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Dual phase high entropy ceramics are attractive due to potential synergetic effects of the constituents on mechanical properties and thermal stability. In this research, dense, dual phase (Hf,Mo,Ti,W,Z) B2-(Hf.Mo.Ti.W,Zr)C powder was synthesized by varying the contents of the transition metals in the final product. The co-synthesis method was used to obtain boride and carbide constituents by boro/ carbothermal reduction of mixtures of oxides and appropriate amounts of carbon black and B4C. Solid solution formation and densification of the reacted powders were done utilizing two step spark plasma sintering or hot pressing processes. Phase compositions of the produced ceramics were identified by x-ray diffraction while chemical compositions were measured using energy dispersive spectroscopy. The final microstructures showed submicron grains due to pining effect of the two phases. Investigation of the mechanical properties showed increasing in Vickers hardness values s up to 48.6 2.2 GPa for applied load of 0.49N for compositions with optimized elemental contents. Room temperature strength was also measured.

Mixtures of ZrO2 and C were prepared by high-energy ball milling. Powders were milled for times from 0 to 120 minutes in air atmosphere. As milling time increased, surface area of powders increased, indicating significant particle size reduction. The thermal treatment cycle included heating at 10 °C/min to 1600 °C followed by an isothermal hold for 2 hours under the vacuum (~20 Pa) in a resistance-heated graphite element furnace. This first step of the process promoted carbothermal reaction of the starting materials. DSC-TGA was used to follow the carbothermal reaction. The onset temperature does not seem to change for non-activated and activated powders. The change in peak area may be related to the amount of the powder that reacts at this temperature. The catbothermal reaction was split into two parts for powders activated 60 and 120 minutes. Only part of the powder reacts at the initial reaction, and then higher temperatures are required for full reaction.

Mechanical activation represents a very useful technique for powder processing prior to sintering process. First of all, it makes powders homogenized, leads to attrition of powder particles, and makes powder mixtures more reactive. Secondly, it can lead to mechano-chemical reaction, and finally, lowering of sintering time and temperature. Mixtures of ZrO2 and C were mechanically activated by high-energy ball milling. Powders were milled for times from 0 to 120 minutes in air atmosphere. Mechanically activated powder mixtures were characterized by various techniques, such as particle size analysis (PSA), X-ray powder diffraction (XRPD), scanning electron microscopy (SEM), Fourier-transform infrared (FTIR) spectroscopy, Raman spectroscopy, and diffraction scanning calorimetry along with thermo gravimetry (DSC-TGA). As milling time increased, surface area of powders increased, indicating significant particle size reduction. Mechanical activation for 15 minutes provides the best balance between particle size reduction and reactivity for the powders.

High entropy carbide/boride (HEC/HEB) ceramics are materials with a wide range of possible applications in harsh environments due to their good mechanical properties, oxidation resistance, and thermal stability. They are usually formed by the solid solutioning of four or more transition metals (TM) in the boride and carbide lattice. In this research, boro/carbothermal reduction was used to form an individual diboride and carbide phases from oxide mixtures. The stoichiometry of the reaction was varied in order to synthesize pure dual phase ceramics. The reacted powders were spark plasma sintered (SPS) or hot pressed (HP), using a two-step process, to produce dense ceramics and to develop the solid solutions. Ceramics processed by SPS still contained residual oxides, while ceramics produced by HP were nominally phase-pure high entropy dual phase materials. Preferential segregation of the TMs was detected by energy dispersive spectroscopy. Vickers hardness measurements confirmed that the highest hardness was obtained for specimens densified by HP at 1950°C that contained no residual oxides and had the smallest grain size. The hardness increased from 25.7 ± 0.2 GPa to 33.6 ± 2.2 GPa with decrease applied load from 9.81N to 0.49N, respectively.

