter analysis shows the samples was resonated at 2.40 GHz and gives different values of bandwidth for microstrip patch antenna application.     

Evaluation of the Static Permittivity of Aqueous Electrolytes

The static (relative) permittivity of aqueous electrolyte solutions at 25 °C, ε(ω = 0) where ω is the frequency of the external field, has been obtained from the literature. The limiting dielectric decrements δ = ? lim(c → 0)dε/dc, where c is the electrolyte concentration (≤ 1 mol·dm^?3), are tabulated. The most appropriate additive individual ionic δ _i values are derived. The effect of ion pairing in the solutions is briefly discussed.     

Observation and interpretation of 157.5 T internal magnetic field in Fe[C(SiMe3)3]2 coordination compound

The compound Fe[C(SiMe₃)₃]₂ has been prepared and investigated by the means of powder X-ray diffractometry and ⁵⁷Fe Mössbauer spectroscopy. The compound’s unique geometry, in which iron is linearly coordinated by the two C(SiMe₃)₃ ligands, results in a unusual electronic structure of iron, which is visualized as an extreme high hyperfine magnetic field of 157.5(8) T as sensed by the ⁵⁷Fe nucleus at T = 20 K. In order to obtain information on the electronic structure of iron and on the bonds to the ligands, DFT (density functional theory) calculations were carried out on Fe[C(SiMe₃)₃]₂. The high-spin state of iron was found to be energetically favored: an Fe(II) electron configuration of 3d^5.83 4s^0.72 is predicted, where the 4s electron density is only slightly polarized, and most of the unpaired electrons have 3d character. By assuming a linear crystal field, and associated 3d level scheme as a starting point, it is suggested that the extreme high hyperfine magnetic field, observed along with an apparently negative quadrupole splitting, is perpendicular to the C–Fe(II)–C bond axis, and can be decomposed mainly into contact (B _c ≈ 44 T), dipolar (B _d ≈ 14 T), and orbital (B _L ≈ 99 T) hyperfine magnetic field contributions.     

Miniaturization of GPS patch antennas based on novel dielectric ceramics Zn(1−x)MgxAl2O4 by sol–gel method

The need for miniaturization and weight reduction of GPS patch antennas has prompted the search for new microwave dielectric materials. In this study, a sol–gel method was used to prepare Zn_(1?x)Mg_xAl₂O₄ thin films and fabricate GPS patch antennas at a low annealing temperature (700 °C). X-ray diffraction (XRD) patterns, field emission scanning electron microscopy images, Fourier transform infrared spectra, and optical band gap analyses confirmed the nanostructure of (Mg/Zn)Al₂O₄. The XRD patterns displayed the characteristic peaks of (Mg/Zn)Al₂O₄ with a face-centered cubic structure. Mg addition decreased the crystallite size, surface morphology, and lattice parameters of the resultant films, evidently affecting their density and dielectric constant (? _r ). Based on the material investigated and microwave antenna theory, GPS patch antennas were fabricated using Zn_(1?x)Mg_xAl₂O₄ and then studied using a PNA series network analyzer. The fabricated patch antennas with different ? _r ceramics decreased in size from 12.5 to 10.8 cm². The patch antennas resonated at a frequency of 1.570 GHz and provided a return loss bandwidth between ?16.6 and ?20.0 dB; their bandwidth also improved from 90 to 255 MHz. The GPS patch antenna fabricated from Zn_0.70Mg_0.30Al₂O₄ showed an excellent combination of return loss (?20.0 dB), small size (10.8 cm²), and wide bandwidth (255 MHz). Therefore, addition of Mg improves antenna performance and decreases the dimensions of the device.     

