Breakdown Performance and Partial Discharge Development in Transformer Oil-Based Metal Carbide Nanofluids

In this work, the influence of semi-conductive SiC nanoparticles on the AC breakdown voltage and partial discharge development in natural ester oil FR3 is examined. Primarily, the dielectric constant and the electrical conductivity of the nanoparticles are measured following the broadband dielectric spectroscopy technique. The nanoparticles are added into the matrix following the ultrasonication process in three weight percentage ratios in order for their effect to be evaluated as a function of their concentration inside the base oil. The processing of the results reveals that the nanofluid containing SiC nanoparticles at 0.004% w/w demonstrates the highest AC dielectric strength improvement and shows the greatest resistance to the appearance of partial discharge activity. The mechanisms behind the aforementioned results are discussed in detail and confirmed by the broadband dielectric spectroscopy technique, which reveals that this particular nanofluid sample is characterized by lower dielectric constant and electrical conductivity than the one with double the weight percentage ratio.

Influence of Oligopeptide Length and Distribution on Polyisoprene Properties

The tuning of binding modes of polar groups is the key step to mimicking the structure and properties of natural rubber through the molecular design of synthetic polyisoprenes. Herein, the ordering and binding distances of oligopeptides could be altered systematically by changing their lengths and distribution along the polyisoprene chain, which impose huge impacts on the mechanical properties and chain dynamics of green rubber. In detail, a series of peptide-functionalized polyisoprenes with terminal blocks (B-2A-PIP, B-3A-PIP) or random sequences (R-2A-PIP, R-3A-PIP) are fabricated by using dipeptides (2A) or tripeptides (3A) as crosslinkers to explore the mechanism of terminal interaction on mechanism properties and chain dynamics. B-4A-PIP and R-4A-PIP served as control samples. It is found that the increased oligopeptide length and the block distribution improves the mechanical properties and confine the chain movement by elevate the contents of ordered and compact microstructures, which is indicated by XRD, broadband dielectric spectroscopy (BDS) and consistent with the result of molecular dynamics simulation. New relaxation signals belonging to oligopeptide aggregates are found which showed elevated dielectric strengths upon temperatures increase. Additionally, it also reveals that the binding modes of oligopeptide do not significantly influence the entanglements of polyisoprene.

Submerged Eutectic-Assisted, Solvent-Free Mechanochemical Formation of a Propranolol Salt and Its Other Multicomponent Solids

Salt preparation via a solid-state reaction offers a solution to challenges posed by current pharmaceutical research, which include combining development of novel forms of active pharmaceutical ingredients with greener, sustainable synthesis. This work investigated in detail the mechanism of salt formation between propranolol (PRO) and capric acid (CAP) and explored the solid eutectic phases comprising this salt, propranolol caprate (PRC). The salt structure was solved by X-ray diffraction, and the properties in the crystalline and supercooled states were fully characterised using thermal analysis, nuclear magnetic resonance, Fourier-transform infrared spectroscopy and broadband dielectric spectroscopy (BDS). PRC forms via a submerged eutectic phase composed of PRO and CAP, below room temperature, by mechanochemistry without an extra input of energy. Two other solid eutectic phases are composed of PRC and either CAP or PRO, at 0.28 and 0.82 mol fraction of PRO, respectively. BDS indicated that the supercooled PRC has ionic character, whereas the supercooled PRC-PRO eutectic had predominantly non-ionic properties despite comprising the salt. In conclusion, knowledge of the mechanism of formation of multicomponent systems can help in designing more sustainable pharmaceutical processes.

Keratinocyte cellular damage induced by pesticide doses below the cytotoxic level evidenced by electrical impedance and broadband dielectric spectroscopy

Cellular response of a normal human keratinocyte cell line exposed to non-cytotoxic doses of a deltamethrin-based pesticide was investigated by means of two different electrical impedance data spectroscopy approaches: Nyquist plot and broadband dielectric spectroscopy. The measurements have shown that the membrane capacity increases with pesticide concentration and this facilitates the electric current through cell membranes. Furthermore, the impedance of the extracellular matrix also increases with pesticide concentration, thus reducing the electric current outside the cell. Dielectric permittivity changes in the cellular samples at frequency larger than 100 Hz. Fluorescence measurements emphasized an increase of neutral membrane lipids as consequence of the pesticide exposure. Comparison of fluorescence response of pesticide exposed cells with the control ones showed a time increase of the emission intensity, suggesting the existence of a membrane lipid response aimed at repairing of the cell damage due to pesticide exposure. Therefore, both the spectroscopic techniques have demonstrated to be potential means to investigate the response to cell stress and damage. This opens up new possibilities in the early diagnosis of cellular modifications related to pesticides exposure of cells.