Suspended viable cells significantly influence the relative complex permittivity (dielectric constant) of the suspension. This influence depends on the concentration, viability, size, and even the cell shape. Hence, by measuring the permittivity, various fermentation processes can be monitored (e.g., in wine making and preparation of milk products). Thereby, the complex impedance (or admittance) between electrodes immersed into the suspension is measured and the permittivity is obtained by a suitable de-embedding procedure. There exist various data in the literature on this influence, but they do not provide sufficient information for wide implementation of the technique. The aim of the paper was to experimentally investigate various aspects of the measurement procedures and establish practical guidelines and limitations. Measurements were performed using an LCR meter, a classical vector network analyzer, and a nanoVNA analyzer, in the frequency range from 10 Hz to 100 MHz. Various suspension containers and systems of electrodes were designed and manufactured. Bipolar systems of electrodes were found to be more suitable for higher frequencies than tetrapolar ones. Open electrode systems were found to be more prone to the influence of the environment than shielded systems (e.g., coaxial). Good results were obtained for simple yeast suspensions. However, the presence of other cells and dispersed solids (e.g., in pressed grape juice) was found to completely overshadow the yeast cells. Electrochemical effects on the electrodes were found to be insignificant above around 200 kHz. Bubbles on electrodes, delamination, high concentrations of ions, and even temperature variations significantly hindered measurements in many cases.

Polyvinylidene fluoride (PVDF) is a novel gel polymer electrolyte alternative which can reduce the risk of irreversible failure in lithium-ion batteries (LIB) [1]. PVDF matrix structures which exhibit inter-crosslinking networks have previously demonstrated favorable thermal and mechanical properties for LIB applications [2]. PVDF based multifunctional material is attracting a great scientific interest due to its excellent piezoelectric, pyroelectric and ferroelectric properties. Such as, its properties strongly depend on synthesis procedures and obtained microstructures. In this research, porous structure and cross-linking patterns of PVDF were prepared by electrospinning method and it has been found that these microstructures can have fractal structure. Fractal analysis can be used as a powerful tool for describing structural and functional properties of these this material. Because of that, in this research we have used different fractal methods for the reconstructions of various PVDF microstructure morphologies. Fractal analysis has been performed by using scanning electron microscope micrographs and computational modeling tools. Theory of Iterated Function Systems and Voronoi tessellation, have been used for modeling PVDF porous structures. A Python algorithm was created to determine the distribution of pore areas in SEM micrographs. Algorithm’s distribution of calculated pore surface areas were compared with measured pore surface areas and fractal reconstructions of different morphologies and their connection with functional properties were analyzed.

Ceramic/polymer composites can be chemically stable, mechanically strong, and flexible, which make them candidates for electric devices, such as pressure or temperature sensors, energy storage or harvesting devices, actuators, and so forth. Depending on the application, various electrical properties are of importance. Polymers usually have low dielectric permittivity, but increased dielectric permittivity can be achieved by the addition of the ceramic fillers with high dielectric constant. With the aim to enhance dielectric properties of the composite without loss of flexibility, 5 wt% of BaTiO3-Fe2O3 powder was added into a polyvinylidene fluoride matrix. The powder was prepared by different synthesis conditions to produce core/shell structures. The effect of the phase composition and morphology of the BaTiO3-Fe2O3 core/shell filler on the structure and lattice dynamics of the polymer composites was investigated. Based on the results of the thermal analysis, various parameters of ceramic/polymer composites were determined. Differences in the phase composition and morphology of the filler have an influence on the formation of various polyvinylidene fluoride allomorphs and the degree of crystallinity. Furthermore, the dielectric performances of pure polyvinylidene fluoride and the polymer/ceramic composites were measured.

