Search Results (133)

Bi₆Fe₂Ti₃O₁₈ (BFTO) ceramics were synthesized via a solid-state reaction route using stoichiometric amounts of Bi₂O₃, TiO₂, and Fe₂O₃ powders. A thermal analysis of the powder mixture was conducted to optimize the heat treatment parameters. Energy-dispersive X-ray spectroscopy (EDS) confirmed the conservation of the chemical composition following calcination. Final densification was achieved through hot pressing. The crystal structure of the sintered samples, examined via X-ray diffraction at room temperature, revealed a tetragonal symmetry for BFTO ceramics sintered at 850 °C. Electron backscatter diffraction (EBSD) provided detailed insight into the crystallographic orientation and microstructure. Broadband dielectric spectroscopy (BBDS) was employed to investigate the dielectric response of BFTO ceramics over a frequency range of 10 mHz to 10 MHz and a temperature range of −30 °C to +200 °C. The temperature dependence of the relative permittivity (ε_r) and dielectric loss tangent (tan δ) were measured within a frequency range of 100 kHz to 900 kHz and a temperature range of 25 °C to 570 °C. The impedance data obtained from the BBDS measurements were validated using the Kramers–Kronig test and modeled using the Kohlrausch–Williams–Watts (KWW) function. The stretching parameter (β) ranged from ~0.72 to 0.82 in the impedance formalism within the temperature range from 200 °C to 20 °C. Full article

Relaxation behavior of water confined in reverse micelles under temperature-induced micelle clustering is undertaken using broadband dielectric spectroscopy in frequency range 1 Hz–20 GHz. All microemulsion systems with sufficiently noticeable micelle water pool (water/surfactant molar ratio W > 10) depict three relaxation processes, in low, high and microwave frequencies, anchoring with relaxation of shell (bound) water, orientation of surfactant anions at water-surfactant interface and relaxation of bulk water confined in reverse micelles. The analysis of dielectric relaxation processes in AOT-based w/o microemulsions under temperature induced clustering of reverse micelles were made according to structural information obtained in NMR and conductometry experiments. The “wait and switch” relaxation mechanism was applied for the explanation of results for water in the bound and bulk states under spatial limitation in reverse micelles. It was shown that surfactant layer predominantly influences the bound water. The properties of water close to AOT interface are determined by strong interactions between water and ionic AOT molecules, which perturb water H-bonding network. The decrease in micelle size causes a weakening of hydrogen bonds, deformation of its steric network and reduction in co-operative relaxation effects. Full article

Three liquid crystalline mixtures were investigated, consisting of compounds abbreviated as MHPOBC and 3F5FPhF6 with molar ratios 0.9:0.1 (MIX5FF6-1), 0.75:0.25 (MIX5FF6-2), and 0.5:0.5 (MIX5FF6-3). The presence of the smectic A*, smectic C*, and smectic C_A* phases was observed in all mixtures. The hexatic smectic X_A* phase, present in pure MHPOBC, disappeared quickly with an increasing admixture of 3F5FPhF6. Vitrification of smectic C_A* was observed for the equimolar mixture, with the glass transition temperature and fragility index comparable to the pure glassforming 3F5FPhF6 component. Partial crystallization to conformationally or orientationally disordered crystal phases was observed on cooling in two mixtures with a smaller fraction of 3F5FPhF6. Broadband dielectric spectroscopy was applied to study the relaxation times in smectic and crystal phases. Vogel–Fulcher–Tammann, Mauro–Yue–Ellison–Gupta–Allan, and critical-like models were applied for analysis of the α-relaxation time in supercooled smectic X_A* and smectic C_A* phases. Full article

The theory of orientational polarization and dielectric relaxation was developed by P. Debye more than 100 years ago. It approximates a molecule by a sphere having one or more dipole moments. While in the beginning the experimentally accessible spectral range was limited to roughly 6 decades in frequency, at the end of the last century, novel spectroscopic techniques were developed and dielectric spectroscopy became broadband, nowadays covering 18 decades with no gaps.This paved the avenue for a multitude of novel fields of research in soft matter and solid-state physics including fundamental questions like the scaling of relaxation processes or the dynamics of glasses. Yet the analysis of dielectric spectra is still based on the classical approach by Debye which does not consider the multitude of intra- and inter-molecular interactions within a molecular system. To experimentally overcome these principal limitations, it is suggested to take advantage of the molecular specificity of the infrared spectral range. This offers the unique possibility to realize a novel “Orientational Polarization Spectroscopy”, in which the orientational response of a molecular system can be analyzed on an atomistic scale. For that, the theory will be outlined and the first experimental results will be presented. Full article

