Thermal Stability and Non-Linear Optical and Dielectric Properties of Lead-Free K0.5Bi0.5TiO3 Ceramics.

Lead-free K0.5Bi0.5TiO3 (KBT) ceramics with high density (~5.36 g/cm3, 90% of X-ray density) and compositional purity (up to 90%) were synthesized using a solid-state reaction method. Strongly condensed KBT ceramics revealed homogenous local microstructures. TG/DSC (Thermogravimetry-differential scanning calorimetry) techniques characterized the thermal and structural stability of KBT. High mass stability (>0.4%) has proven no KBT thermal decomposition or other phase precipitation up to 1000 °C except for the co-existing K2Ti6O13 impurity. A strong influence of crystallites size and sintering conditions on improved dielectric and non-linear optical properties was reported. A significant increase (more than twice) in dielectric permittivity (εR), substantial for potential applications, was found in the KBT-24h specimen with extensive milling time. Moreover, it was observed that the second harmonic generation (λSHG = 532 nm) was activated at remarkably low fundamental beam intensity. Finally, spectroscopic experiments (Fourier transform Raman and far-infrared spectroscopy (FT-IR)) were supported by DFT (Density functional theory) calculations with a 2 × 2 × 2 supercell (P42mc symmetry and C4v point group). Moreover, the energy band gap was calculated (Eg = 2.46 eV), and a strong hybridization of the O-2p and Ti-3d orbitals at Eg explained the nature of band-gap transition (Γ â†’ Γ).

Magnetoelectric Properties of Multiferroic Composites Based on BaTiO3 and Nickel-Zinc Ferrite Material.

The purpose of the present study was to learn the morphological, structural, ferroelectric, dielectric, electromechanical, magnetoelectric, and magnetic properties, and DC conductivity of BaTiO3-Ni0.64Zn0.36Fe2O4 (BT-F) multiferroic composites compacted via the free sintering method. The influence of the ferrite content in ceramic composite materials on the functional properties is investigated and discussed. X-ray diffraction studies confirmed the presence of two main phases of the composite, with strong reflections originating from BaTiO3 and weak peaks originating from nickel-zinc ferrite. BT-F ceramic composites have been shown to exhibit multiferroism at room temperature. All studied compositions have high permittivity values and low dielectric loss, while the ferroelectric properties of the BT component are maintained at a high level. On the other hand, magnetic properties depend on the amount of the ferrite phase and are the strongest for the composition with 15 wt.% of F (magnetization at RT is 4.12 emu/g). The magnetoelectric coupling between BT and F phases confirmed by the lock-in technique is the largest for 15 wt.% ferrite. In the present work, the process conditions of the free sintering method for obtaining BT-F multiferroic composite with good electrical and magnetic properties (in one material) were optimized. An improved set of multifunctional properties allows the expansion of the possibilities of using multiferroic composites in microelectronics.

Properties of PBZTS Ferroelectric Ceramics Obtained Using Spark Plasma Sintering.

In this paper, spark plasma sintering was used to obtain and investigate (Pb0.97Ba0.03)(Zr0.98Ti0.02)1-xSnxO3 (PBZTS) ceramic materials for x = 0, 0.02, 0.04, 0.06, and 0.08. Crystal structure, microstructure, dielectric and ferroelectric properties, and electrical conductivity tests of a series of samples were carried out. The SPS sintering method ensures favorable dielectric and ferroelectric properties of PBZTS ceramic materials. X-ray studies have shown that the material has a perovskite structure. The samples have a densely packed material structure with properly crystallized grains. The fine-grained microstructure of the PZBZTS material with high grain homogeneity allows the application of higher electric fields. Ceramic samples obtained by the SPS method have higher density values than samples obtained by the classical method (FS). The permittivity at room temperature is in the range of 245-282, while at the phase transition temperature is in the range of 10,259-12,221. At room temperature, dielectric loss factor values range from 0.006 to 0.036. The hysteresis loops of PBZTS ceramics have a shape typical for ferroelectric hard materials, and the remnant polarization values range from 0.32 to 0.39 µC/cm2. The activation energy Ea values of the PBZTS samples result mainly from the presence of oxygen vacancies. The PZT material doped with Ba and Sn and sintered via the SPS method has favorable physical parameters for applications in modern devices such as actuators or pulse capacitors.