Magnesium aluminate spinel (MgAl2O4) is a material with good mechanical, chemical, and thermal properties, low dielectric permeability and loss tangent. Based on those properties, MgAl2O4 has found a significant application in refractory ceramics, ceramics windows, integrated electronic devices, etc. Also, it possesses a high chemical and radiation resistance. In this research, MgO was calcined at 1000ºC for an hour, with a step of 10ºC/min to avoid presence of hydroxide or carbonate. MgO and Al2O3 powders were mixed in a one-to-one molar ratio afterwards. The powders were mechanically activated for 15, 30, and 60 minutes. The mass ratio of powder and balls was 1:40. The mechanically activated powders are pressed in the tablets, under the pressure of 0.5 t. The pressed powders were heated up to 1300 ºC with a step of 10 ºC/min and held for 1 h for the reaction. Reacted pellets were crushed and sieved. Obtained spinel powders were sintered at 1450 ºC for 2 h. Both sintered and non-sintered samples were investigated by XRD and SEM. The particle size distribution of the reacted powders was investigated by laser diffraction analysis. Raman spectroscopy was used to determine the lattice vibration in the sintered samples. All results are in accordance with our previous results, and the pure dense spinel phase is obtained.

A powder of Cu0.2Ni0.5Zn1.0 Mn1.3O4 composition for custom thermistor was prepared by using a certain mixture of metal oxides and solid state reaction at 1000 °C/4h in air. The obtained thermistor powder was milled in the planetary ball mill and agate mill for a prolonged time to achieve submicron powder. The prepared thermistor powder was further characterized by using XRD and SEM techniques. After that, the thermistor powder was pressed into small disc-shaped samples and sintered at 1150 °C/2h. The sintered samples were also characterized by using XRD and SEM. The main electrical properties such as nominal resistance R and thermistor exponential factor B were measured in the climatic test chamber. After that, the thick film paste was prepared using the same powder, an organic vehicle and a glass frit. The paste was printed on alumina substrate, dried at 150 °C / 30 min and sintered in air at 850 °C / 10 min in the hybrid conveyor furnace. The planar electrodes were printed on the sintered NTC thermistor layer using the PdAg thick film paste. The electric properties of sintered thick film thermistor were also measured in the climatic test chamber. The obtained results were used for development of novel self-heating thermistor applications.

Zirconium diboride(ZrB2) belongs to the group of ultrahigh temperature ceramics (UHTCs) because of its high melting point (3250°C). Due to its excellent properties, such as the melting temperature, high strength and hardness, high thermal and electrical conductivities relative to other ceramics and good corrosion resistance to molten metals, it has attracted great interest from materials scientists. Fully dense ZrB2 ceramics were successfully obtained by hot pressing at 2150oC for 10 minutes. Prior to hot pressing, commercially available ZrB2 powder was ball milled for 24hr with ZrB2 media. Carbon was added as a densification aid in the amount of 0.5 wt.% using phenolic resin. For mechanical testing, three different methods were compared. Three point bending was performed in air at room temperature and the obtained strength was 546±55 MPa. Four-point bend strengths were measured under same conditions resulting in strengths of 476±112 MPa. Finally, the fracture toughness of pure ZrB2 ceramics was determined by the chevron notched beam method to be 4.1 ± 0.5 MPa•m1/2. The obtained results of mechanical testing make this ceramic material applicable as cutting tools, and parts for hypersonic aerospace vehicles.

Iron-doped strontium-titanate (SrTiO3) powders with various iron(III) oxide (Fe2O3) weight percentages (1.5, 3 and 6 wt%) were prepared by a solid-state method in the presence of mechanical activation (10, 30 and 120 min). A systematic investigation by XRD, SEM and Raman spectroscopy has been undertaken to evaluate the role of dopant on the microstructural and morphological study of the perovskite oxide obtained. The optical properties of the different iron-doped and activated Fe-SrTiO3 powders have been also evaluated. The results demonstrated that Fe has been substituted into the lattice and surface layers of particles of SrTiO3 powders and the absorption edge shifted to higher wavelength values with increasing activation time and dopant weight percentage. The lowest value of the band gap (Eg=3.20 eV) was registered for the longest activation (120 min) and the highest weight percentage of dopant (6 wt%). Combining doping with mechanical activation, led to lower values of Eg and that fact could be used in subsequent studies to make Fe-SrTiO3 more suitable photocatalysts.