Cross-linked polyethylene (XLPE) cables will gradually experience aging under various stresses during long-term operation, which may lead to faults and seriously affect the safe and stable operation of the power system. This article prepares aged cable samples by accelerating the thermal aging of XLPE cables, and combines frequency-domain dielectric spectroscopy (FDS) and the polarization–depolarization current method (PDC) for detection and analysis. By measuring the dielectric loss of aged cables using frequency-domain dielectric spectroscopy, it was found that the dielectric loss value in the low-frequency region significantly increases with aging time, indicating that aging leads to an increase in polarity groups and polarization loss. The high-frequency dielectric loss also significantly increases with the strengthening of dipole polarization. At the same time, using the polarization–depolarization current method to measure the polarization current and depolarization current of cables, it was found that the stable value of polarization current increases with aging time, further verifying the changes in the conductivity and polarization characteristics of insulation materials. Combining the broadband dielectric response characteristics of FDS (0.001 Hz–1 kHz) with the time-domain charge transfer analysis of PDC, the molecular structure degradation (dipole polarization enhancement) and interface defect accumulation (space charge effect) of cable aging are revealed from both frequency- and time-domain perspectives. The experimental results show that the integral value of the low-frequency region of the frequency-domain dielectric spectrum and the stable value of the polarization depolarization current are positively correlated with the aging time, and can make use of effective indicators to evaluate the aging state of XLPE cables. Full article

The dielectric relaxation dynamics in polymer composites critically determine their functional performance in advanced electrical systems. This study systematically investigates hybrid epoxy composites comprising neat epoxy resin (EP) and paper-reinforced systems (EIP), modified with 10–50 wt% polypropylene glycol diglycidyl ether (PEGDGE) plasticizer. Through synergistic application of differential scanning calorimetry (DSC) and broadband dielectric spectroscopy (10⁻¹–10⁶ Hz), the quantitative relationships between plasticizer content, glass transition temperature (Tg), and dielectric relaxation processes were established. DSC analysis reveals a linear Tg dependence with increasing PEGDGE content, attributed to enhanced molecular mobility. Dielectric characterization demonstrates three distinct relaxation regimes: α-relaxation below Tg, interfacial polarization at epoxy/PEGDGE boundaries, and paper/epoxy interfacial effects in EIP systems. A quantitative dielectric relaxation model was developed based on complex modulus formalism, coupled with Vogel–Fulcher–Tammann (VFT) analysis of DC conductivity. Activation energy mapping through Arrhenius decomposition reveals three characteristic values: (1) 82.01–87.80 kJ/mol for α-relaxation, (2) 55.96–64.64 kJ/mol for epoxy/PEGDGE interfaces, and (3) 30.88–44.38 kJ/mol for epoxy/paper interfaces. Crucially, the plasticizer content modulates these activation energies, demonstrating its role in tailoring interfacial dynamics. Full article

This report discusses the impact of nanoparticles on glass-forming systems composed of a liquid crystalline (LC) mixture E7 and paraelectric BaTiO₃ particles ($d\approx 50 \mathrm{n}\mathrm{m}$, globular), tested via broadband dielectric spectroscopy. In the isotropic phase, critical changes in the dielectric constant are shown. They are related to the weakly discontinuous nature of the isotropic–nematic transition. In the nematic phase, two primary relaxation times/processes and DC electric conductivity are considered, down to the glass temperature $T_g$. The prevalence of portrayals via the ‘double exponential’ MYEGA equation and the critical & activated Drozd-Rzoska relation for dynamic properties are shown. For the primary loss curve, critical-like changes of its maximum (peak) are evidenced: ${\epsilon }_{peak}^{″}\propto 1/\left(T-T_g^{*}\right)$ for $T_g<T<\left(T_g+25 \mathrm{K}\right)$, where $T_g^{*}<T_g$ denotes the extrapolated singular temperature. Dielectric constant monitoring revealed the permanent arrangement of rod-like LC molecules by nanoparticles’ endogenic impact in the nematic phase. The heuristic model regarding this unique behavior is presented. It considers a hypothetical link between the glass transition and a hidden near-critical discontinuous phase transition, uniquely avoiding a symmetry change. The uniaxiality of LC molecules enables the detection of critical-like features when approaching the glass transition, hypothetically associated with a specific ‘amorphous’ phase transition. Full article

