Search Results (25)

Polymer-matrix composites with ceramic fillers have various applications, one of which is the modification of the electric field. For this purpose, in this work, high-permittivity silicone composites with different polarization titanates were produced by mechanical mixing. The ceramic fillers chosen were CaCu₃Ti₄O₁₂, K_xFe_yTi_8−yO₁₆, and BaTiO₃ powders with high permittivity values and uniformly distributed in the polymer volume. Ceramic powders were studied by X-ray phase analysis and scanning electron microscopy methods. The proportion of ceramic powder was 25 wt.%. In parallel, composites were prepared with the addition of 25 wt.% glycerin. The functional properties of silicone composites were studied using the following parameters: the electrical strength and permittivity. The addition of all types of ceramic fillers, both together and without glycerin, led to a decrease in electrical strength (below 15 kV·mm⁻¹); the exception is the sample with the CCTO without glycerin (about 28 kV·mm⁻¹). The permittivity and the dielectric loss tangent of the composites increased as a result of the addition of fillers, especially noticeable in combination with glycerol in the low-frequency region. The obtained results are in good agreement with the literature data and can be used in the field of insulation in a high-permittivity layer to equalize equipotential fields. Full article

Three-phase polymer composites are promising materials for creating electronic device components. The qualitative and quantitative composition of such composites has a significant effect on their functional, in particular dielectric properties. In this study, ceramic filler K₂Ni_0.93Ti_7.07O₁₆ (KNTO) with Ag coating as conductive additive (0.5, 1.0, 2.5 wt.%) was introduced into the polyvinylidene difluoride (PVDF) polymer matrix in amounts of 7.5, 15, 22.5, and 30 vol.%. to optimize the dielectric constant and dielectric loss tangent. The filler was characterized by X-ray phase analysis, Fourier-transform infrared spectroscopy and Scanning electron microscopy methods. The dielectric constant, dielectric loss tangent, and conductivity of three-phase composites KNTO@Ag-PVDF were studied in comparison with two-phase composites KNTO-PVDF in the frequency range from 10² Hz to 10⁶ Hz. The dielectric constant values of composites containing 7.5, 15, 22.5, and 30 vol.% filler were 12, 13, 17.4, 19.2 for pure KNTO and 13, 19, 25, 31 for KNTO@Ag filler (2.5 wt.%) at frequency 10 kHz. The dielectric loss tangent ranged from 0.111 to 0.340 at a filler content of 7.5 to 30 vol.%. A significantly enhanced balance of dielectric properties of PVDF-based composites was found with K₂Ni_0.93Ti_7.07O₁₆ as ceramic filler for 1 wt.% of silver. Composites KNTO@Ag(1 wt.%)-PVDF can be applied as dielectrics for passive elements of flexible electronics. Full article

The development of new electrode materials for electrochemical systems for various purposes is a significant and in-demand task of scientific research. Layered transition metal carbides and nitrides, known as MXenes, show great potential for use as electrodes in electrochemical energy storage devices operating in aqueous electrolytes. In this work, a multilayer Ti₃C₂T_x MXene was obtained from a Ti₃AlC₂ precursor and studied as the electrode material of a symmetrical supercapacitor with an aqueous LiCl electrolyte. The formation of the MXene structure was confirmed by the data from X-ray phase analysis and scanning electron microscopy. The X-ray diffraction pattern showed the disappearance of the main reflections related to the Ti₃AlC₂ phase and the shift of the reflection peak (002) from 9.4° to 6.7°, which indicated successful etching of the Al layers from the Ti₃AlC₂ precursor. At electrolyte concentrations of 1, 5, 10, and 20 M, the supercapacitors demonstrated high specific capacitances of 105, 120, 126, and 151 F·g⁻¹ at a scan rate of 5 mV·s⁻¹. In addition, an increase in the LiCl concentration contributed to the expansion of the potential window from 0.7 to 1 V. It was shown that the contribution of the surface capacitance to the total capacitance of the electrode is about 40% and depends little on the scan rate. In addition, the symmetrical supercapacitor with 5 M electrolyte showed good cyclic stability with capacitance retention of 88% over 10,000 cycles. The parameters of the main components of the physical processes of supercapacitors based on Ti₃C₂T_x were determined by the method of impedance spectroscopy. Full article