Magnetic hollow poly(N-isopropylacrylamide-co-N,N′-methylenebisacrylamide-co-glycidyl acrylate) particles prepared by inverse emulsion polymerization

To prepare functionalized magnetic polymer particles that are thermally responsive, inverse emulsion copolymerization of N-isopropylacrylamide, N,N′-methylenebisacrylamide and glycidyl acrylate (GA) was investigated in paraffin oil in the presence of γ-Fe₂O₃ nanoparticles dispersed in a water/glycerol mixture. The resulting polymer particles were characterized regarding the morphology, size, polydispersity, iron content, and the temperature-dependent phase transition using optical microscopy, transmission electron microscopy, scanning electron microscopy, atomic absorption spectroscopy, and differential scanning calorimetry. Magnetic properties were examined using hysteresis loop measurements and by analyzing the magnetic susceptibility with respect to temperature. We have also investigated the influence of the concentration of γ-Fe₂O₃ and GA in monomers on properties of the particles (morphology, size, and presence of oxirane groups). The particles possessed a hollow structure as a result of phase separation between water/glycerol hydrophilic solvents in the polymerization feed and the forming polymer. Depending on the concentration of γ-Fe₂O₃ in the monomer phase, the magnetic hollow particles contained 5–24 wt% iron. In water, the particles gradually collapsed when the temperature was raised to 40 °C because the elevated temperature weakened hydration and the PNIPAAm chains gradually became more hydrophobic.     

Similarity examination of truncated virial equation of state correspondence to linear isothermal regularity (LIR) by applying square-well (SW) potential

Linear isotherm regularity works very well for fluids at high densities, and it has been shown that it is compatible with the EOSs based on statistical–mechanical theory. On the other hand, at low densities, the first few terms of virial EOS have the most contribution to express the deviations from ideal behavior. For finding similarities between dense and dilute states, experimental p–v–T data of 14 fluids (He, Ne, Ar, Kr, H₂, O₂, N₂, CO, NH₃, CH₃OH, CH₄, C₂H₄, C₂H₆ and C₃H₈) are examined. Comparing the thermal dependencies of the attraction and repulsion terms (A and B) of the LIR with the second and third virial coefficients (B ₂ and B ₃) in liquid and supercritical regions (0.7 < T _r < 3.0) shows a remarkable similarity. Square-well potential is applied to examination and comparison of theoretical results with experimental results. It is shown that in liquid and supercritical regions, (1) the short-range potential governs among particles in dense fluids, and the long-range interactions become important in the less dense fluid, (2) similar to Boyle temperature, T _B, in dilute state, there is a temperature as T′_B (in dense fluids) that the attractive forces and the repulsive forces acting on the dense-fluid particles balance out; thus, probably there is a maximum σ (molecular diameter) at nearly 2T _c (T′_B), and (3) in the liquid and supercritical regions (0.7 < T _r < 3.0), in the first-order approximation, there are no significant interactions higher than triple interactions in dense-fluid particles.     

Dielectric properties of polyester resins—1

The dielectric properties of unsaturated polyester resins mixed with styrene have been investigated in the microwave 1–12 GHz range. The frequency dependence of the permittivity (a_r^′anda_r^′′) is typical of an orientational polarization relaxation process. A Davidson-Cole like model fits the experimental results reasonably well. A hypothesis on the molecular process is discussed, correlating the influence of temperature and sample composition.     

Dielectric relaxation study of aniline,N-methylaniline and N,N-dimethylaniline and alcohol in 1, 4-dioxane using picosecond time-domain reflectometry

A time-domain reflectometry technique has been used to measure complex dielectric permittivity ε*(ω) = ε?(ω) ? jε″(ω) of 1-propanol–dioxane, 2-propanol–dioxane, aniline–dioxane, N-methylaniline–dioxane and N,N-dimethylaniline–dioxane mixtures in the frequency range of 10 MHz to 30 GHz. The complex permittivity spectrum has been fitted with a single relaxation time with a small amount of Davidson–Cole behaviour. The least squares fit method has been used to obtain the static dielectric constant (ε₀), relaxation time (τ), Bruggeman factor and Kirkwood correlation factor. The Luzar theoretical model is used to compute the binding energies and average number of hydrogen bond between co-solvent–co-solvent and co-solvent–dioxane molecules.