Electric and Magnetic Properties of the Multiferroic Composites Made Based on Pb(Fe1/2Nb1/2)1-xMnxO3 and the Nickel-Zinc Ferrite.

This work presents the electrophysical properties of the multiferroic ceramic composites obtained as a result of combining both magnetic and ferroelectric material. The ferroelectric components of the composite are materials with the following chemical formulas: PbFe0.5Nb0.5O3 (PFN), Pb(Fe0.495Nb0.495Mn0.01)O3 (PFNM1), and Pb(Fe0.49Nb0.49Mn0.02)O3 (PFNM2), while the magnetic component of the composite is the nickel-zinc ferrite (Ni0.64Zn0.36Fe2O4 marked as F). The crystal structure, microstructure, DC electric conductivity, and ferroelectric, dielectric, magnetic, and piezoelectric properties of the multiferroic composites are performed. The conducted tests confirm that the composite samples have good dielectric and magnetic properties at room temperature. Multiferroic ceramic composites have a two-phase crystal structure (ferroelectric from a tetragonal system and magnetic from a spinel structure) without a foreign phase. Composites with an admixture of manganese have a better set of functional parameters. The manganese admixture increases the microstructure's homogeneity, improves the magnetic properties, and reduces the electrical conductivity of composite samples. On the other hand, in the case of electric permittivity, a decrease in the maximum values of εm is observed with an increase in the amount of manganese in the ferroelectric component of composite compositions. However, the dielectric dispersion at high temperatures (associated with high conductivity) disappears.

Electrophysical Properties of the Three-Component Multiferroic Ceramic Composites.

Using the free (pressureless) sintering method, multiferroic ceramic composites based on two ferroelectric materials, i.e., BaTiO3 (B) and Pb0.94Sr0.06 (Zr0.46Ti0.54)0.99Cr0.01O3 (P), and magnetic material, i.e., zinc-nickel ferrite (F) were obtained. Three composite compositions (BP-F) were obtained with a constant 90/10 content (ferroelectric/magnetic) and a variable content of the ferroelectric component (B/P), i.e., 70/30, 50/50, and 30/70. Crystalline structure, microstructural, DC electrical conductivity, dielectric, and ferroelectric properties of multiferroic composites were investigated. The concept of a composite consisting of two ferroelectric components ensures the preservation of sufficiently high ferroelectric properties of multiferroic composites sintered by the free sintering method. Research has shown that the percentage of individual ferroelectric components in the composite significantly affects the functional properties and the entire set of physical parameters of the multiferroic BP-F composite. In the case of the dielectric parameters, the best results were obtained for the composition with a more significant amount of BaTiO3; i.e., permittivity is 1265, spontaneous polarization is 7.90 µC/cm2, and remnant polarization is 5.40 µC/cm2. However, the most advantageous set of performance parameters shows the composite composition of 50BP-F.

Influence of the Sintering Method on the Properties of a Multiferroic Ceramic Composite Based on PZT-Type Ferroelectric Material and Ni-Zn Ferrite.