Barium titanate (BaTiO3) and polyvinylidene fluoride (PVDF) based multifunctional materials are attracting a great scientific interest due to their excellent piezoelectric, pyroelectric and ferroelectric properties. These materials undergo controlled transformations through physical interactions and respond to environmental stimuli, such as temperature, pressure, electric and magnetic fields. Their properties strongly depend on synthesis procedures and obtained microstructures. This include intergranular contact surfaces of BaTiO3 based materials, as well as, porous structure and cross-linking patterns of PVDF prepared by electrospinning. It has been found that these microstructures can have fractal structure and that the fractal analysis can be used as a powerful tool for describing structural and functional properties of these materials. Having this in mind, in this research we have used different fractal methods for the reconstructions of various BaTiO3 and PVDF microstructure morphologies. Fractal analysis has been performed by using scanning electron microscope micrographs and computational modeling tools. Fractal dimension of irregular morphologies which exhibit fractal regularity were determined by using box-counting method. This method enables the analysis of self-similar microstructure morphologies by quantifying the rate at which an object's geometrical details develop at increasingly fine scales. Theory of Iterated Function Systems and Voronoi tessellation, have been used for modeling BaTiO3 random microstructures and PVDF porous structures. A python algorithm was created to determine the distribution of pore areas in SEM micrographs. Algorithm’s distribution of calculated pore surface areas was compared with measured pore surface areas and fractal reconstructions of different morphologies and their connection with functional properties were analyzed.

The thermal properties of zirconium diboride (ZrB2) ceramics with tungsten additions of up to 5 wt% were characterized up to 2000°C. Densification was promoted by the addition of 0.5 wt% carbon. ZrB2 ceramics were prepared from commercially available powder by hot pressing. The crystalline phases present were determined by x-ray diffraction. The microstructure and density change as a result of the addition of tungsten, but this does not affect much the thermal behavior of ZrB2 at room and elevated temperatures. Thermal diffusivity at 200°C decreased from 0.158 cm2/s for nominally pure ZrB2 to 0.149 cm2/s for ZrB2 with 5 wt% Tungsten carbide (WC). The thermal diffusivity decreased with increasing temperature, reaching a value of 0.145 cm2/s at 2000°C for ZrB2 with 5 wt% Tungsten carbide (WC). Heat capacity, unlike thermal diffusivity, did not change during thermal cycling. Thermal conductivity, which was calculated from thermal diffusivity, heat capacity, and density, was as high as 77.9 W/(m·K) at 2000°C for ZrB2 with 5 wt% Tungsten carbide (WC). Any level of Tungsten carbide (WC) contamination reduces thermal conductivity. Properties, including hardness, oxygen content, elastic modulus, strength were measured and will be discussed.

The synthesis, densification behavior, and crystallographic site occupancy were investigated for four different spinel-based ceramics, including a high-entropy spinel (Co0.2Cu0.2Mg0.2Ni0.2 Zn0.2)Al2O4. Each composition was reacted to form a single phase, but analysis of X-ray diffraction patterns revealed differences in cation site occupancy with the high-entropy spinel being nearly fully normal. Densification behavior was investigated and showed that fully dense ceramics could be produced by hot pressing at temperatures as low as 1375°C for all compositions. Vickers’ hardness values were at least 10 GPa for all compositions. The cations present in the high-entropy spinel appear to have a stabilizing effect that led to nearly normal site occupancy compared to full cation inversion behavior of nickel aluminate spinel. This is the first report that compares cation site occupancy of a high-entropy spinel to conventional spinel ceramics.