Effective low-grade waste heat harvesting and its conversion into electric energy by the means of thermoelectrochemical cells (TECs) are a strong theme in the field of renewable energy investigation. Despite considerable scientific research, TECs have not yet been practically applied due to the high cost of electrode materials and low effectiveness levels. A large hypothetical Seebeck coefficient allow the harvest of the low-grade waste heat and, particularly, to use TECs for collecting human body heat. This paper demonstrates the investigation of estimated hypothetical Seebeck coefficient dependency on KOH electrolyte concentration for TECs with hollow nanostructured Ni/NiO microsphere electrodes. It proposes a thermoelectrochemical cell with power density of 1.72 W·m⁻² and describes the chemistry of electrodes and near-electrode space. Also, the paper demonstrates a decrease in charge transfer resistance from 3.5 to 0.52 Ω and a decrease in capacitive behavior with increasing electrolyte concentration due to diffusion effects. Full article

In this paper, Li_xCa_(1−x)Cu₃Ti₄O₁₂ (LCCTO) solid solutions were successfully synthesized. XRD diagrams showed that dopant acceptor Li⁺ cations, in a concentration range of x = 0.01–0.10, were successfully merged into CCTO structure. It was found that doping with low concentrations of lithium (x < 0.05) inhibited grain growth during annealing; however, for x > 0.05, the grain growth process resumed. Permittivity and dielectric losses of obtained LCCTO ceramics were analyzed by the means of impedance spectroscopy in a frequency range from 10⁻¹ to 10⁶ Hz. It was revealed that acceptor doping with lithium at an appropriate concentration of x = 0.05 allowed to obtain ceramics with a permittivity level of ε′ = 3 × 10⁴ and low dielectric losses tanδ < 0.1 at 1 kHz. Further addition of lithium in a concentration range of x = 0.075–0.10 led to a sharp decline in permittivity and an increase in dielectric losses. It was discovered that lithium addition to CCTO ceramics drastically decreased grain boundary resistivity from 115 MΩ·cm to 5–40 MΩ·cm at x = 0.01–0.10. Using Havriliak–Negami equation, the relaxation times for grain dipoles and grain boundary dipoles were found to be ranging from 0.8 × 10⁻⁶ to 1.7 × 10⁻⁶ s and from 0.4 × 10⁻⁴ to 7.1 × 10⁻⁴ s, respectively. The developed materials can be used in the manufacture of Multilayer Ceramic Capacitors (MLCC) as a dielectric. Full article

In this work we have synthesized Ti₃C₂T_X MXene powder and studied its structure. Composite electrochemical coatings (CECs) of Ni-Ti₃C₂T_X MXene were obtained from a sulfate– chloride bath in the galvanostatic regime. The microstructure of CEC was researched using X-ray phase analysis and scanning electron microscopy methods. It has been established that a Ni–Ti₃C₂T_X MXene CEC microhardness rises by about 1.80 times compared with electrolytic Ni without a dispersed phase. For corrosion research, different corrosive media is applied. The corrosion–electrochemical behavior of Ni–Ti₃C₂T_X MXene CECs by the chronovoltamperometry method in 0.5 M H₂SO₄ solution has been investigated. Trials in 3.5% NaCl have shown that Ti₃C₂T_X MXene inclusion into the matrix of the electrochemical Ni results in a decrease in the corrosion rate by 1.60–1.75 times. These effects are due to the addition of Ti₃C₂T_X MXene into the nickel matrix and the formation of CECs with a strengthening fine-grained structure. Full article