This paper presents the research results of multiferroic ceramic composites obtained with three sintering methods, i.e., free sintering FS (pressureless), hot pressing HP, and spark plasma sintering SPS. The multiferroic composite was obtained by combining a ferroelectric material of the PZT-type (90%) and zinc-nickel ferrite (10%). Research has shown that the combination of a magnetic material and ferroelectric materials maintains the multiferroic good ferroelectric and magnetic properties of the composites for all sintering methods. A sample sintered with the HP hot pressing method exhibits the best parameters. In the HP method, the composite sample has high permittivity, equal to 910 (at room temperature) and 7850 (at the phase transition temperature), residual polarization 2.80 µC/cm2, a coercive field of 0.95 kV/mm, and the magnetization of 5.3 and 4.95 Am2/kg at -268 °C and RT, respectively. Optimal technological process conditions are ensured by the HP method, improving the sinterability of the ceramic sinter which obtains high density and proper material compaction. In the case of the SPS method, the sintering conditions do not allow for homogeneous growth of the ferroelectric and magnetic component grains, increasing the formation of internal pores. On the other hand, in the FS method, high temperatures favor excessive grain growth and an increase in the heterogeneity of their size. In obtaining optimal performance parameters of multiferroic composites and maintaining their stability, hot pressing is the most effective of the presented sintering methods.

Advanced Ceramic Materials with Functional Properties.

With the dynamic progress in technology worldwide, the research into new engineering materials applies to a wide range of materials with exciting properties [...].

A Combination of Calcination and the Spark Plasma Sintering Method in Multiferroic Ceramic Composite Technology: Effects of Process Temperature and Dwell Time.

This study reports a combined technological process that includes synthesis by the calcination powder route and sintering by the Spark Plasma Sintering (SPS) method for multiferroic ceramic composites in order to find the optimal sintering conditions. The effects of temperature on the SPS process and dwell time on the microstructure and dielectric properties of the PF composites were discussed. Research has shown that using the SPS method in the technological process of the multiferroic composites favors the correct densification of powders and allows for obtaining a fine-grained microstructure with good properties and electrophysical parameters in the composite material. The optimal set of parameters and properties is demonstrated by the sample obtained at the temperature of 900 °C for 3 min, i.e., resistivity (6.4 × 108 Ωm), values of the dielectric loss factor (0.016), permittivity at room temperature (753) and permittivity at the phase transition temperature (3290). Moreover, due to the high homogeneity of the microstructure, the strength of the material against electric breakdown increases (when examining the ferroelectric hysteresis loop, the application of a high electric field (3-3.5 kV/mm) is also possible at higher temperatures). In the case of the composite material tested, both the lower and higher temperatures as well as the shorter and longer dwell times (compared to the optimal SPS process conditions) did not contribute to the improvement of the microstructure or the set of usable parameters of the composite materials. The strength of the ceramic samples against electric breakdown has also diminished, while the phenomenon of leakage current increased.

Effect of Chemical Composition on Magnetic and Electrical Properties of Ferroelectromagnetic Ceramic Composites.

In this paper, ferroelectric-ferrimagnetic ceramic composites based on multicomponent PZT-type (PbZr1-xTixO3-type) material and ferrite material with different percentages in composite compositions were obtained and studied. The ferroelectric component of the composite was a perovskite ceramic material with the chemical formula Pb0.97Bi0.02(Zr0.51Ti0.49)0.98(Nb2/3Mn1/3)0.02O3 (P), whereas the magnetic component was nickel-zinc ferrite with the chemical formula Ni0.5Zn0.5Fe2O4 (F). The process of sintering the composite compounds was carried out by the free sintering method. Six ferroelectric-ferrimagnetic ceramic P-F composite compounds were designed and obtained with different percentages of its components, i.e., 90/10 (P90-F10), 85/15 (P85-F15), 80/20 (P80-F20), 60/40 (P60-F40), 40/60 (P40-F60), and 20/80 (P20-F80). X-ray diffraction patterns, microstructural, ferroelectric, dielectric, magnetic properties, and DC electrical conductivity of the composite materials were investigated. In this study, two techniques were used to image the microstructure of P-F composite samples: SB (detection of the signals from the secondary and backscattered electron detectors) and BSE (detection of backscattered electrons), which allowed accurate visualization of the presence and distribution of the magnetic and ferroelectric component in the volume of the composite samples. The studies have shown that at room temperature, the ceramic composite samples exhibit good magnetic and electrical properties. The best set of physical properties and performance of composite compositions have ceramic samples with a dominant phase of ferroelectric component and a small amount of the ferrite component (P90-F10). Such a composition retains the high ferroelectric properties of the ferroelectric component in the composite while also acquiring magnetic properties. These properties can be prospectively used in new types of memory and electromagnetic converters.