Multi-phase ceramics based on ZrB2, TiB2 and doped with CrB2 and SiC were prepared by powder metallurgy and hot pressing to explore the possibility of obtaining multi-scale microstructures by super-saturation of complex (Zr,Ti,Cr)B2 solid solutions. Core–shell structures formed in TiB2 grains, whereas ZrB2 appeared to form a homogeneous solid solution with the other metals. Precipitation of nano-inclusions within both micron-sized borides was assessed by transmission electron microscopy and thermodynamics elucidated the preferential formation of boride inclusions due to the specific sintering atmosphere. In addition, atomic size factors explicated the precipitation of CrB2 nano-particles into ZrB2-rich grains and of ZrB2 nano-particles into TiB2-rich grains. The hardness of the constituent phases measured by nanoindentation ranged from 36 to 43 GPa.

Magnesium aluminate and other alumina-based spinels attract attention due to their high hardness, high mechanical strength, and low dielectric constant. MgAl2O4 was produced by solid-state reaction between MgO and α-Al2O3 powders. Mechanical activation of 30 minutes in a planetary ball mill was used to increase the reactivity of powders. Yttrium oxide and graphene were added to prevent abnormal grain growth during sintering. Samples were sintered by hot-pressing under vacuum at 1450 °C. Phase composition and microstructure of sintered specimens were characterized by X-ray diffraction analysis and scanning electron microscopy. Rietveld analysis revealed 100 % pure spinel phase in all sintered specimens, and decrease in crystallite size with the addition of yttria or graphene. Density measurements indicated that the mechanically activated specimen reached 99.6 % relative density, while other specimens were above 96.5 % relative density. Furthermore, the highest solar absorbance and highest spectral selectivity as a function of temperature were detected for the mechanically activated specimen with graphene addition. Mechanical activation is an efficient method to improve the densification behaviour of MgAl2O4 produced from mixed oxide powders, while additives improve microstructure and optical properties.

ZrB2 ceramics are considered potential materials for hypersonic systems in view of the melting point exceeding 3000 °C and excellent ablation resistance. Second phases, including SiC or CrB2, further improve the oxidation behavior, whereas a lighter phase, like TiB2 can decrease the overall weight. In this work, a powder mixture containing ZrB2, TiB2, CrB2 and SiC was mechanically activated using high energy ball-milling. Sintering was performed by hot pressing following different thermal cycles, and subsequent annealing to remove oxide phases and reduce micro-cracking. The microstructure and hardness of the dense ceramics are compared in relationship to the thermal history. Fully dense ceramics were obtained with different oxide-phases amount depending on the sintering cycle and hardness approaching 24 GPa were achieved. Future works will explore the strength and oxidation resistance of this multi-phase system to check its suitability for hypersonic systems.

Ceramic/polymer dielectric composites are widely used as components for electric devices, mainly because of their high chemical stability, mechanical strength, and flexibility. In order to increase dielectric permittivity, ceramic fillers with high dielectric constant have been usually incorporated in the polymer matrix in large amounts. With the aim to enhance dielectric properties of matrix, 5 wt.% of BaTiO3/Fe2O3 core/shell composite was added into the PVDF matrix. Prior to addition, five BaTiO3/Fe2O3 powders were prepared by different synthesis conditions. The changes in crystal structure and lattice dynamics of the obtained ceramic/polymer composite were correlated with changes in the phase composition and morphology of BaTiO3/Fe2O3 core/shell filler. Thermal analysis such as DTA/TG/DSC are useful methods to determine various parameters in ceramic/polymer composites. We were able to corroborate that differences in phase composition and morphology of BaTiO3/Fe2O3 core/shell filler have influence on formation of various PVDF allomorph modification, as well as a level of crystallinity.