The results of experimental studies of ohmic conductivity degradation in the ensembles of nanostructured anatase bridges under a long-term effect of direct current are presented. Stochastic sets of partially conducting inter-electrode bridges consisting of close-packed anatase nanoparticles were formed by means of the seeding particles from drying aqueous suspensions on the surfaces of silica substrates with interdigital platinum electrodes. Multiple-run experiments conducted at room temperature have shown that ohmic conductivity degradation in these systems is irreversible. It is presumably due to the accumulated capture of conduction electrons by deep traps in anatase nanoparticles. The scaling analysis of voltage drops across the samples at the final stage of degradation gives a critical exponent for ohmic conductivity as ≈1.597. This value satisfactorily agrees with the reported model data for percolation systems. At an early stage of degradation, the spectral density of conduction current fluctuations observed within the frequency range of 0.01–1 Hz decreases approximately as $1/\omega$, while near the percolation threshold, the decreasing trend changes to $\approx 1/{\omega }^2$. This transition is interpreted in terms of the increasing contribution of blockages and subsequent avalanche-like breakdowns of part of the local conduction channels in the bridges into electron transport near the percolation threshold. Full article

In this study, we report the effect of intercalation of dimethyl sulfoxide (DMSO) and urea molecules into the interlayer space of Ti₃C₂T_x MXene on the dielectric properties of poly(vinylidene fluoride) (PVDF)/MXene polymer nanocomposites. MXenes were obtained by a simple hydrothermal method using Ti₃AlC₂ and a mixture of HCl and KF, and they were then intercalated with DMSO and urea molecules to improve the exfoliation of the layers. Then, nanocomposites based on a PVDF matrix loading of 5–30 wt.% MXene were fabricated by hot pressing. The powders and nanocomposites obtained were characterized by using XRD, FTIR, and SEM. The dielectric properties of the nanocomposites were studied by impedance spectroscopy in the frequency range of 10²–10⁶ Hz. As a result, the intercalation of MXene with urea molecules made it possible to increase the permittivity from 22 to 27 and to slightly decrease the dielectric loss tangent at a filler loading of 25 wt.% and a frequency of 1 kHz. The intercalation of MXene with DMSO molecules made it possible to achieve an increase in the permittivity up to 30 at a MXene loading of 25 wt.%, but the dielectric loss tangent was increased to 0.11. A discussion of the possible mechanisms of MXene intercalation influence on the dielectric properties of PVDF/Ti₃C₂T_x MXene nanocomposites is presented. Full article

Tm₂(Ti_2−xTm_x)O_7−x/2 (x = 0, 0.1, 0.18, 0.28, 0.74) solid electrolytes have been investigated as potential electrolyte materials for solid oxygen fuel cells (SOFCs), operating in the medium temperature range (600–700 °C). The design of new oxygen-conducting materials is of importance for their possible utilization in the solid oxide fuel cells. The oxygen–ion conductivity of the Tm₂(Ti_2−xTm_x)O_7−x/2 (x = 0, 0.1, 0.18, 0.28, 0.74) “stuffed” pyrochlores ceramics was investigated by electrochemical impedance spectroscopy (two-probe AC) in dry and wet air. The synthesis of precursors via co-precipitation and the precipitate decomposition temperature have been shown to be of key importance for obtaining dense and highly conductive ceramics. At ~770 °C, the highest total conductivity, ~3.16 × 10⁻³ S/cm, is offered by Tm₂Ti₂O₇. The conductivity of the fluorite-like solid solution Tm₂(Ti_2−xTm_x)O_7−x/2 (x = 0.74) is an order of magnitude lower. However, for the first time a proton contribution of ~5 × 10⁻⁵ S/cm at 600 °C has been found in Tm₂(Ti_2−xTm_x)O_7−x/2 (x = 0.74) fluorite. Until now, compositions with proton conductivity were not known for the intermediate and heavy rare earth titanates Ln₂(Ti_2−xLn_x)O_7−x/2 (Ln = Ho − Lu) systems. The use of X-ray diffraction (structural analysis with Rietveld refinement), optical spectroscopy and dielectric permittivity data allowed us to follow structural disordering in the solid solution series with increasing thulium oxide content. High and low cooling rates have been shown to have different effects on the properties of the ceramics. Slow cooling initiates’ growth of fluorite nanodomains in a pyrochlore matrix. The fabrication of such nanostructured dense composites is a promising direction in the synthesis of highly conductive solid electrolytes for SOFCs. We assume that high-temperature firing of nanophase precursors helps to obtain lightly doped “stuffed” pyrochlores, which also provide the high oxygen–ion conductivity. Full article