Mechanochemical Activation and Spark Plasma Sintering of the Lead-Free Ba(Fe1/2Nb1/2)O3 Ceramics.

This paper investigates the impact of the technological process (Mechanochemical Activation (MA) of the powder in combination with the Spark Plasma Sintering (SPS) method) on the final properties of lead-free Ba(Fe1/2Nb1/2)O3 (BFN) ceramic materials. The BFN powders were obtained for different MA duration times (x from 10 to 100 h). The mechanically activated BFN powders were used in the technological process of the BFN ceramics by the SPS method. The measurements of the BFNxMA ceramic samples included the following analysis: Scanning Electron Microscopy (SEM), Energy Dispersive Spectrometry (EDS), DC electrical conductivity, and dielectric properties. X-ray diffractions (XRD) tests showed the appearance of the perovskite phase of BFN powders after 10 h of milling time. The longer milling time (up 20 h) causes the amount of the perovskite phase to gradually increase, and the diffraction peaks are more clearly visible. Short high energy milling times favor a large heterogeneity of the grain shape and size. Increasing the MA milling time to 40 h significantly improves the microstructure of BFN ceramics sintered in the SPS technology. The microstructure becomes fine-grained with clearly visible grain boundaries and higher grain size uniformity. Temperature measurements of the BFN ceramics show a number of interesting dielectric properties, i.e., high values of electric permittivity, relaxation properties with a diffusion phase transition, as well as negative values of dielectric properties occurring at high temperatures. The high electric permittivity values predestines the BFNxMA materials for energy storage applications e.g., high energy density batteries, while the negative values of dielectric properties can be used for shield elements against the electromagnetic radiation.

Investigation of Selected Polymer Composite-Aluminum Oxide Coating Tribological Systems.

The tribotesting of friction systems requires discussion on proper selection of its conditions and data presentation. System tribology is based, for example, on analysis of the friction contact, the roughness of the cooperating surfaces, and the wear rate of the rubbing elements or coefficient of friction in relation to the sliding distance. Friction pairs, consisting of an aluminum alloy sample with an oxide layer (Al2O3) with and without the addition of inorganic fullerenes like tungsten disulphide (IF-WS2) nanoparticles on its surface cooperating with a counter-sample made of polymer composites prepared on the basis of phenol-formaldehyde resin with different fillers, were tested using a device with a pin-on-plate friction pair system. The results of the experiments showed sufficient durability of the Al2O3 and Al2O3/IF-WS2 oxide coatings in combination with the polymer composite. It was found that resin fillers such as cotton fibers, jute fibers, molybdenum disulphide (MoS2) or graphite (C) influence the friction behavior of the tribological pairs. Although the values of the coefficient of friction obtained in the tests were quite high, their course during the tests ensured stable cooperation of the aluminum coating/polymer composite friction pair on a 15 km distance, under a load of 0.5 MPa. The lowest coefficients of friction were obtained for oxide layers formed on aluminum combined with a polymer composite filled with cotton fibers and graphite. These studies provide information on the tribological properties of commercially available polymer composites cooperating with the produced oxide coatings, supplementing the available literature with the results of research on new, so far unexplored tribological partners. Microscopic investigation of the structure and morphology of the formed surface oxide layers and also microgeometry studies of both the friction elements were used to better understand the obtained research results.

The Effect of Mixed Doping on the Microstructure and Electrophysical Parameters of the Multicomponent PZT-Type Ceramics.