Industrial/technological growth is directly connected with environmental pollution, but its influence can be minimized through pollution abatement approaches such as the treatment of industrial wastewater. In this study, novel porous amine-functionalized silicate minerals, specifically, cordierite was investigated for the removal of toxic heavy metals from industrial wastewaters. Cordierite supports were synthesized by mixing MgO, Al2O3, and SiO2 powders in 2:2:5 molar ratios, and mechanically activated via ball milling in ethanol for 10, 40, or 80 min. Pellets were sintered by heating in air at 20 degrees C min(-1) to 1,350 degrees C, for 2 h. Porous supports were produced by coarsely crushing the sintered pellets and mixing the crushed and sieved cordierite powder with 20 wt.% of a pore-forming agent, either nanocellulose or yeast. The resulting pellets were sintered by heating at 5 degrees C min(-1) to 700 degrees C in air. The synthetic cordierite support was modified by treatment in poly-ethylenimine. Activated supports were then tested for the removal of Ni2+ and Cd2+ ions. The phase composition of the cordierite supports was analyzed by the X-ray diffraction, Fourier-transform infrared spectroscopy, and scanning electron microscopy. Analysis of adsorption isotherms, kinetics, and thermodynamic parameters indicated that adsorption was a spontaneous, endothermic process with a maximum adsorption capacity of 36 mg g(-1) for Cd2+ and 43 mg g(-1) for Ni2+. This work has shed light on the mechanism of heavy metal removal from the aquatic medium using the novel hybrid functionalized cordierite-based ceramic.

In this study, the structure, morphology and composition of the synthesized magnetite/3D-printed wollastonite (3D_W/M) composite were characterized, and its adsorption performance with respect to As(V) and Cr(VI) were studied. Magnetite (MG) modified 3D printed wollastonite was obtained by two step procedure: modification of 3D_W with 3-aminoproylsilane (APTES) followed by controlled magnetite (MG) deposition to obtain 3D_W/M adsorbent. The structure/properties of 3D_W/M were confirmed by applying FTIR, XRD, TGD/DTA, and SEM analysis. The adsorption properties of hybrid adsorbents were carried out for As(V) and Cr(VI) removal-one relative to the initial pH value, the adsorbent mass, the temperature, and the adsorption time. Time-dependent adsorption study was best described by pseudo-second order equation, while Weber Morris analysis showed that intraparticle diffusion controled diffusional transport. Similar activation energy, 17.44 and 14.49 kJ•mol-1 for adsorption As(V) and Cr(VI) on 3D_W/M, respectively, indicated main contribution of physical adsorption. Determination of adsorption parameters was performed by applying different adsorption isotherm models, and the best fit was obtained using Freundlich model. The adsorption capacity of 24.16 and 29.6 mg g-1 for As(V) and Cr(VI) at 2o C, Co = 5.5 and 5.3 mg L-1, respectively, were obtained. Thermodynamic study indicated favourable process at a higher temperature. Preliminary fixed-bed column study and results fitting with Bohart-Adams, Yoon-Nelson, Thomas, and Modified dose-response model showed good agreement with results from the batch study.

MgTiO3 is a material often used in different types of high-frequency capacitors, temperature compensating capacitors, and chip capacitors, so the enhancement of this material is still the focus of many research groups due to its remarkable dielectric properties. Outstanding features can only be achieved when the ceramics are highly dense. Densification of magnesium titanate by Spark Plasma Sintering (SPS) was the aim of this work. Magnesium titanate ceramics were prepared by applying mechanical activation as the first step. Powders prepared in this way were SPS sintered, at 1200 °C with a heating rate of 100 °C/min. After reaching the desired temperature, a uniaxial pressure of 50 MPa was applied. The dwell time at this condition was 5 min, followed by cooling to room temperature at 5°C/min. X-ray diffraction was performed in order to establish the phase composition of milled powders and obtained ceramics. Differences between samples milled in various times intervals, as well as sintered ceramics were examined by means of scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). The presence of MgTiz0s phase was detected in XRD and was confirmed by EDS analysis for the non-milled ceramics. In the samples obtained from milled powders, no MgTi2O5 was detected in XRD patterns, but this phase was detected in EDS spectra in a lower amount. Dielectric measurements were performed at a wide range of frequencies, while the hardness of the SPS samples was measured at loads up to 10 N. The highest value of the hardness was obtained from powder milled for 15 min before SPS.