The production of three-phase composites is a relevant and effective approach to obtain materials with the required mechanical and dielectric properties. In this work, dust, which is a waste product of steelmaking and is formed during the gas cleaning of electric arc furnaces at the production base of Severstal, was used as a functional filler for the low-density polyethylene polymer matrix. The fractional, elemental, qualitative, and quantitative phase composition of the native dust was studied using laser diffraction, energy-dispersive X-ray phase analysis, and X-ray fluorescence spectrometry. An increase in the permittivity of the dust was achieved due to its reduction in a hydrogen atmosphere and, as a consequence, a change in the elemental and phase composition causing an increase in the concentration of metallic iron. Composite films were obtained using a blending roll mill at temperatures of 130 and 140 °C. The concentration of the main filler was 18.75, 37.5, and 75 wt.%. Additionally, a conductive additive in the form of MWCNTs was introduced into the composition of the composites in an amount of 0.25 wt.%. The uniformity of the filler distribution in the polymer matrix was assessed from electron micrographs. The dielectric properties of fillers and composite films based on polyethylene filled with electric arc furnace dust and MWCNTs were studied using impedance spectroscopy in the frequency range of 10–10⁶ Hz. The use of reduced dust at a concentration of 25.8 vol.% combined with 0.25 wt.% MWCNTs in the composition of the composite film provided an increase in ε′ to 13.5 at tan δ = 0.038. Thus, three-phase polymer matrix composites based on LDPE using dust as a filler with a conductive microadditive of MWCNTs have a synergistic effect, which manifests itself in an increase in the permittivity and a decrease in dielectric losses. Full article

Some solid solutions with the chemical composition K_xFe_yTi_8-yO₁₆ (KFTO) and a hollandite-like structure were successfully synthesized by modified sol–gel method. The obtained powders were characterized using X-ray diffraction (XRD) and scanning electron microscopy (SEM). The ceramic pellets based on KFTO powders were obtained by compressing and sintering at 1080 °C for 4 h. The sinters were characterized by X-ray and impedance spectroscopy. XRD results show that KFTO powders have a mono-phase tetragonal structure at x = 1.4–1.8 and y = 1.4–1.6. However, it was recognized that the hollandite-like phase could be broken during sintering to form TiO₂ and Fe₂TiO₅ crystals distributed throughout the volume of the ceramics. A frequency dependency of dielectric properties for the sinters was studied by impedance spectroscopy. It was found that an increase in the TiO₂ (rutile) phase during the sintering contributes to a decrease in dielectric losses. At the same time, the KFTO ceramics with reduced content of potassium had increased permittivity. The contribution of electron-pinned defect dipoles (EPDD) and internal barrier layer capacitance (IBLC) in the permittivity of the obtained ceramics was estimated using the Havriliak–Negami equation. It is shown that the KFTO ceramics have the polydisperse characteristic of dielectric relaxation. The observed grain and grain boundary dipole relaxation times were 1.03 × 10⁻⁶ to 5.51 × 10⁻⁶ s and 0.197 to 0.687 s, respectively. Full article