This work shows the influence of admixture on the basic properties of the multicomponent PbZr1-xTixO3 (PZT)-type ceramics. It presents the results of four compositions of PZT-type material with the general chemical formula, Pb0.99M0.01((Zr0.49Ti0.51)0.95Mn0.021Sb0.016W0.013)0.9975O3, where, in the M position, a donor admixture was introduced, i.e., samarium (Sm3+), gadolinium (Gd3+), dysprosium (Dy3+) or lanthanum (La3+). The compositions of the PZT-type ceramics were obtained through the classic ceramic method, as a result of the synthesis of simple oxides. The X-ray diffraction (XRD) pattern studies showed that the obtained multicomponent PZT materials have a tetragonal structure with a P4mm point group. The microstructure of the obtained compositions is characterized by a well crystallized grain, with clearly visible grain boundaries. The composition with the admixture of lanthanum has the highest uniformity of fine grain microstructure, which positively affects its final dielectric and piezoelectric properties. In the multicomponent PZT-type ceramic, materials utilize the mixed (acceptor and donor) doping of the main compound. This dopiong method has a positive effect on the set of the electrophysical parameters of ceramic materials. Donor dopants W6+ (at positions B) and M3+ = Sm3+, Gd3+, Dy3+, and La3+ (at positions A) increase the dielectric and piezoelectric properties, while the acceptor dopant Sb3+ (at positions B) increases the time and temperature stability of the electrophysical parameters. In addition, the suitable selection of the set of admixtures improved the sinterability of the ceramic samples, as well as resulted in obtaining the required material with good piezoelectric parameters for the poling process. This research confirms that all ceramic compositions have a set of parameters suitable for applications in micromechatronics, for example, as actuators, piezoelectric transducers, and precision microswitches.

Correction: Wodecka-Dus, B. et al., Chemical and Physical Properties of the BLT4 Ultra Capacitor-A Suitable Material for Ultracapacitors Materials 2020, 13, 659.

The authors wish to make the following corrections to this paper [...].

Preparation and Dielectric Properties of K1/2Na1/2NbO3 Ceramics Obtained from Mechanically Activated Powders.

Alkaline based materials have been considered as a replacement for environmentally harmful Pb(Zr,Ti)O3 (PZT) electro-ceramics. In this paper, the K1/2Na1/2NbO3 (KNN) ceramics were prepared in a three stage process: first Nb2O5, Na2CO3, and K2CO3 were milled in a high energy mill (shaker type) for different periods, between 25 h and 100 h, consecutively a solid state reaction was carried out at 550 °C. Finally, the uniaxially pressed samples were sintered at 1000 °C. The reaction temperature is lower for mechanically activated powders than in the case of the conventional solid-state method. The ceramic samples, prepared from the mechanically activated powders, were investigated by dielectric spectroscopy. The influence of the duration of the mechanical activation on the properties of the ceramic materials, e.g., ceramic microstructures, phase transition temperatures, character of the temperature dependences of dielectric permittivity, are discussed.

Electrophysical Properties of PMN-PT-Ferrite Ceramic Composites.

Ferroelectromagnetic composites based on (1-x)PMN-(x)PT (PMN-PT) powder and Ni-Zn ferrite powder were obtained and are described in this work. As a ferroelectric component, we used (1-x)PMN-(x)PT solid solution (with x = 0.25, 0.28, 0.31, 0.34, 0.37, 0.40), synthesized using the sol-gel method. As a magnetic component, we used nickel-zinc ferrite, obtained using classic ceramic technology. The six compositions of PMN-PT used have rhombohedral symmetry, tetragonal one and mixture of these phases (morphotropic phase area), depending on x. The final ceramic composite samples were obtained using the classic methods involving the calcination route and pressureless final sintering (densification). The properties of the obtained ceramic composite samples were investigated, including microstructure SEM (scanning electron microscope), dielectric properties, electromechanical properties, and DC (Direct Current) electrical conductivity. Results showed that the microstructures of the PP-F composite samples characterized by larger grains were better crystallized, compared with the microstructures of the PMN-PT ceramic samples. The magnetic properties do not depend on the ferroelectric component of the composite samples, while the insertion of ferrite into the PMN-PT compound reduces the values of remnant and spontaneous polarization, as well as the coercive field. The dielectric measurements also indicated that the magnetic subsystem influences the dielectric properties. The present results show that the PP-F ceramic composite has good dielectric, magnetic, and piezoelectric properties, which predisposes this type of material to specific applications in microelectronics and micromechatronics.