The eco-friendly flame retardancy of polycarbonate (PC) was achieved by blending with phosphorylated-PC in the range of 1–5% w/w. Dynamic properties were characterized using broadband dielectric relaxation spectroscopy (DRS), while structural and thermal properties were investigated using Fourier transform infrared spectroscopy, wide-angle X-ray diffraction, small-angle X-ray scattering, differential scanning calorimetry, and thermogravimetric analysis. A reduction in the single glass transition temperature with increasing phosphorylated-PC content was observed, indicating that the blends were miscible. No crystalline phases were detected in any of the samples. The thermo-oxidative stability and UL-94 ratings of flame-retardant polycarbonates (FRPCs) improved compared to neat PC, with char residue increasing as the phosphorylated-PC content rose. DRS analysis revealed the formation of a well-defined local (β) relaxation in the FRPC samples, originating from the motion of phosphorylated branches. All samples exhibited the segmental (α) relaxation of PC chains above the glass transition temperature. The size of the cooperatively rearranging domain played a significant role in the dynamic fragility of the rigid FRPCs. Additionally, DRS analysis highlighted the presence of physical crosslinks from nanoclusters of phosphorylated polar groups, approximately 14 nm in size. Full article

Based on data from broadband dielectric spectroscopy (BDS) and a molecular model based on the Landau–de Gennes concept, the effect of confinement on the structural, dielectric, and dynamic properties of 4-n-pentyl-4′-cyanobiphenyl (5CB) in the nematic phase is studied. The dielectric permittivity and relaxation times were previously obtained by the BDS technique in a wide frequency range ($1\mathrm{MHz}\le \mathrm{f}\le 1\mathrm{GHz}$) in the nematic phase composed of 5CB molecules confined to Anopore membranes with pore sizes of 0.2 $\mathsf{\mu }$m. The distance-dependent values of the order parameter $P_2\left(r\right)$, the relaxation time $\tau \left(r\right)\equiv {\tau }_{00}^1\left(r\right)$, the rotational diffusion coefficient $D_{\perp }\left(r\right)$, and both rotational viscosity coefficients ${\gamma }_i\left(r\right)$ ($i=1,2$) as functions of the distance r away from the bounding surface are calculated by a combination of existing statistical-mechanical approaches and data obtained by the BDS technique. Reasonable agreement between the calculated and experimental values of ${\gamma }_i(i=1,2)$ for bulk 5CB is obtained. Full article

This report presents the first results on broadband dielectric spectroscopy insights into ODIC-forming neopentyl glycol (NPG) under compression up to the GPa domain. Particular attention was paid to the strongly discontinuous phase transition: orientationally disordered crystal (ODIC)–solid crystal. The insights cover static, dynamic, and energy-related properties, namely evolutions of the dielectric constant, DC electric conductivity, and dissipation factor. Worth stressing are results regarding the pressure-related Mossotti catastrophe-type behavior of the dielectric constant, the novel approach to non-Barus dynamics, and the discussion on fundamentals of dissipation factor changes in NPG. The results presented in the given report also introduce new experimental evidence and model discussions regarding the nature of ODIC mesophase and discontinuous phase transitions. Notable is the significance of understanding the nature of the colossal barocaloric effect in NPG. Full article

Background: It is generally accepted that water as a plasticizer can decrease the glass transition temperatures (T_gs) of amorphous drugs and drug delivery systems, resulting in physical instabilities. However, a recent study has reported an anti-plasticizing effect of water on amorphous lidocaine (LID). In co-amorphous systems, LID might be used as a co-former to impair the plasticizing effect of water. Method: Flurbiprofen (FLB) was used to form a co-amorphous system with a mole fraction of LID of 0.8. The effect of water on the stability of co-amorphous FLB-LID upon hydration was investigated. The crystallization behaviors of anhydrous and hydrated co-amorphous FLB-LID systems were measured by an isothermal modulated differential scanning calorimetric (iMDSC) method. The relaxation times of the co-amorphous FLB-LID system upon hydration were measured by a broadband dielectric spectroscopy (BDS), and the differences in Gibbs free energy (ΔG) and entropy (ΔS) between the amorphous and crystalline phases were determined by differential scanning calorimetry (DSC). Results: It was found that the crystallization tendency of co-amorphous FLB-LID decreased with the addition of water. Molecular mobility and thermodynamic factors were both investigated to explain the difference in crystallization tendencies of co-amorphous FLB-LID upon hydration. Conclusions: The results of the study showed that LID could be used as an effective co-former to decrease the crystallization tendency of co-amorphous FLB-LID upon hydration by enhancing the entropic (ΔS) and thermodynamic activation barriers (TΔS)³/ΔG²) to crystallization. Full article