Herein, we report the synthesis, structure and magnetic properties of two mononuclear complexes of general formula [Dy(acac)₃(L)], where L = 2,2-dimethyl-1,3-dioxolo[4,5-f][1,10] phenanthroline (1) or 1,10-phenanthroline-5,6-dione (2), and acac⁻ = acetylacetonate anion. A distorted square-antiprismatic N₂O₆ environment around the central Dy(III) ion is formed by three acetylacetonate anions and a phenanthroline-type ligand. Both complexes display a single-molecule magnet (SMM) behavior at zero applied magnetic field. Modification of the peripheral part of ligands L provide substantial effects both on the magnetic relaxation barrier U_eff and on the quantum tunneling of magnetization (QTM). Ab initio quantum-chemical calculations are used to analyze the electronic structure and magnetic properties. Full article

In this work, protonated forms of potassium polytitanate were obtained by treating the precursor in HCl solution at pH 2.0, 3.0, 4.0, 5.0, 6.0, or 7.0. The synthesized materials were studied using XRD, FTIR, and XRF. The ion-exchange properties were studied using a LiCl solution with a concentration of C(Li⁺) = 0.01 mol/L. It was shown that extraction of lithium by potassium polytitanates is dependent on their protonation degree. It has been established that the samples with the highest degree of protonation obtained at pH = 2.0 and 3.0 have the highest efficiency in the ion-exchange extraction of Li⁺ ions from an aqueous solution. For determination of exchange ion rates and the mechanism of the ion-exchange process, pseudo-first- and pseudo-second-order models as well as the Weber–Morris intraparticle diffusion model, were employed. Experimental data with their participation are in good agreement with the pseudo-second-order kinetic model. The calculated kinetic parameters were q_e = 0.47–0.52 mmol/g and k₂ = 0.25–0.43, depending on the protonation degree of potassium polytitanate. The obtained experimental and calculated values of the sorption capacity were compared with the cation-exchange capacity of materials studied. According to the kinetics study, the mechanism of lithium adsorption by potassium polytitanates with a higher protonation degree is the ion-exchange chemical reaction. Low-cost protonated potassium polytitanates are promising to extract Li⁺ ions from aqueous solutions with a low concentration, as confirmed by the analysis of the results. Full article

New three-phase composites, destined for application as dielectrics in the manufacturing of passive elements of flexible electronics, and based on polymer (PVDF) matrix filled with powdered ceramics of the hollandite-like (KFTO(H)) structure (5.0; 7.5; 15; 30 vol.%) and carbon (MWCNT) additive (0.5; 1.0; 1.5 wt.% regarding the KFTO(H) amount), were obtained and studied by XRD, FTIR and SEM methods. Chemical composition and stoichiometric formula of the ceramic material synthesized by the sol–gel method were confirmed with the XRF analysis data. The influence of the ceramic and carbon fillers on the electrical properties of the obtained composites was investigated using impedance spectroscopy. The optimal combination of permittivity and dielectric loss values at 1 kHz (77.6 and 0.104, respectively) was found for the compositions containing K_1.6Fe_1.6Ti_6.4O₁₆ (30 vol.%) and MWCNTs (1.0 wt.% regarding the amount of ceramic filler). Full article

In this work, polymer matrix composites with the compositions PTFE/KFTO(H) and PTFE/KFTO(H)@CB and with filler volume fractions of 2.5, 5.0, 7.5, 15, and 30% (without and with carbon modification at a content of 2.5 wt.% regarding ceramic material) were produced by calendering and hot pressing and studied using FTIR, SEM, and impedance spectroscopy methods. Ceramic filler (KFTO(H)) was synthesized using the sol–gel Pechini method. Its structure was investigated and confirmed by the XRD method with following Rietveld refinement. The carbon black (CB) modification of KFTO(H) was carried out through the calcination of a mixture of ceramic and carbon materials in an argon atmosphere. Afterwards, composites producing all the components’ structures weren’t destroyed according to the FTIR results. The effect of carbon additive at a content of 2.5 wt.% relating to ceramic filler in the system of polymer matrix composites was shown, with permittivity increasing up to ε’ = 28 with a simultaneous decrease in dielectric loss (tanδ < 0.1) at f = 10³ Hz for composites of PTFE/KFTO(H)@CB (30 vol.%). Full article