Comparison of Electrophysical Properties of PZT-Type Ceramics Obtained by Conventional and Mechanochemical Methods.

In the paper, the multicomponent PZT-type ceramics with Pb(Zr0.49Ti0.51)0.94Mn0.015Sb0.01W0.015Ni0.03O3 composition have been obtained by conventional and mechanochemical methods. With conventional ceramic technology, PZT-type ceramics have been synthesized by the method of calcination powder (850 °C/4 h). Instead of this step, the mechanochemical synthesis process for different milling periods (15 h, 25 h, 50 h, 75 h) has been applied for a second batch of samples. To obtain the dense PZT-type ceramic samples, powders have been sintered by free sintering method at conditions of 1150 °C/2 h. Studies have shown that the perovskite structure of the PZT-type material is formed during mechanochemical activation of powders during the technological process at low temperature. The application of the mechanochemical synthesis to obtain the PZT-type materials also allows shortening of the technological process, and the useful electrophysical properties of ceramic samples are not reduced at the same time. The presented results have confirmed that the investigated materials can be used in microelectronic applications, especially as elements of actuators and piezoelectric transducers.

Ferroelectromagnetic Properties of PbFe1/2Nb1/2O3 (PFN) Material Synthesized by Chemical-Wet Technology.

In this work, PbFe1/2Nb1/2O3 (PFN) ceramic samples synthesized by chemically wet method (precipitation from the solution) were obtained. Due to the tendency to form powder agglomerates, the synthesized powder was subjected to ultrasound. The sintering was carried out under various technological conditions, mainly through controlling the sintering temperature. -X-ray powder-diffraction (XRD), scanning electron microscope (SEM) microstructure analysis, as well as the examinations of dielectric, ferroelectric, and magnetic properties of the PFN ceramics were carried out. Studies have shown that hard ceramic agglomerates can be partially minimized by ultrasound. Due to this treatment, closed porosity decreases, and the ceramic samples have a higher density. Optimization and improvement of the technological process of the PFN material extends the possibility of its use for the preparation of multiferroic composites or multicomponent solid solutions based on PFN. Such materials with functional properties find applications in microelectronic applications, e.g., in systems integrating ferroelectric and magnetic properties in one device. The optimal synthesis conditions of PFN ceramics were determined to be 1050 °C/2 h.

Electrophysical Properties of the PMN⁻PT⁻PS Solid Solution.

The (1 - y) ((1 - x)Pb(Mg1/3Nb2/3)O3⁻xPbTiO3)⁻yPbSnO3 solid solution (PMN⁻PT⁻PS) was obtained and investigated in the present paper. For the analysis of the influence of the PbSnO3 component on the electrophysical parameters, the compositions from the rhombohedral phase, tetragonal phase, and a mixture of these phases were selected. The six compositions of the PMN⁻PT have been obtained using sol⁻gel methods (for values of x equal to 0.25, 0.28, 0.31, 0.34, 0.37, and 0.40). The ceramic samples of the 0.9(PMN⁻PT)⁻0.1(PS) solid solution have been obtained using the conventional ceramic route. X-ray diffraction (XRD), energy dispersive spectrometry (EDS), and microstructure measurements were performed, as well as tests regarding the dielectric, ferroelectric, piezoelectric properties and electric conductivity of the PMN⁻PT⁻PS ceramic samples versus temperature. Results of the measurements show that the obtained PMN⁻PT⁻PS materials have good electrophysical properties and are well suited for use in micromechatronic and microelectronic applications.