The present work focuses on the synthesis and characterization of biobased lignin-poly(lactic) acid (PLA) composites. Organosolv lignin, extracted from beechwood, was used as a filler at 0.5, 1.0, and 2.5 wt% loadings, with ultrasonication reducing the lignin particle size to ~700 nm. The PLA–lignin composites were prepared via in situ ring-opening polymerization (ROP) of L-lactide in the presence of lignin. This method ensured uniform lignin dispersion in the PLA matrix due to grafting of PLA chains onto lignin particles, preventing aggregation. Strong polymer–filler interactions were confirmed through spectroscopic analysis (FTIR and XPS) and their effects on static and dynamic glass transitions (DSC). These interactions enhanced mechanical properties, including a two-fold increase in tensile strength and elongation at 1 wt% lignin. Crystallization was suppressed due to shorter PLA chains, and a 15% drop in dynamical fragility was observed via Broadband Dielectric Spectroscopy (BDS). Antioxidant activity improved significantly, with PLA–2.5% ultrasonicated organosolv lignin reducing DPPH• content to 7% after 8 h, while UV-blocking capability increased with lignin content. Full article

This work connects the calorimetric responses of different rubber–resin blends with varying resin contents with their alpha relaxation dynamics. We used differential scanning calorimetry and broadband dielectric spectroscopy to characterize the calorimetric and dielectric responses of styrene–butadiene, polybutadiene, and polyisoprene with different resin contents. To model the results, we used the Gordon–Taylor equation combined with an extension of the Adam–Gibbs approach. Thus, we propose a simple and effective model that allows us to estimate the blend dynamics from the temperature dependence of the relaxation times of the pure components and the calorimetric measurement of the glass transition temperature of only one blend composition. By estimating an effective interaction parameter from calorimetry, we achieved accurate alpha relaxation dynamics predictions for different resin concentrations. Our highly predictive approach provides a realistic description of the expected dynamics. This study offers valuable insights into the dynamic properties of polymer compounds, paving the way for the fast and effective development of advanced and more sustainable materials. Full article

This study presents the synthesis and characterization of a series of multiblock copolymers, poly(ethylene 2,5-furandicarboxylate)-poly(ε-caprolactone) (PEF-PCL), created through a combination of the two-step melt polycondensation method and ring opening polymerization, as sustainable alternatives to fossil-based plastics. The structural confirmation of these block copolymers was achieved through Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy (ATR-FTIR), ensuring the successful integration of PEF and PCL segments. X-ray Photoelectron Spectroscopy (XPS) was employed for chemical bonding and quantitative analysis, providing insights into the distribution and compatibility of the copolymer components. Differential Scanning Calorimetry (DSC) analysis revealed a single glass transition temperature (T_g), indicating the effective plasticizing effect of PCL on PEF, which enhances the flexibility of the copolymers. X-ray Diffraction (XRD) studies highlight the complex relationship between PCL content and crystallization in PEF-PCL block copolymers, emphasizing the need to balance crystallinity and mechanical properties for optimal material performance. Broadband Dielectric Spectroscopy (BDS) confirmed excellent distribution of PEF-PCL without phase separation, which is vital for maintaining consistent material properties. Mechanical properties were evaluated using Nanoindentation testing, demonstrating the potential of these copolymers as flexible packaging materials due to their enhanced mechanical strength and flexibility. The study concludes that PEF-PCL block copolymers are promising candidates for sustainable packaging solutions, combining environmental benefits with desirable material properties. Full article

This new equimolar mixture comprises the liquid crystalline compounds MHPOBC and partially fluorinated 3F2HPhF6. The phase sequence of the mixture was determined by differential scanning calorimetry, polarizing optical microscopy, X-ray diffraction, and broadband dielectric spectroscopy. The enantiotropic smectic A*, C*, and C_A* phases were observed for the mixture. Only partial crystallization of the mixture was observed during cooling at 2–40 K/min, and the remaining smectic C_A* phase underwent vitrification. In contrast, the crystallization of the pure components was complete or almost complete for the same range of cooling rates. The kinetics of the non-isothermal and isothermal crystallization of the mixture and its pure components were investigated by differential scanning calorimetry. The non-isothermal data were analyzed by the isoconversional method, while the isothermal data were analyzed using the Avrami model. As is typical, the nucleation-controlled crystallization kinetics were observed. Full article