An analysis of the P2S6 cluster electronic structure and its comparison with the crystal valence band in the paraelectric and ferroelectric phases has been done by first-principles calculations for Sn2P2S6 ferroelectrics. The origin of ferroelectricity has been outlined. It was established that the spontaneous polarization follows from the stereochemical activity of the electron lone pair of tin cations, which is determined by hybridization with P2S6 molecular orbitals. The chemical bonds covalence increase and rearrangement are related to the valence band changes at transition from the paraelectric phase to the ferroelectric phase.

Metal–organic frameworks (MOFs), formed of metal centers coupled by organic molecules, exhibit inherent porosity and crystallinity. Although these systems have been examined for many potential applications, their multiferroic properties remain poorly understood. One of the approaches to get an insight into the ferroic features of these materials is the study of frameworks templated by protonated organic molecules possessing rotational and conformational freedom. The embedded organic cation with an internal electric dipole moment may be ordered on cooling, leading to the appearance of ferroelectric-like properties. Herein, we report a study of two structural phase transitions in one such material, the methylhydrazinium zinc formate [CH₃NH₂NH₂][Zn(HCOO)₃] framework (MHyZn), using various experimental techniques. High-temperature (HT) improper ferroelectric phase transition and low-temperature (LT) biferroic phase transition in MHyZn single crystals have been investigated in a broad temperature range using X-ray diffraction, longitudinal ultrasonic velocity and attenuation measurements, pyrocurrent measurements, and broadband dielectric spectroscopy. In addition, noncentrosymmetric to centrosymmetric structural transformation was confirmed for the HT phase transition with the use of temperature-resolved second harmonic generation on powder samples, while polarizing microscopy observation of a large deformation of ferroelastic-like domains attested to the noncontinuous character of the crystallographic system transformation (trigonal to triclinic) in the LT biferroic phase transition. Finally, we proved that the spontaneous electric polarization occurs due to freezing of motion around the 2- and 3-axes of the methylhydrazinium cation.

To address the ever-increasing electromagnetic interference (EMI) pollution, a hybrid filler approach for novel composites was chosen, with a focus on EMI absorbance. Carbon nanofiller loading was limited to 0.6 vol.% in order to create a sustainable and affordable solution. Multiwall carbon nanotubes (MWCNT) and iron oxide (Fe₃O₄) nanoparticles were mixed in nine ratios from 0.1 to 0.6 vol.% and 8.0 to 12.0 vol.%, respectively. With the addition of surfactant, excellent particle dispersion was achieved (examined with SEM micrographs) in a bio-based and biodegradable poly(butylene succinate) (PBS) matrix. Hybrid design synergy was assessed for EMI shielding using dielectric spectroscopy in the microwave region and transmittance in the terahertz range. The shielding effectiveness (20–52 dB) was dominated by very high absorption at 30 GHz, while in the 0.1 to 1.0 THz range, transmittance was reduced by up to 6 orders of magnitude. Frequency-independent AC electrical conductivity (from 10⁻² to 10⁷ Hz) was reached upon adding 0.6 vol.% MWCNT and 10 vol.% Fe₃O₄, with a value of around 3.1 × 10⁻² S/m. Electrical and thermal conductivity were mainly affected by the content of MWCNT filler. The thermal conductivity scaled with the filler content and reached the highest value of 0.309 W/(mK) at 25 °C with the loading of 0.6 vol.% MWCNT and 12 vol.% Fe₃O₄. The surface resistivity showed an incremental decrease with an increase in MWCNT loading and was almost unaffected by an increase in iron oxide loading. Thermal conductivity was almost independent of temperature in the measured range of 25 to 45 °C. The nanocomposites serve as biodegradable alternatives to commodity plastic-based materials and are promising in the field of electromagnetic applications, especially for EMI shielding.

We report on the design of highly absorptive thermostable composite materials for microwave applications. Ceramics comprising the thermostable phosphate host and silicon carbide particles or whiskers were studied in a wide frequency range from several Hertz up to microwaves. It was demonstrated that a thin layer of ceramics placed on the back-reflector absorbs perfectly at the 30 GHz frequency. In the case of a free-standing ceramic composite layer being 1 mm thick, it provides more than 50% of absorption.

The dielectric properties of epoxy/MWCNT (multi-walled carbon nanotubes)/MgO hybrid composites with a fixed MWCNT amount of 0.12 vol.% (0.2 wt.%) and varying MgO concentrations up to 3 vol.% were investigated in broad frequency (20–40 GHz) and temperature (20–500 K) ranges. The composites with up to 2 vol.% MgO nanoparticles concentration showed a significant increase of DC conductivity in relation to their non MgO-containing counterparts. The optimal content of MgO was found, i.e., 0.46 vol.%, which gave up to 2.5 orders of magnitude larger DC conductivity than those of the samples prepared without MgO additives. Using various amounts of MgO, it is possible to predictably vary the broadband electromagnetic properties of the composites, even entirely eliminating the electrical percolation. Electrical transport at different temperatures can be substantially controlled by the addition of given amounts of MgO. The broadband properties are discussed in terms of the distribution of relaxation times, which are proven to be an effective, noninvasive, and simple tool for checking composite fabrication issues, such as the distribution of MWCNT aggregates within the epoxy matrix.