Non-Debye Relaxations: The Ups and Downs of the Stretched Exponential vs. Mittag–Leffler’s Matchings

Experimental data collected to provide us with information on the course of dielectric relaxation phenomena are obtained according to two distinct schemes: one can measure either the time decay of depolarization current or use methods of the broadband dielectric spectroscopy. Both sets of data are usually fitted by time or frequency dependent functions which, in turn, may be analytically transformed among themselves using the Laplace transform. This leads to the question on comparability of results obtained using just mentioned experimental procedures. If we would like to do that in the time domain we have to go beyond widely accepted Kohlrausch–Williams–Watts approximation and become acquainted with description using the Mittag–Leffler functions. To convince the reader that the latter is not difficult to understand we propose to look at the problem from the point of view of objects which appear in the stochastic processes approach to relaxation. These are the characteristic exponents which are read out from the standard non-Debye frequency dependent patterns. Characteristic functions appear to be expressed in terms of elementary functions whose asymptotics is simple. This opens new possibility to compare behavior of functions used to describe non-Debye relaxations. It turnes out that the use of Mittag-Leffler function proves very convenient for such a comparison.

Molecular Dynamics and Kinetics of Isothermal Cold Crystallization in the Chiral Smectogenic 3F7HPhH6 Glassformer

An investigation of the glass transition of the antiferroelectric smectic C*A phase and cold crystallization of (S)-4’-(1-methylheptylcarbonyl)biphenyl-4-yl 4-[7-(2,2,3,3,4,4,4-heptafluoro- butoxy)heptyl-1-oxy]benzoate (denoted as 3F7HPhH6) by differential scanning calorimetry, polarizing optical microscopy and broadband dielectric spectroscopy is presented. The fragility index mf = 72, classifying 3F7HPhH6 as a glassformer with intermediate fragility, was obtained from the temperature dependence of the α-process relaxation time, measured upon cooling. Duplication of the α-process was observed exclusively upon heating, before the onset of cold crystallization, and is connected with the pre-transitional effect. The presence of two crystal phases likely influences the kinetics of cold crystallization; the idea stems from a comparison with previous results for the 3F7HPhF6 and 3F7HPhH7 compounds. Additionally, the presence of the smectic C*α; sub-phase in a narrow temperature range was proved based on the differential scanning calorimetry and broadband dielectric spectroscopy results, as well as the fractal dimension analysis of the textures obtained by polarizing optical microscopy.

Recent Advances in the Application of Characterization Techniques for Studying Physical Stability of Amorphous Pharmaceutical Solids

The amorphous form of a drug usually exhibits higher solubility, faster dissolution rate, and improved oral bioavailability in comparison to its crystalline forms. However, the amorphous forms are thermodynamically unstable and tend to transform into a more stable crystalline form, thus losing their advantages. In order to investigate and suppress the crystallization, it is vital to closely monitor the drug solids during the preparation, storage, and application processes. A list of advanced techniques—including optical microscopy, surface grating decay, solid-state nuclear magnetic resonance, broadband dielectric spectroscopy—have been applied to characterize the physicochemical properties of amorphous pharmaceutical solids, to provide in-depth understanding on the crystallization mechanism. This review briefly summarizes these characterization techniques and highlights their recent advances, so as to provide an up-to-date reference to the available tools in the development of amorphous drugs.

Epoxy-Based/BaMnO4 Nanodielectrics: Dielectric Response and Energy Storage Efficiency

Compact capacitive energy storing/harvesting systems could play a key role in the urgent need for more energy-efficient technologies to address both energy and environmental issues. Therein, the purpose of the present work is to develop and investigate epoxy/BaMnO4 nanocomposites at various filler concentrations, which could be applicable as compact materials systems for energy storage and harvesting. Broadband dielectric spectroscopy was used for studying the dielectric properties and the relaxation processes of the examined nanodielectrics. The energy storing/retrieving ability of the nanocomposites was also evaluated via DC charge–discharge experiments. The coefficient of energy efficiency (neff) was found for all prepared nanocomposites to evaluate the energy performance of the systems. Dielectric data divulge the existence of two matrix-related relaxations, i.e., α-mode and β-mode, attributed to the glass-to-rubber transition of the polymer matrix and re-orientation of polar side groups, respectively. Interfacial polarization was also identified in the low-frequency and high-temperature region. The 7 phr BaMnO4 nanocomposite exhibits the best performance in terms of the stored and harvested energies compared to all systems. On the other hand, the 5 phr, 3 phr and 1 phr nanocomposites display optimum energy performance, reaching high values of neff.